US3790416A - Composite propellant including (u) polyfunctional amine - Google Patents
Composite propellant including (u) polyfunctional amine Download PDFInfo
- Publication number
- US3790416A US3790416A US00087513A US3790416DA US3790416A US 3790416 A US3790416 A US 3790416A US 00087513 A US00087513 A US 00087513A US 3790416D A US3790416D A US 3790416DA US 3790416 A US3790416 A US 3790416A
- Authority
- US
- United States
- Prior art keywords
- binder
- propellant
- polyfunctional amine
- percent
- propellant composition
- 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 abstract description 116
- 150000001412 amines Chemical class 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims description 27
- 239000000203 mixture Substances 0.000 claims abstract description 84
- 239000011230 binding agent Substances 0.000 claims abstract description 75
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 239000003431 cross linking reagent Substances 0.000 claims description 20
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical group FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 12
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical group NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 10
- 229920002873 Polyethylenimine Polymers 0.000 claims description 8
- 229920001228 polyisocyanate Polymers 0.000 claims description 7
- 239000005056 polyisocyanate Substances 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- LNPMZQXEPNWCMG-UHFFFAOYSA-N 4-(2-aminoethyl)aniline Chemical group NCCC1=CC=C(N)C=C1 LNPMZQXEPNWCMG-UHFFFAOYSA-N 0.000 claims description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical group NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical group NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 4
- -1 aliphatic amines Chemical class 0.000 description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 19
- 239000000945 filler Substances 0.000 description 14
- 150000002118 epoxides Chemical class 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000004615 ingredient Substances 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 8
- 239000004014 plasticizer Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 125000003277 amino group Chemical group 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000004449 solid propellant Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000004132 cross linking Methods 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
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NIYNIOYNNFXGFN-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol;7-oxabicyclo[4.1.0]heptane-4-carboxylic acid Chemical compound OCC1CCC(CO)CC1.C1C(C(=O)O)CCC2OC21.C1C(C(=O)O)CCC2OC21 NIYNIOYNNFXGFN-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- NPCUWXDZFXSRLT-UHFFFAOYSA-N chromium;2-ethylhexanoic acid Chemical compound [Cr].CCCCC(CC)C(O)=O NPCUWXDZFXSRLT-UHFFFAOYSA-N 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- HFPDJZULJLQGDN-UHFFFAOYSA-N hydrazine;perchloric acid Chemical compound [NH3+]N.[O-]Cl(=O)(=O)=O HFPDJZULJLQGDN-UHFFFAOYSA-N 0.000 description 2
- OTVFPXIRFAUIDK-UHFFFAOYSA-N hydrazine;perchloric acid Chemical compound NN.OCl(=O)(=O)=O.OCl(=O)(=O)=O OTVFPXIRFAUIDK-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 235000013849 propane Nutrition 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEECYHUVEPKMQZ-UHFFFAOYSA-N (5-methyl-7-oxabicyclo[4.1.0]heptan-4-yl)methyl 5-methyl-7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2C(C)C1C(=O)OCC1CCC2OC2C1C LEECYHUVEPKMQZ-UHFFFAOYSA-N 0.000 description 1
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical class FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
- WOGVOIWHWZWYOZ-UHFFFAOYSA-N 1,1-diisocyanatoethane Chemical compound O=C=NC(C)N=C=O WOGVOIWHWZWYOZ-UHFFFAOYSA-N 0.000 description 1
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- IKYNWXNXXHWHLL-UHFFFAOYSA-N 1,3-diisocyanatopropane Chemical compound O=C=NCCCN=C=O IKYNWXNXXHWHLL-UHFFFAOYSA-N 0.000 description 1
- FWCBNLQJGUYQRQ-UHFFFAOYSA-N 1-(2-hydroxyethoxy)-3-(3-methyl-7-oxabicyclo[4.1.0]heptan-4-yl)-2-[(3-methyl-7-oxabicyclo[4.1.0]heptan-4-yl)methyl]propan-2-ol Chemical compound C1C2OC2CC(C)C1CC(O)(COCCO)CC1CC2OC2CC1C FWCBNLQJGUYQRQ-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- SZCFDTYKNQJQKT-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxy)-6-oxabicyclo[3.1.0]hexane Chemical compound C1CC2OC2C1OCC1CO1 SZCFDTYKNQJQKT-UHFFFAOYSA-N 0.000 description 1
- DDNLLYYWFSTMHR-UHFFFAOYSA-N 2-[2-[2-chloro-4-[2-(oxiran-2-yl)ethoxy]cyclohexyl]oxyethyl]oxirane Chemical compound ClC1CC(OCCC2OC2)CCC1OCCC1CO1 DDNLLYYWFSTMHR-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- KXYAVSFOJVUIHT-UHFFFAOYSA-N 2-vinylnaphthalene Chemical class C1=CC=CC2=CC(C=C)=CC=C21 KXYAVSFOJVUIHT-UHFFFAOYSA-N 0.000 description 1
- GRWFFFOEIHGUBG-UHFFFAOYSA-N 3,4-Epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclo-hexanecarboxylate Chemical compound C1C2OC2CC(C)C1C(=O)OCC1CC2OC2CC1C GRWFFFOEIHGUBG-UHFFFAOYSA-N 0.000 description 1
- PBOAYFLHQXMTBK-UHFFFAOYSA-N 4-(2-ethylhexoxycarbonyl)-7-oxabicyclo[4.1.0]heptane-3-carboxylic acid Chemical compound C1C(C(O)=O)C(C(=O)OCC(CC)CCCC)CC2OC21 PBOAYFLHQXMTBK-UHFFFAOYSA-N 0.000 description 1
- UJWRVYWLRMVCIR-UHFFFAOYSA-N 4-benzylbenzene-1,2,3-triol Chemical class OC1=C(O)C(O)=CC=C1CC1=CC=CC=C1 UJWRVYWLRMVCIR-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- JBQKDXQJSYBVEN-UHFFFAOYSA-N 6-dodecoxy-6-oxohexanoic acid Chemical compound CCCCCCCCCCCCOC(=O)CCCCC(O)=O JBQKDXQJSYBVEN-UHFFFAOYSA-N 0.000 description 1
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ADAHGVUHKDNLEB-UHFFFAOYSA-N Bis(2,3-epoxycyclopentyl)ether Chemical compound C1CC2OC2C1OC1CCC2OC21 ADAHGVUHKDNLEB-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-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
- ZFIVKAOQEXOYFY-UHFFFAOYSA-N Diepoxybutane Chemical compound C1OC1C1OC1 ZFIVKAOQEXOYFY-UHFFFAOYSA-N 0.000 description 1
- WPYCRFCQABTEKC-UHFFFAOYSA-N Diglycidyl resorcinol ether Chemical compound C1OC1COC(C=1)=CC=CC=1OCC1CO1 WPYCRFCQABTEKC-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical compound NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Chemical class 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 241000724822 Teia Species 0.000 description 1
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- AVUYXHYHTTVPRX-UHFFFAOYSA-N Tris(2-methyl-1-aziridinyl)phosphine oxide Chemical compound CC1CN1P(=O)(N1C(C1)C)N1C(C)C1 AVUYXHYHTTVPRX-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 229940067597 azelate Drugs 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- WRUOQYMMDKPTCY-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-ylmethyl) benzene-1,4-dicarboxylate Chemical compound C1CC2OC2CC1COC(=O)C(C=C1)=CC=C1C(=O)OCC1CC2OC2CC1 WRUOQYMMDKPTCY-UHFFFAOYSA-N 0.000 description 1
- MAGPJIIPJYBADN-ARJAWSKDSA-N bis[(3-methyl-7-oxabicyclo[4.1.0]heptan-4-yl)methyl] (z)-but-2-enedioate Chemical compound C1C2OC2CC(C)C1COC(=O)\C=C/C(=O)OCC1CC2OC2CC1C MAGPJIIPJYBADN-ARJAWSKDSA-N 0.000 description 1
- SSNKDSAZVVJGHJ-UHFFFAOYSA-N bis[(3-methyl-7-oxabicyclo[4.1.0]heptan-4-yl)methyl] benzene-1,4-dicarboxylate Chemical compound C1C2OC2CC(C)C1COC(=O)C(C=C1)=CC=C1C(=O)OCC1CC2OC2CC1C SSNKDSAZVVJGHJ-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- YMZYRUGVHTYUBH-GNOQXXQHSA-K chromium(3+) (Z)-octadec-9-enoate Chemical compound [Cr+3].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O YMZYRUGVHTYUBH-GNOQXXQHSA-K 0.000 description 1
- ZJUZSYOZFGLOCJ-UHFFFAOYSA-K chromium(3+);3,3,5,5-tetramethylhexanoate Chemical compound [Cr+3].CC(C)(C)CC(C)(C)CC([O-])=O.CC(C)(C)CC(C)(C)CC([O-])=O.CC(C)(C)CC(C)(C)CC([O-])=O ZJUZSYOZFGLOCJ-UHFFFAOYSA-K 0.000 description 1
- IVKVYYVDZLZGGY-UHFFFAOYSA-K chromium(3+);octadecanoate Chemical compound [Cr+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O IVKVYYVDZLZGGY-UHFFFAOYSA-K 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- BQQUFAMSJAKLNB-UHFFFAOYSA-N dicyclopentadiene diepoxide Chemical compound C12C(C3OC33)CC3C2CC2C1O2 BQQUFAMSJAKLNB-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical group OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 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
- 238000009472 formulation Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 description 1
- ZBKFYXZXZJPWNQ-UHFFFAOYSA-N isothiocyanate group Chemical group [N-]=C=S ZBKFYXZXZJPWNQ-UHFFFAOYSA-N 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 1
- VIJMMQUAJQEELS-UHFFFAOYSA-N n,n-bis(ethenyl)ethenamine Chemical compound C=CN(C=C)C=C VIJMMQUAJQEELS-UHFFFAOYSA-N 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- WLJVNTCWHIRURA-UHFFFAOYSA-M pimelate(1-) Chemical compound OC(=O)CCCCCC([O-])=O WLJVNTCWHIRURA-UHFFFAOYSA-M 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XRVCFZPJAHWYTB-UHFFFAOYSA-N prenderol Chemical compound CCC(CC)(CO)CO XRVCFZPJAHWYTB-UHFFFAOYSA-N 0.000 description 1
- 229950006800 prenderol Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000003263 primary aromatic amine group Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 150000005619 secondary aliphatic amines Chemical group 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001394 sodium malate Substances 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C06B23/001—Fillers, gelling and thickening agents (e.g. fibres), absorbents for nitroglycerine
-
- 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
- oxidizer oxygen containing ammonium UNITED STATES PATENTS salt
- the propellant of this invention comprises in the form of a cured admixture a crosslinkable binder prepolymer, a crosslinking agent, an oxygen containing ammonium salt and a polyfunctional amine which contains at least one amine group more basic than ammonia and at least one amine group which is reactive with the polymeric binder.
- this invention relates to composite propellant compositions in which dewetting of the propellant composition is substantially reduced through the incorporation of certain polyfunctional amines in controlled amounts, said polyfunctional amines capable of providing a primary chemical bond between the surface of the oxygen containing ammonium salt and propellant binder in the cured propellant.
- Composite solid propellants are comprised of oxidizers and fuels in the form of small solid particles, sometimes referred to hereinafter as fillers, uniformly distributed in a polymeric binder.
- the polymeric binder functions to hold and uniformly distribute the tiller particles throughout the binder.
- Mechanical and ballistic properties of propellants are of primary importance in the selection of a propellant for any particular use. Mechanical and ballistic properties are known to depend on the nature of the interface between the solid filler particles and the polymeric binder. It has been discovered by various researchers in the field of solid propellants that mechanical failure of solid propellants resulting from environmental and operating stresses usually occurs at or about the binderfiller interface within the cured propellant matrix rather than in the propellant binder. Failure of composite propellant at the binder-filler interface is referred to as dewetting.
- triethanolamine was employed in an attempt to eliminate dewetting. While improved mechanical properties were achieved in a polyurethane binder employing triethanolamine as an additive, evolution of ammonia gas from these propellants caused difficulties in curing and in reproducibility of mechanical properties and resulted in porous propellant.
- Another additive employed in an attempt to reduce binder-filler dewetting was dihyoroxypropyl-bis-Z-cyanoethylamine. This material was considered superior to triethanolamine for use in polyurethane type composite propellants because ammonia was not liberated as reaction product during mixing and cure of the composition.
- Recent studies by C. 0. Parker and T. E. Stevens reported in Redstone Research Laboratories Technical Report 8-205 of January 1969 show that use of dihydroxypropyl-bis-2-cyanoethylamine increases the mix viscosity of composite propellant and complicates propellant processing.
- composite propellant compositions are provided in which the tendency of the propellant to dewet under conditions of stress is substantially reduced, said propellant compositions comprising in the form of a cured admixture a crosslinkable binder prepolymer, a crosslinking agent, an oxygen containing ammonium salt selected from the group consisting of ammonium perchlorate, ammonium nitrate, hydrazine perchlorate and hydrazine diperchlorate, and a polyfunctional amine having at least one amine group more basic than ammonia and at least one amine group reactive with and available for reaction with the polymeric binder after ammonia has been displaced from the surface of the oxygencontaining ammonium salt.
- the composite propellant compositions of this invention comprise by weight in the form of a cured admixture from about 60 to about percent of oxygen-containing ammonium salt, from about 5 to about 20 percent of a crosslinkable binder prepolymer and crosslinking agent and from about 0.005 to about 0.05 percent of a polyfunctional amine.
- These compositions can optionally contain a metal or metal hydride fuel in amounts of from 0 to about 20 percent by weight.
- the polyfunctional amines which can be employed in this invention include amines having one or more aliphatic amine groups which are more strongly basic than ammonia and at least one primary aromatic amine group which is less basic than ammonia; and polyfunctional aliphatic amines containing primary and secondary amine groups in which all of the amine groups are more basic than ammonia, but for steric or electronic reasons at least one of the secondary aliphatic amine groups remains free, i.e., it will not displace ammonia from the surface of ammonium perchlorate.
- the free amine group(s) of this latter class of amines are available to react with polymeric binder.
- X is either LL Jy l wherein Ar is phenylene, amino-substituted phenylene, naphthylene, amino-substituted naphthylene; m is from 1 to 20, n is from 2 to 5, y is from 1 to 5 and R is hydrogen or lower alkyl having from one to four carbon atoms.
- a preferred class of polyfunctional amines having the general formula I-a has the structural formula set forth below:
- Illustrative polyfunctional amines which can be employed in the compositions of this invention wherein X of the general formula I is group (I-a) defined above include B -(4-aminophenyl) ethylamine; triaminophenyl) butylamine, ,B-(2,4-diaminophenyl) hexylamine; ,8- (4-aminophenyl) decylamine; B-(Z, 4-diaminophenyl) tetradecylamine; 2-amino-7-naphthalenethylamine; 2-amin0-7-naphthalenebutylamine; 3,5-diamino-6-naphthalenedecylamine and the like.
- Illustrative polyfunctional amines of formula I wherein X is group (I-b) defined above include diethylenetriamine, triethylenetetramine; tetraethylenepentamine, pentaethylenehexamine, and the like. Another suitable polyfunctional amine is polyethyleneimine. This polyfunctional amine is available commercially @QE e IE L .UT1UlQ.:MQDIQ Binder systems which can be employed in the propellant compositions of this invention include all binder systems which are reactive with the polyfunctional amines described herein. These binders include those derived from polyester prepolymers such as polyesters having terminal carboxy groups and which are linear condensation products of polyhydric alcohols and polybasic acids such as set forth in US. Pat. No.
- polyurethane binders prepared by reaction of a compound having two or more hydroxyl or thiol groups with an organic compound having two or more isocyanate or isothiocyanate groups such as disclosed in US. Pat. No. 3,296,043; and polymeric binders derived from carboxy-terminated prepolymers fully described hereinafter.
- the number of functional groups on at least a portion of the binder prepolymer and/or crosslinking agent must be greater than 2 so that a crosslinked propellant composition results.
- Binder prepolymers 1-7 in Table I cure principally via the epoxide-carboxyl reaction.
- Binder prepolymers 8-18 cure via formation of urethane linkages from the interaction of hydroxyl and isocyanate groups.
- Binder prepolymer 19 cures via an isocyanate hydroxyl reaction.
- Crosslinking agents which can be employed with the crosslinkable propellant binder prepolymer to effect Crosslinking thereof and which will react with the polyfunctional amine to provide a chemical bond between the polyfunctional amine and the propellant binder when in a cured admixture include polyisocyanates, polyisothiocyanates, polyepoxides, and polyimines.
- Illustrative polyisocyanates which can be employed include alkane diisocyanates, such as: ethylene diisocyanate and trimethylene diisocyanate; alkene diisocyanates such as l-propylene-l,2-diisocyanate and 2-propylene-l ,2-diisocyanate; alkylidene diisocyanates such as ethylidene diisocyanate; cycloalkylene diisocyanates; cycloalkylidene diisocyanates; aromatic diisocyanates such as m-phenylene diisocyanate; 2,4- tolylene diisocyanate and 2,6-tolylene diisocyanate; aliphatic-aromatic diisocyanates such as xylene-1,4-
- Illustrative polyimines which can be employed as cross-linking agents include the alkyleneimine tris-1,2- methyl aziridinyl phosphine oxide sold under the tradename MAPO; tris-l ,Z-methyl aziridinyl phosphine sulfide; ethylene glycol-bis-B-propylene imine propionate; and terephtaloyl-bis-ethylene imine, mixtures thereof and the like.
- Illustrative polyepoxides which can be employed are preferably mixtures of di and triepoxides fully defined hereinafter. Any of the diepoxides and triepoxide mixtures set forth herein can be employed for binder systems other than the preferred binder referred to hereinafter.
- the preferred binder prepolymer to be employed in I this invention is a carboxy-terminated prepolymer containing on the average not less than about two free carboxyl groups per polymer molecule and is preferably a homopolyrner of an olefin such as isobutylene or a conjugated diene containing four to eight carbon atoms, such as butadiene-l,3; isoprene; octadiene-1,3 and the like; a copolymer of more than one olefin or conjugated diene such as an ethylene-propylene copolymer; a copolymer of a conjugated diene with other copolymerizable monomers which are preferably vinylsubstituted aromatic compounds such as styrene, the lor 2-vinyl naphthalenes and their alkyl, aryl, alkoxy, cy cloalkyl, alkaryl, aralkyl, aryloxy, and
- the preferred carboxy-terminated prepolymers can be produced in known manner from the above monomers, as, for example, by carrying out the polymerization in the presence of, as initiators, organoalkali metal compounds of the formula RM where R is an aliphatic, cycloaliphatic or aromatic hydrocarbon radical, M is an alkali metal such as sodium, potassium, lithium, cesium, or rubidium, and v is 2 to 4, and then replacing the alkali metal atoms on the ends of the polymer molecule with COOH groups by reacting with carbon dioxide and then hydrolyzing.
- organoalkali metal compounds of the formula RM where R is an aliphatic, cycloaliphatic or aromatic hydrocarbon radical, M is an alkali metal such as sodium, potassium, lithium, cesium, or rubidium, and v is 2 to 4, and then replacing the alkali metal atoms on the ends of the polymer molecule with COOH groups by reacting with carbon dioxide and then hydrolyzing.
- Polymers containing two or more carboxyl groups per polymer molecule can be prepared by polymerizing an unsaturated carboxylic acid containing a single carbon to carbon double bond such as acrylic, methacrylic, itaconic, vinyl acetic, oleic, fumaric, maleic, and like acids with itself or with a different copolymerizable monomer such as, for example, a different unsaturated acid, an olefin or a conjugated diene, according to any of the known methods.
- an unsaturated carboxylic acid containing a single carbon to carbon double bond such as acrylic, methacrylic, itaconic, vinyl acetic, oleic, fumaric, maleic, and like acids
- a different copolymerizable monomer such as, for example, a different unsaturated acid, an olefin or a conjugated diene, according to any of the known methods.
- the carboxy-te rminated prepolymers which are par ticularly useful in this invention are the carboxyterminated polymers of butadiene and isobutylene,
- molecular weights ranging from about 1,000 to about 20,000, and preferably from about 3,000 to about 10,000.
- the curing agent which is employed in curing the preferred prepolymer of this invention is a mixture of diepoxides and triepoxides having a diepoxideztriepoxide mole ratio of from about 15:1 to 1:1, and preferably from 8:1 to 3:1. Maintenance of the ratio of the difunctional epoxides to the trifunctional epoxides within the above ranges is important to the production of propellants having a satisfactory mechanical property balance since below the ratio of 1:1 the propellant elongation is low, and above the ratio of 15:1 the propellant tensile strength is low.
- diepoxides which can be employed are the saturated or unsaturated aliphatic, cycloaliphatic, aromatic or heterocyclic diepoxides which also contain, if desired, non-interfering substituents.
- Preferred diepoxides are the aliphatic diepoxides containing four to 30 carbon atoms, the cycloaliphatic diepoxides containing 12 to 40 carbon atoms and the diglycidyl ethers of dihydric phenols.
- Typical diepoxides include butadiene dioxide; l,2,5,6-diepoxyhexane; diglycidyl ether; diglycidyl ether of 1,3-butanediol; l,8-bis(2,3- epoxypropoxy) octane; l,4-bis(2,3-epoxypropoxy) cyclohexane; 1,4-bis(3,4-epoxybutoxy)-2- chlorocyclohexane; the di(epoxycyclohexanecarboxylates) of aliphatic diols exemplified by the bis(3,4- epoxycyclohexanecarboxylate) of 1,5-pentanedio1, S-methyl-l ,S-pentanediol, 2-methoxymethyl-2,4- dimethyl-l,S-pentanediol; ethylene glycol, 2,2-diethyl- 1,3-propanediol;
- epoxypentoxy)-5-chlorobenzene 4,4-bis-( 2,3- epoxypropoxy) diphenylether; 2,2-bis( 2,3-epoxypropoxyphenyl) methane; 2,2-bis[p-(2,3-
- epoxypropoxy) phenyl] propane i.e., the diglycidyl ether of bisphenol A; quinoline diepoxide and the like, as well as mixtures thereof.
- Triepoxides can be employed and contain three epoxide groups per molecule and are aliphatic, cycloaliphatic or aromatic triepoxides.
- Preferred triepoxides are the triepoxyalkanes containing six to 25 carbon atoms; the triepoxycyclohexane carboxylates and the triglycidylethers of trihydric alcohols such as glycerol, 1 ,1,l-tri(hydroxymethyl) propane, 1,2,6-hexanetriol and the higher alcohols containing up to about 25 carbon atoms; and the triglycidyl ethers of trihydric phenols, such as phloroglucinol, the trihydroxydiphenyl methanes and propanes, the trihydroxyaminophenols, the trisphenols; mixtures thereof and the like.
- Epoxide mixtures containing the diglycidyl ethers of bisphenol A and the triepoxides of the aminophenols
- both the diepoxide and the triepoxide of the mixture will be in the relatively pure state, i.e., having a purity of about to percent.
- the ratio of the epoxy groups in the epoxide mixture to the functional groups of the resin binder should be in substantially stoichiometric proportions. Although a slight excess of either is not harmful, it is preferred that a slight excess of epoxy groups over resin binder functional groups be present in the binder.
- a-catalyst which promotes the carboxyl-epoxide reaction.
- the catalyst must also have high activity in the presence of the other propellant ingredients and must not adversely affect the desirable properties of the cured propellant, as by side reactions.
- Catalysts which have been found to fit all of the above requirements are chromium salts of aliphatic carboxylic acids containing two to 22 carbon atoms are preferably two to 18 carbon atoms, chromium naphthenate or vanadium naphthenate.
- the preferred catalysts include chromium acetate, chromium 2- ethylhexanoate, chromium neodecanoate, chromium stearate, chromium oleate, chromium naphthenate and vanadium naphthenate.
- the amount of catalyst necessary to promote the reaction will, of course, depend on many factors, as for example, on the particular metal salt employed, the binder materials and other propellant ingredients present, and the cure rate desired. In general, the amount of catalyst utilized will vary from a very small catalytic amount up to about 0.1 percent of the propellant composition and preferably will be from about 0.005 to about 0.03 percent by weight of the composition.
- the composite propellant of this invention is prepared by intimately blending or mixing the ingredients heretofore described using conventional techniques and standard equipment.
- the solid propellant compositions of this invention are prepared by admixing the binder forming ingredients comprising a prepolymer and a crosslinking agent therefor and a polyfunctional organic amine as defined herein. To this admixture is added the oxygen containing ammonium salt. As is often the case in preparing composite propellants, the oxygen containing ammonium salt may be added in more than one particle size in order to effectively control the cured propellant burning rate.
- oxidizer having more than one particle size range it is generally preferable to admix the oxidizer having the smallest average particle size last, since the smallest particles have the highest surface to mass ratio and will scavenge the polyfunctional organic amine from the admixture.
- the order of mixing of ingredients as set forth can be varied. For example, when the polyfunctional amine additive reacts with the binder forming ingredients at a much faster rate than with the oxygen containing ammonium salt, it is generally preferable to add the polyfunctional amine after the oxidizer has been admixed with the binder forming ingredients.
- Examples 1-6 A binder solution is prepared by admixing 0.0108
- a chromium 2-ethylhexanoate catalyst containing 10.95 percent chromium into 7.727 parts of a carboxy-terminated polybutadiene having a molecular weight of about 6,000, and a carboxyl content of 1.48 to 1.53 equivalents per grams of polybutadiene and containing 1.0 to 1.5 percent 2,2-methylene-bis(4- methyl-6-tert-butyl) phenol as antioxidant.
- An epoxide crosslinking mixture is added in several increments with stirring after each addition.
- Two plasticizers comprising 1.906 parts dioctyl adipate and 1.906 parts of a random polymer of butadiene are then added to the binder mixture.
- the epoxide mixture is a solution of diepoxides having an epoxy equivalency of 156 and 89 percent pure, and a triepoxide having an epoxy equivalency of 103 and 99 percent pure.
- a polyfunctional amine as specified in Table I.
- the resulting admixture is agitated until the polyfunctional amine is completely dispersed and dis solved in the binder. Mixing time required is generally from about 15 20 minutes.
- the solid ingredients are added as follows.
- Aluminum is added to the binder mixture and mixed for about 3 minutes.
- Ammonium perchlorate is added to the binder in three particle size ranges.
- Ammonium perchlorate having an average particle size of 200a and 400p is added to the binder and aluminum mixture and the resulting propellant matrix is agitated under a reduced pressure of 2.4 mm Hg for about 15 minutes.
- Ammonium perchlorate having an average particle size of 10p. is then added to the propellant matrix and mixing is continued for an additional 15 minutes under a reduced pressure of 2.4 mm Hg.
- the resulting propellant is cast into a JANAF dogbone mold preheated at F.
- the cast propellant is deareated at reduced pressure of about 2.4 mm Hg for 1 hour.
- the propellant containing mold is sealed in a polyethylene bag containing a drying agent and the propellant is cured at 180F. for 7 days.
- the cured propellant is cooled to ambient temperature and is cut into 0.25 inch thick dogbone test samples. These dogbones are stored over a drying agent at the testing temperature. These dogbones are tested for mechanical properties employing an Instron Tester at the temperatures set forth in Table 11. Details of the binder composition, the polyfunctional amine employed, and the mechanical properties of the cured propellants are set forth in Table 11. In each example a control propellant was prepared without the addition of polyfunctional amine and was tested for mechanical properties for comparison purposes.
- Example 1 illustrates improved tensile strength and employing triethylenetetramine as the polyfunctional elongations for propellant containing triethyleneamine and following the general mixing procedure as tetramine as the polyfunctional amine.
- Carboxylated rubber 8.626; diepoxide, 0.417; triepoxide, 0.064; catalyst, 0.079; hydrocarbon plasticizer, 1.882; ester plasticizer, 1.02.
- propellant in the binder phase i.e., dewetting is sub- Examples 7, 8, 9, l0, ll,and 12 (Table III) illustrate stantially eliminated.
- Microstructure failure analysis of both improved tensile strengths and elongations from the control propellant at the same test conditions propellant prepared with triethylenetetramine as the showed failure at the binder-filler interface illustrating polyfunctional amine and, in addition, the effect of dewetting.
- concentration of triethylenetetramine on mechanical Examples 2 and 3 illustrate improved tensile 4 properties and mix viscosity. At 0.0135 percent constrengths, elongations, and improved creep properties nt a (Ex mpl and 1 the tensile r g compared to the control rounds.
- Propellants of Examand elongation of the propellant is significantly better ples 2 and 3 employ triethylenetetramine as the polythan at the 0.030 percent concentration level (Examfunctional amine and fail in the binder phase when subples 8, l0, and 12) and resistance to creep failure is imjected to high stress.
- the control propellants dewet i.e., 45 proved markedly.
- Example 6 illustrates the importance of concentra- E l 13-18 tion of the polyfunctional amine in achieving improvement in mechanical properties.
- the percentage 7 of triethylenetetramine is increased to 0.06 percent by Six additional propellant compositions are prepared weight, inferior mechanical properties result.
- Propellant composi- Six additional propellant compositions are prepared tions and results of testing are set forth in Table IV.
- Example 13 illustrates that at the 0.002 percent concentration level, APE has very little effect on mechanical properties or microstructural failure mode. This propellant and its control both fail at the binder-filler 5 interface. However, at this low amine level the mix viscosity is reduced about 18 percent.
- Examples 14 through 18 illustrate that at APE levels between 0.0113 and 0.060 percent, failure occurs exclusively in the binder phase whereas the corresponding control propellants fail at the binder-filler interface (dewetting). At these levels, resistance to creep failure is markedly improved.
- Examples 14 and I5 illustrate that the upper limit of usefulness of APE appears to be about 0.060 percent 15 in a diepoxide crosslinked carboxy-terminated rubber binder. At this concentration level (Example 15) the creep life is extended from minutes (control) to 5.5 hours. At the 0.040 percent concentration level of Example 14, the propellant appears to have infinite creep 20 life as evidenced by the fact that after 48 hours the rate of change of elongation with time is zero. The improvement in tensile strength and elongation is considerably greater at the lower (0.040 percent) APE concentration level. The mix viscosity is decreased significantly atboth levels.
- Example 16' illustrates that infinite creep life is obtained at APE concentration levels as low as 0.0113
- Examples 17 and 18 illustrate that at an epoxide to carboxyl ratio of 1.08/10, somewhat better mechanical properties are obtained with APE concentration levels of 0.01 13 percent (Example 17) than at 0.020 percent (Example 18). in both cases the resulting propellants appear to have infinite creep life.
- the propellant compositions of this invention prepared in Examples l-l 8 showed no porosity. While ammonia gas is liberated during mixing of the compositions, the amount of ammonia gas liberated is so small due to the small quantities of polyfunctional amine employed that substantially no porosity results.
- the propellant compositions of this invention have the following general compositions:
- the propellant composition contains by weight from about to about percent oxidizer and from about 5 to about 20 percent cured binder.
- the cured binder includes the binder prepolymer and crosslinking agent.
- a curing catalyst is employed as needed.
- From about 40 to about weight percent of the cured binder in the formulation is binder prepolymer, from about 1 to about 10 weightpercent is the crosslinking agent, and the binder plasticizer can be from about 0 to about 50 weight percent, and preferably is from about 20 to about 40 weight percent of the binder.
- the composite propellant of this invention can also contain other additives such as metal fuels, plasticizers, and the various compounding ingredients commonly employed in making composite propellants, as for exes 4 (m'aximuni'rii'iiiii ii Ex. 14-18 fail in the binder phase; the APE containing propellant of Ex. 13 and all control propellants fail at the binder-filler interface. or
- APE is fi-(4-aminophenyl)cthylamin0.
- metal fuels such as powdered aluminum, beryllium, magnesium, zirconium or boron, alloys such as the aluminum alloys of boron, magnesium, manganese, copper, and the like, and plasticizers such as dioctyl phthalate, dicotyl azelate, dioctyl adipate, dodecyl adipate, polybutadiene, polyisobutylene, and the like can be utilized.
- Surfactants such as lecithin or mixtures of sorbitan monooleate and polyoxyethylene esters of mixed fatty and resin acids; ballistic modifiers such as di-n-butyl ferrocene, iron oxide, chromium oxide or oxamide, and radar attenuators such as molybdenum trioxide, can also be present in minor amounts in the propellant composition of this invention.
- a composite propellant composition comprising in the form of a cured admixture:
- an oxidizer consisting essentially of an oxygen containing ammonium salt selected from the group consisting of ammonium perchlorate, ammonium nitrate, hydrazine perchlorate, hydrazine diperchlorate, and mixtures thereof,
- crosslinkable binder prepolymer having reactive functional groups selected from the group consisting of hydroxyl, carboxyl and isocyanate groups and a crosslinking agent therefore said crosslinking agent having reactive functional groups selected from the groups consisting of polyepoxides, polyisocyanates, polythioisocyanates, and polyimines,
- a polyfunctional amine selected from the polyethyleneimine and amines having the general formula l l. HZN x NHR where X is either a) (CH ),,,Ar or said propellant composition comprising by weight from about 60 to about percent of said oxygen containing ammonium salts, from about 5 to about 20 percent of crosslinkable binder prepolymer and crosslinking agent and from about 0.005 to about 0.05 percent of polyfunctional amine.
- z is O, l, 2, 3 or 4, and R is hydrogen or lower alkyl having from one to four carbon atoms and R is hydrogen.
- the propellant composition of claim 1 wherein the polyfunctional amine is B-(4-aminophenyl) ethylam- 8.
- the composite propellant composition of claim 1 wherein the oxygen containing ammonium salt is ammonium perchlorate, the crosslinkable binder prepolymer is a carboxyl terminated prepolymer, and the crosslinking agent is a mixture of diepoxides and trie poxides.
- the Elongation (percent) determined at 77F should read 36, not 96.
- the Elongation (percent) determined at 77F should read 36, not 96.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Molecular Biology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Propellant compositions are provided in which dewetting of the propellant composition under applied stress is substantially reduced. Reduced dewetting is achieved through the use of polyfunctional amines which are capable of forming a chemical bond between the oxidizer (oxygen containing ammonium salt) and the binder in the cured propellant.
Description
Elite tats Ptemt 1191 Dehm Feb. 5, 1974 [54] COMPOSITE PROPELLANT KNCLUDHNG 3,454,436 7 1967 Bedell 149/19 (U) POLYFUNCTHONAL A E 3,529,042 9/1970 Lippert 3,476,622 11/1969 Harada et a1. lnvemori Henry Dehm, Salt Lake y, 3,586,552 6/1971 Potts a a1 149/19 Utah [73] Assignee: Hercules Incorporated, Wilmington, Primary Examiner-Carl D. Quarforth Del. Assistant ExaminerE. A. Miller [22] Filed y 22 1970 Attorney, Agent, or Firm-Michael B. Keehan 21 A l.N .187513 1 pp 57 ABSTRACT [52 U.S. c1 149/19 149/36 149/60 ProP?ant P are Pmvided in which dewei- 149/76 ting of the propellant composition under applied stress 51 1m. (:1 C06d 5/06 is substantially reduced- Reduced deweiiiiig is 58 Field of Search 149/19 76 36 60 achieved through the use of Poiyfunciionai amines i which are capable of forming a chemical bond be- [56] References Cited tween the oxidizer (oxygen containing ammonium UNITED STATES PATENTS salt) and the binder in the cured propellant.
3,305,523 2/1967 Burnside 149/19 X i 11 Claims, N0 Drawings COMPOSITE PROPELLANT INCLUDENG (U) POLYFUNCTIONAL AMINE This invention relates to novel composite propellant compositions having superior load bearing properties, stability, and mechanical properties. The propellant of this invention comprises in the form of a cured admixture a crosslinkable binder prepolymer, a crosslinking agent, an oxygen containing ammonium salt and a polyfunctional amine which contains at least one amine group more basic than ammonia and at least one amine group which is reactive with the polymeric binder. More particularly, this invention relates to composite propellant compositions in which dewetting of the propellant composition is substantially reduced through the incorporation of certain polyfunctional amines in controlled amounts, said polyfunctional amines capable of providing a primary chemical bond between the surface of the oxygen containing ammonium salt and propellant binder in the cured propellant.
Composite solid propellants are comprised of oxidizers and fuels in the form of small solid particles, sometimes referred to hereinafter as fillers, uniformly distributed in a polymeric binder. The polymeric binder functions to hold and uniformly distribute the tiller particles throughout the binder.
Mechanical and ballistic properties of propellants are of primary importance in the selection of a propellant for any particular use. Mechanical and ballistic properties are known to depend on the nature of the interface between the solid filler particles and the polymeric binder. It has been discovered by various researchers in the field of solid propellants that mechanical failure of solid propellants resulting from environmental and operating stresses usually occurs at or about the binderfiller interface within the cured propellant matrix rather than in the propellant binder. Failure of composite propellant at the binder-filler interface is referred to as dewetting.
Studies by Oberth and Bruenne'r reported in CPIA Publication No. 94C, Vol. 11, dated October 1965, show that subscale motors containing propellants that fail in the binder phase of the propellant have markedly improved recycle properties compared to substantially identical propellants that dewet at the binder-filler interface under similar stress conditions. Still other studies have shown that composite propellants that fail under conditions of high stress exclusively in the binder I phase rather than at the binder-filler interface exhibit markedly improved load bearing capability and, in general, are physically more stable propellants. Failure of propellants in the binder phase rather than at the binder-filler interface was achieved employing various additives which function to bond the ammonium perchlorate oxidizer to the propellant binder.
In some of the studies conducted by Oberth and Bruenner, triethanolamine was employed in an attempt to eliminate dewetting. While improved mechanical properties were achieved in a polyurethane binder employing triethanolamine as an additive, evolution of ammonia gas from these propellants caused difficulties in curing and in reproducibility of mechanical properties and resulted in porous propellant. Another additive employed in an attempt to reduce binder-filler dewetting was dihyoroxypropyl-bis-Z-cyanoethylamine. This material was considered superior to triethanolamine for use in polyurethane type composite propellants because ammonia was not liberated as reaction product during mixing and cure of the composition. Recent studies by C. 0. Parker and T. E. Stevens reported in Redstone Research Laboratories Technical Report 8-205 of January 1969 show that use of dihydroxypropyl-bis-2-cyanoethylamine increases the mix viscosity of composite propellant and complicates propellant processing.
Broadly, in accordance with this invention, composite propellant compositions are provided in which the tendency of the propellant to dewet under conditions of stress is substantially reduced, said propellant compositions comprising in the form of a cured admixture a crosslinkable binder prepolymer, a crosslinking agent, an oxygen containing ammonium salt selected from the group consisting of ammonium perchlorate, ammonium nitrate, hydrazine perchlorate and hydrazine diperchlorate, and a polyfunctional amine having at least one amine group more basic than ammonia and at least one amine group reactive with and available for reaction with the polymeric binder after ammonia has been displaced from the surface of the oxygencontaining ammonium salt. The composite propellant compositions of this invention comprise by weight in the form of a cured admixture from about 60 to about percent of oxygen-containing ammonium salt, from about 5 to about 20 percent of a crosslinkable binder prepolymer and crosslinking agent and from about 0.005 to about 0.05 percent of a polyfunctional amine. These compositions can optionally contain a metal or metal hydride fuel in amounts of from 0 to about 20 percent by weight.
The polyfunctional amines which can be employed in this invention include amines having one or more aliphatic amine groups which are more strongly basic than ammonia and at least one primary aromatic amine group which is less basic than ammonia; and polyfunctional aliphatic amines containing primary and secondary amine groups in which all of the amine groups are more basic than ammonia, but for steric or electronic reasons at least one of the secondary aliphatic amine groups remains free, i.e., it will not displace ammonia from the surface of ammonium perchlorate. The free amine group(s) of this latter class of amines are available to react with polymeric binder.
Illustrative polyfunctional amines defined above have the following structural formula:
where X is either LL Jy l wherein Ar is phenylene, amino-substituted phenylene, naphthylene, amino-substituted naphthylene; m is from 1 to 20, n is from 2 to 5, y is from 1 to 5 and R is hydrogen or lower alkyl having from one to four carbon atoms.
A preferred class of polyfunctional amines having the general formula I-a has the structural formula set forth below:
where z is 0,1, 2, 3 or 4.
Illustrative polyfunctional amines which can be employed in the compositions of this invention wherein X of the general formula I is group (I-a) defined above include B -(4-aminophenyl) ethylamine; triaminophenyl) butylamine, ,B-(2,4-diaminophenyl) hexylamine; ,8- (4-aminophenyl) decylamine; B-(Z, 4-diaminophenyl) tetradecylamine; 2-amino-7-naphthalenethylamine; 2-amin0-7-naphthalenebutylamine; 3,5-diamino-6-naphthalenedecylamine and the like. Illustrative polyfunctional amines of formula I wherein X is group (I-b) defined above include diethylenetriamine, triethylenetetramine; tetraethylenepentamine, pentaethylenehexamine, and the like. Another suitable polyfunctional amine is polyethyleneimine. This polyfunctional amine is available commercially @QE e IE L .UT1UlQ.:MQDIQ Binder systems which can be employed in the propellant compositions of this invention include all binder systems which are reactive with the polyfunctional amines described herein. These binders include those derived from polyester prepolymers such as polyesters having terminal carboxy groups and which are linear condensation products of polyhydric alcohols and polybasic acids such as set forth in US. Pat. No. 3,155,552; polyurethane binders prepared by reaction of a compound having two or more hydroxyl or thiol groups with an organic compound having two or more isocyanate or isothiocyanate groups such as disclosed in US. Pat. No. 3,296,043; and polymeric binders derived from carboxy-terminated prepolymers fully described hereinafter. The number of functional groups on at least a portion of the binder prepolymer and/or crosslinking agent must be greater than 2 so that a crosslinked propellant composition results.
Illustrative binder prepolymers and crosslinkings agents which will react with the polyfunctional amines hereinabove defined to produce the propellant compositions of this invention are set forth in Table I which follows.
TABLE I Prepolymer Curing agent functional functional group group rereacting in the acting in the curing reaction curing Binder prepolymer reaction Carboxyl-terminated polybuta- Carboxyl.... Epxide,imine.
y- Do.
acrylate ester. 7, .4
TABLE I -Cominucd Prepolymer Curingngentfunctional functionnlgronp group rereacting in the acting in the curing reaction curing Binder prepolymer reaction 12. Ethyl acrylatel1ydroxyethyl .....d0 Do.
acrylate copolymer (hydrocarbon backbone). 13. Hydroxyl-terminated fiuoro- .do Do.
carbon. 14.... Hydroxyl-terminated polyester ....do Do.
(polyester backbone) as in U.S. 3,296,043, col. 10, lines 62:75; col. 11, lines 1-30. 15. Low molecular weight diols .do..." D0.
(U.S. 3,296,043, col. 10, lines 7-61 16.... I-Iydroxyl-terminatcd polyether ..do Do. 17. Hydroxyl-tcrminatcd polysul- ..do Do.
fide (as in U.S. 3,296,043, col. 11, lines 33-37). Nitrocellulose ..do Do. Isocyanate-terrninatcd poly- Isocyanato.. Hydroxyl.
ester (polyester backbone).
1 As in U.S. 3,296,043, col. 12, lines 11-24. W
Binder prepolymers 1-7 in Table I cure principally via the epoxide-carboxyl reaction. Binder prepolymers 8-18 cure via formation of urethane linkages from the interaction of hydroxyl and isocyanate groups. Binder prepolymer 19 cures via an isocyanate hydroxyl reaction.
Crosslinking agents which can be employed with the crosslinkable propellant binder prepolymer to effect Crosslinking thereof and which will react with the polyfunctional amine to provide a chemical bond between the polyfunctional amine and the propellant binder when in a cured admixture include polyisocyanates, polyisothiocyanates, polyepoxides, and polyimines.
Illustrative polyisocyanates which can be employed include alkane diisocyanates, such as: ethylene diisocyanate and trimethylene diisocyanate; alkene diisocyanates such as l-propylene-l,2-diisocyanate and 2-propylene-l ,2-diisocyanate; alkylidene diisocyanates such as ethylidene diisocyanate; cycloalkylene diisocyanates; cycloalkylidene diisocyanates; aromatic diisocyanates such as m-phenylene diisocyanate; 2,4- tolylene diisocyanate and 2,6-tolylene diisocyanate; aliphatic-aromatic diisocyanates such as xylene-1,4-
diisocyanate, mixtures thereof and the like. Polyisothiocyanates corresponding to the polyisocyanates described hereinabove can be employed in place of a polyisocyanate crosslinking agent. H
Illustrative polyimines which can be employed as cross-linking agents include the alkyleneimine tris-1,2- methyl aziridinyl phosphine oxide sold under the tradename MAPO; tris-l ,Z-methyl aziridinyl phosphine sulfide; ethylene glycol-bis-B-propylene imine propionate; and terephtaloyl-bis-ethylene imine, mixtures thereof and the like.
Illustrative polyepoxides which can be employed are preferably mixtures of di and triepoxides fully defined hereinafter. Any of the diepoxides and triepoxide mixtures set forth herein can be employed for binder systems other than the preferred binder referred to hereinafter.
The preferred binder prepolymer to be employed in I this invention is a carboxy-terminated prepolymer containing on the average not less than about two free carboxyl groups per polymer molecule and is preferably a homopolyrner of an olefin such as isobutylene or a conjugated diene containing four to eight carbon atoms, such as butadiene-l,3; isoprene; octadiene-1,3 and the like; a copolymer of more than one olefin or conjugated diene such as an ethylene-propylene copolymer; a copolymer of a conjugated diene with other copolymerizable monomers which are preferably vinylsubstituted aromatic compounds such as styrene, the lor 2-vinyl naphthalenes and their alkyl, aryl, alkoxy, cy cloalkyl, alkaryl, aralkyl, aryloxy, and dialkyl amino derivatives; or a mixture of any of the above homopolymers or copolymers.
The preferred carboxy-terminated prepolymers can be produced in known manner from the above monomers, as, for example, by carrying out the polymerization in the presence of, as initiators, organoalkali metal compounds of the formula RM where R is an aliphatic, cycloaliphatic or aromatic hydrocarbon radical, M is an alkali metal such as sodium, potassium, lithium, cesium, or rubidium, and v is 2 to 4, and then replacing the alkali metal atoms on the ends of the polymer molecule with COOH groups by reacting with carbon dioxide and then hydrolyzing. Polymers containing two or more carboxyl groups per polymer molecule can be prepared by polymerizing an unsaturated carboxylic acid containing a single carbon to carbon double bond such as acrylic, methacrylic, itaconic, vinyl acetic, oleic, fumaric, maleic, and like acids with itself or with a different copolymerizable monomer such as, for example, a different unsaturated acid, an olefin or a conjugated diene, according to any of the known methods.
The carboxy-te rminated prepolymers which are par ticularly useful in this invention are the carboxyterminated polymers of butadiene and isobutylene,
having molecular weights ranging from about 1,000 to about 20,000, and preferably from about 3,000 to about 10,000.
The curing agent which is employed in curing the preferred prepolymer of this invention is a mixture of diepoxides and triepoxides having a diepoxideztriepoxide mole ratio of from about 15:1 to 1:1, and preferably from 8:1 to 3:1. Maintenance of the ratio of the difunctional epoxides to the trifunctional epoxides within the above ranges is important to the production of propellants having a satisfactory mechanical property balance since below the ratio of 1:1 the propellant elongation is low, and above the ratio of 15:1 the propellant tensile strength is low.
Illustrative diepoxides which can be employed are the saturated or unsaturated aliphatic, cycloaliphatic, aromatic or heterocyclic diepoxides which also contain, if desired, non-interfering substituents. Preferred diepoxides are the aliphatic diepoxides containing four to 30 carbon atoms, the cycloaliphatic diepoxides containing 12 to 40 carbon atoms and the diglycidyl ethers of dihydric phenols. Typical diepoxides include butadiene dioxide; l,2,5,6-diepoxyhexane; diglycidyl ether; diglycidyl ether of 1,3-butanediol; l,8-bis(2,3- epoxypropoxy) octane; l,4-bis(2,3-epoxypropoxy) cyclohexane; 1,4-bis(3,4-epoxybutoxy)-2- chlorocyclohexane; the di(epoxycyclohexanecarboxylates) of aliphatic diols exemplified by the bis(3,4- epoxycyclohexanecarboxylate) of 1,5-pentanedio1, S-methyl-l ,S-pentanediol, 2-methoxymethyl-2,4- dimethyl-l,S-pentanediol; ethylene glycol, 2,2-diethyl- 1,3-propanediol; 1,6-hexanediol and Z-butene-l ,4-dio1; the oxyalkylene glycol epoxycyclohexanecarboxylates exemplified v by bis(2-ethylhexyl-4,5- epoxycyclohexane-1,2-dicarboxylate) of dipropylene glycol, bis( 3,4-epoxy-6-mcthylcyclohexanecarboxylate) of diethylene glycol and bis(3,4-epoxycyclohexanecarboxylate) of triethylene glycol; the epoxycyclohexylalkyl epoxycyclohexanecarboxylates exemplifled by 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate; 3 ,4-epoxyl -methylcyclohexylmethyl 3,4-epoxy-l-methyl cyclohexanecarboxylate; 3,4- epoxy-2-methylcyclohexylmethyl 3,4-epoxy-2- methylcyclohexanecarboxylate; 3,4-epoxy-6-methylcyclohexylmethyl 3,4-epoxy-6-methylcyclohexanecarboxylate; (lchloro-3,4-epoxycyclohexan-l-yl) methyl l-chloro-3,4-epoxycyclohexanecarboxylate; l-bromo- 3 ,4-epoxycyclohexanl -yl) methyl l-bromo-3 ,4- epoxycyclohexanecarboxylate and l-chloro-Z-methyl- 4,5-epoxycyclohexan-l-yl) methyl l-chloro-Z-methyl- 4,5-epoxycyclohexanecarboxylate; epoxycyclohexylalkyl'dicarboxylates exemplified by bis(3,4-epoxycyclohexylmethyl) pimelate and oxalate and bis(3,4- epoxy-6-methylcyclohexylmethyl) maleate, succinate, sebacate and adipate; epoxycyclohexylalkyl phenylenedicarboxylates exemplified by bis(3,4- epoxycyclohexylmethyl) terephthalate and bis(3,4- epoxy-6-methylcyclohexylmethyl) terephthalate; bis(- 3,4-epoxy-6-methylcyclohexylmethyl) diethylene glycol ether; vinyl cyclohexene dioxide; diepoxide of dicyclohexene; dicyclopentadiene dioxide; bis(2,3-epoxycyclopentyl) ether; glycidyl 2,3-epoxycyclopentyl ether; 2,3-epoxycyclopentyl 2'-methylglycidyl ether; l,2,5,6-diepoxy-3-hexyne; 1,3-epoxypropoxy) benzene; l,4-bis(2,3-epoxypropoxy) benzene; 1,3-bis(4,5-
epoxypentoxy)-5-chlorobenzene; 4,4-bis-( 2,3- epoxypropoxy) diphenylether; 2,2-bis( 2,3-epoxypropoxyphenyl) methane; 2,2-bis[p-(2,3-
epoxypropoxy) phenyl] propane, i.e., the diglycidyl ether of bisphenol A; quinoline diepoxide and the like, as well as mixtures thereof.
Triepoxides can be employed and contain three epoxide groups per molecule and are aliphatic, cycloaliphatic or aromatic triepoxides. Preferred triepoxides are the triepoxyalkanes containing six to 25 carbon atoms; the triepoxycyclohexane carboxylates and the triglycidylethers of trihydric alcohols such as glycerol, 1 ,1,l-tri(hydroxymethyl) propane, 1,2,6-hexanetriol and the higher alcohols containing up to about 25 carbon atoms; and the triglycidyl ethers of trihydric phenols, such as phloroglucinol, the trihydroxydiphenyl methanes and propanes, the trihydroxyaminophenols, the trisphenols; mixtures thereof and the like. Epoxide mixtures containing the diglycidyl ethers of bisphenol A and the triepoxides of the aminophenols are particularly preferred.
For best results, both the diepoxide and the triepoxide of the mixture will be in the relatively pure state, i.e., having a purity of about to percent. The ratio of the epoxy groups in the epoxide mixture to the functional groups of the resin binder should be in substantially stoichiometric proportions. Although a slight excess of either is not harmful, it is preferred that a slight excess of epoxy groups over resin binder functional groups be present in the binder.
When employing carboxy-terminated prepolymer as the binder with an epoxide mixture as the crosslinking agent, the presence of a-catalyst is required which promotes the carboxyl-epoxide reaction. The catalyst must also have high activity in the presence of the other propellant ingredients and must not adversely affect the desirable properties of the cured propellant, as by side reactions. Catalysts which have been found to fit all of the above requirements are chromium salts of aliphatic carboxylic acids containing two to 22 carbon atoms are preferably two to 18 carbon atoms, chromium naphthenate or vanadium naphthenate. The preferred catalysts include chromium acetate, chromium 2- ethylhexanoate, chromium neodecanoate, chromium stearate, chromium oleate, chromium naphthenate and vanadium naphthenate. The amount of catalyst necessary to promote the reaction will, of course, depend on many factors, as for example, on the particular metal salt employed, the binder materials and other propellant ingredients present, and the cure rate desired. In general, the amount of catalyst utilized will vary from a very small catalytic amount up to about 0.1 percent of the propellant composition and preferably will be from about 0.005 to about 0.03 percent by weight of the composition.
The composite propellant of this invention is prepared by intimately blending or mixing the ingredients heretofore described using conventional techniques and standard equipment. The solid propellant compositions of this invention are prepared by admixing the binder forming ingredients comprising a prepolymer and a crosslinking agent therefor and a polyfunctional organic amine as defined herein. To this admixture is added the oxygen containing ammonium salt. As is often the case in preparing composite propellants, the oxygen containing ammonium salt may be added in more than one particle size in order to effectively control the cured propellant burning rate. When employing oxidizer having more than one particle size range it is generally preferable to admix the oxidizer having the smallest average particle size last, since the smallest particles have the highest surface to mass ratio and will scavenge the polyfunctional organic amine from the admixture. The order of mixing of ingredients as set forth can be varied. For example, when the polyfunctional amine additive reacts with the binder forming ingredients at a much faster rate than with the oxygen containing ammonium salt, it is generally preferable to add the polyfunctional amine after the oxidizer has been admixed with the binder forming ingredients.
The following examples will more fully illustrate this invention. All parts and percentages are by weight unless otherwise specified.
Examples 1-6 A binder solution is prepared by admixing 0.0108
parts of a chromium 2-ethylhexanoate catalyst containing 10.95 percent chromium into 7.727 parts of a carboxy-terminated polybutadiene having a molecular weight of about 6,000, and a carboxyl content of 1.48 to 1.53 equivalents per grams of polybutadiene and containing 1.0 to 1.5 percent 2,2-methylene-bis(4- methyl-6-tert-butyl) phenol as antioxidant. An epoxide crosslinking mixture is added in several increments with stirring after each addition. Two plasticizers comprising 1.906 parts dioctyl adipate and 1.906 parts of a random polymer of butadiene are then added to the binder mixture. The epoxide mixture is a solution of diepoxides having an epoxy equivalency of 156 and 89 percent pure, and a triepoxide having an epoxy equivalency of 103 and 99 percent pure. To this binder solution is added a polyfunctional amine as specified in Table I. The resulting admixture is agitated until the polyfunctional amine is completely dispersed and dis solved in the binder. Mixing time required is generally from about 15 20 minutes.
Following preparation of the binder mixture the solid ingredients are added as follows. Aluminum is added to the binder mixture and mixed for about 3 minutes. Ammonium perchlorate is added to the binder in three particle size ranges. Ammonium perchlorate having an average particle size of 200a and 400p is added to the binder and aluminum mixture and the resulting propellant matrix is agitated under a reduced pressure of 2.4 mm Hg for about 15 minutes. Ammonium perchlorate having an average particle size of 10p. is then added to the propellant matrix and mixing is continued for an additional 15 minutes under a reduced pressure of 2.4 mm Hg. The resulting propellant is cast into a JANAF dogbone mold preheated at F. The cast propellant is deareated at reduced pressure of about 2.4 mm Hg for 1 hour. The propellant containing mold is sealed in a polyethylene bag containing a drying agent and the propellant is cured at 180F. for 7 days. The cured propellant is cooled to ambient temperature and is cut into 0.25 inch thick dogbone test samples. These dogbones are stored over a drying agent at the testing temperature. These dogbones are tested for mechanical properties employing an Instron Tester at the temperatures set forth in Table 11. Details of the binder composition, the polyfunctional amine employed, and the mechanical properties of the cured propellants are set forth in Table 11. In each example a control propellant was prepared without the addition of polyfunctional amine and was tested for mechanical properties for comparison purposes.
0004 3 333 0004 3 5 03. 55:82am 0 0 92200 M556 000 0 63552.5 0 0 $255 0 c232 02030625 3 0505 E 0 2 5 5m u 5 0505 3 0 0 8 5 00 m 3 0505 0 8 8 5 o 2 2 2 5 W985 056m D2 95 b00503 5255 2: 03 im 000 c um; 2: 33.62 cm B :0 3 0 253 5.5 23 80:: 3 06553 8 mm Q E FSE E M 65253305350050 w 0:050532253205 0* 0 02. 335505 22E 8 259 "$23 RE d 00 0:0 um OR 520 ww 25955 :o mmco Sm A was 50:22 0:509
000 0 2 25 2:362 H h 0 @850 255225 a $35005 2553 a mm 5 35305 zosawcoa 0:. 0mm 5 2 :3 2 Q OR 00 $0.05 525525 n 0205005 25x002 00 mm mm 3:00.55 :SfimEE m0 3 mm 3 4:23:25 0:259
0mm 0mm 03 .1. I. w v 56 2 m 02 0m 22 EDE UEEV v $3.502; 323x32 0 0 in 0 0 E RZ EV 00 2533 20 08m 2:203:08 3x35331065 63am 1255 555552 0N 02 5:22:20: 53 5554 0 8 0 0 08 0 0 05 0 0 0M0 0 0 020 0 0 50 .E 1 11.34 85 0 H 4890 35 5 M Hnmm 5 0 N dawn. 35 0 04,570 35 0 04,090 65 0 13km? E350 00:00:50 553955 2 m f5 0 3! m M A H 0 M N am H am 3 HAMWFH Example 1 illustrates improved tensile strength and employing triethylenetetramine as the polyfunctional elongations for propellant containing triethyleneamine and following the general mixing procedure as tetramine as the polyfunctional amine. Microstructure set forth for Examples l-6. Results of testing are set failure analysis of this propellant shows failure of the forth in Table Ill.
" TABLE 111 w ht Ex. 7 Ex. 8 Ex. Ex. 10 Ex. 11 Ex. 12
erg Propellant composition component percent TE'IAL? Control TEIAL2 TE'IAI'2 Control 'IEIAI'2 'IETAI-2 Control 'IETAI-2 Amine additive 5 0. 0135 0 0. 030 0. 0135 0 0. 030 0. 0135 0 0. 030
Ammonium perchlorate:
Ratio, epoxide/carboxyl (equivalents) Ratio, diepoxide/tn'epoxide (equivalents) 6.5/1 6.5/1 6. 5/1 6. 5/1 6.5/1 6. 5/1 6. 5/1
Mechanical properties 3 (maximum stress) at 170 F.:
Modulus (p.s.i.) 388 348 308 452 533 428 298 398 419 Tensile strength p.s.i.) 65 44 56 67 51 04 43 23 37 Elongation (percent) 40 23 39 34 16 34 53 46 58 Mechanical IIOJeItleS 4 (maximum stress) at 77 F.:
Modulus (p.s.i.) 710 680 450 606 908 620 499 745 568 Tensile strength (p.s.i.) 97 86 82 101 84 93 87 85 86 Elongation (percent) 48 43 47 52 31 43 51 42 Mechanical properties 5 (maximum stress) at F.:
Modulus (p.s.i.) 6, 300 5, 520 5, 780 5, 190 8, 330 6, 643 5, 853 6, 643 6, 680 Tensile strength (p. 387 316 407 349 413 409 437 409 432 Elongation (percent). 48 25 41 10 22 31 22 2G Creep life at 77 F. and 65 p.s.
stress (hrs) 35 20 min. 3.5 48 20 min. 20 24 20min. 13 Mix viscosity (centipoises X10 at 140 F. at the end of propellant mixing) 700 720 816 504 701 672 481 590 639 1 TEIA is triethylenetetramine.
2 All 'IE'IA containing propellants fail in the binder; all control propellants fail at the binder-filler interface.
3 Strain rate of 0.074 in./in./min.
4 Strain rate ol 0.74 in./1n./min. 139 5 Strain rate of 74 in./in./min.
Carboxylated rubber, 8.626; diepoxide, 0.417; triepoxide, 0.064; catalyst, 0.079; hydrocarbon plasticizer, 1.882; ester plasticizer, 1.02.
propellant in the binder phase, i.e., dewetting is sub- Examples 7, 8, 9, l0, ll,and 12 (Table III) illustrate stantially eliminated. Microstructure failure analysis of both improved tensile strengths and elongations from the control propellant at the same test conditions propellant prepared with triethylenetetramine as the showed failure at the binder-filler interface illustrating polyfunctional amine and, in addition, the effect of dewetting. concentration of triethylenetetramine on mechanical Examples 2 and 3 illustrate improved tensile 4 properties and mix viscosity. At 0.0135 percent constrengths, elongations, and improved creep properties nt a (Ex mpl and 1 the tensile r g compared to the control rounds. Propellants of Examand elongation of the propellant is significantly better ples 2 and 3 employ triethylenetetramine as the polythan at the 0.030 percent concentration level (Examfunctional amine and fail in the binder phase when subples 8, l0, and 12) and resistance to creep failure is imjected to high stress. The control propellants dewet i.e., 45 proved markedly. Also at the 0.0135 percent concenfail at the binder-filler interface as determined by mitration level the mix viscosity is reduced significantly crostructure analysis when subjected to the same test. (Examples 9 and l 1). At the 0.030 percent concentra- Examples 4 and 5 illustrate improved elongation and tion level the mix viscosity is increased about 13 pertensile strengths of propellant compositions of this incent (Example 8) and about 8 percent (Example 12). vention over the control propellants when employing The addition of 0.0135 percent triethylenetetramine in tetraethylenepentamine and polyethyleneimine as the Example 9 reduced the mix viscosity 28 percent compolyfunctional amine. The control propellants of Expared to the control sample and gave a propellant that amples 4 and 5 dewet at the binder-filler interface as appeared to have infinite creep life at 65 psi. determined by microstructure analysis when subjected to the same testing conditions.
Example 6 illustrates the importance of concentra- E l 13-18 tion of the polyfunctional amine in achieving improvement in mechanical properties. ,When the percentage 7 of triethylenetetramine is increased to 0.06 percent by Six additional propellant compositions are prepared weight, inferior mechanical properties result. employing fl-(4- i h 1) thylamine (APE) a the polyfunctional amine following the general mixing procedure set forth for Examples 16. Propellant composi- Six additional propellant compositions are prepared tions and results of testing are set forth in Table IV.
Examples 71 2 Ex. 15 Ex. 16 Ex. 18 Ex. 17 APE L2 Control APE L2 Control APE APE Control TABLE IV Ex. 14 Control APE L? Weight percent Propellant composition component Example 13 illustrates that at the 0.002 percent concentration level, APE has very little effect on mechanical properties or microstructural failure mode. This propellant and its control both fail at the binder-filler 5 interface. However, at this low amine level the mix viscosity is reduced about 18 percent.
Examples 14 through 18 illustrate that at APE levels between 0.0113 and 0.060 percent, failure occurs exclusively in the binder phase whereas the corresponding control propellants fail at the binder-filler interface (dewetting). At these levels, resistance to creep failure is markedly improved.
Examples 14 and I5 illustrate that the upper limit of usefulness of APE appears to be about 0.060 percent 15 in a diepoxide crosslinked carboxy-terminated rubber binder. At this concentration level (Example 15) the creep life is extended from minutes (control) to 5.5 hours. At the 0.040 percent concentration level of Example 14, the propellant appears to have infinite creep 20 life as evidenced by the fact that after 48 hours the rate of change of elongation with time is zero. The improvement in tensile strength and elongation is considerably greater at the lower (0.040 percent) APE concentration level. The mix viscosity is decreased significantly atboth levels.
Example 16' illustrates that infinite creep life is obtained at APE concentration levels as low as 0.0113
percent.
Examples 17 and 18 illustrate that at an epoxide to carboxyl ratio of 1.08/10, somewhat better mechanical properties are obtained with APE concentration levels of 0.01 13 percent (Example 17) than at 0.020 percent (Example 18). in both cases the resulting propellants appear to have infinite creep life.
All of the control propellants for Examples 1 through 18 fail the creep test at 77F and 65 psi in less than 20 minutes. Conversely, the propellant compositions of this invention can be tailored to have a very long creep life as exemplified in Examples 9, l4, l6, l7 and 18.
The propellant compositions of this invention prepared in Examples l-l 8 showed no porosity. While ammonia gas is liberated during mixing of the compositions, the amount of ammonia gas liberated is so small due to the small quantities of polyfunctional amine employed that substantially no porosity results.
The propellant compositions of this invention have the following general compositions:
570/150 F. 430ll57 F.
1 04 1 00 0 5 1 0 5 1 367 378 526 66 5s 83 29 20 21 3 588 540 S6 98 110 31 a0 26 7, 280 7,080 8, 000 10, 100 595 056 500 31 3s 15 4s 5 .5 20 min. sea 135 F. 528/140 F. 720/140 F. e o 141 F. Lo) 0 7, 400 507 405 17 17 7 min.
21 min.
J A Jr 0 Component Weight Oxygen Containing Ammonium Salt -90 Cured Binder 520 Polyfunctional Organic Amine 0.0050.05 Metal Fuel 0-20 I I I l I I Preferably, the propellant composition contains by weight from about to about percent oxidizer and from about 5 to about 20 percent cured binder. The cured binder includes the binder prepolymer and crosslinking agent. A curing catalyst is employed as needed. From about 40 to about weight percent of the cured binder in the formulation is binder prepolymer, from about 1 to about 10 weightpercent is the crosslinking agent, and the binder plasticizer can be from about 0 to about 50 weight percent, and preferably is from about 20 to about 40 weight percent of the binder.
The composite propellant of this invention can also contain other additives such as metal fuels, plasticizers, and the various compounding ingredients commonly employed in making composite propellants, as for exes 4 (m'aximuni'rii'iiiii ii Ex. 14-18 fail in the binder phase; the APE containing propellant of Ex. 13 and all control propellants fail at the binder-filler interface. or
LII
Elongation (percent) Creep life at 77 F. and 65 p.s.i. (initial stress) (hrs.)
1 APE is fi-(4-aminophenyl)cthylamin0.
2 The APE containing propellants in 3 Strain Rate 01' 0.074 in./in./min.
4 Strain Rate of 0.74 in./in./min.
5 Strain Rate of 74 in./in./min.
'Carboxyloted rubber, 7.727; diepoxide, 0.301; Triepoxide, 0.060; catalyst, 0.0108; hydrocarbon plasticizer, 1.906; ester plasticizer, 1.00. O\
Mix viscosity (centipoisesXlO at F. at the 0nd of propellant 1nixing) ample, oxidation inhibitors, reinforcing agents, wetting agents, surfactants, ballistic modifiers, radar attenuators, and the like. In this connection, metal fuels such as powdered aluminum, beryllium, magnesium, zirconium or boron, alloys such as the aluminum alloys of boron, magnesium, manganese, copper, and the like, and plasticizers such as dioctyl phthalate, dicotyl azelate, dioctyl adipate, dodecyl adipate, polybutadiene, polyisobutylene, and the like can be utilized. Surfactants such as lecithin or mixtures of sorbitan monooleate and polyoxyethylene esters of mixed fatty and resin acids; ballistic modifiers such as di-n-butyl ferrocene, iron oxide, chromium oxide or oxamide, and radar attenuators such as molybdenum trioxide, can also be present in minor amounts in the propellant composition of this invention.
What I claim and desire to protect by Letters Patent l. A composite propellant composition comprising in the form of a cured admixture:
a. an oxidizer consisting essentially of an oxygen containing ammonium salt selected from the group consisting of ammonium perchlorate, ammonium nitrate, hydrazine perchlorate, hydrazine diperchlorate, and mixtures thereof,
b. a crosslinkable binder prepolymer having reactive functional groups selected from the group consisting of hydroxyl, carboxyl and isocyanate groups and a crosslinking agent therefore said crosslinking agent having reactive functional groups selected from the groups consisting of polyepoxides, polyisocyanates, polythioisocyanates, and polyimines,
c. a polyfunctional amine selected from the polyethyleneimine and amines having the general formula l l. HZN x NHR where X is either a) (CH ),,,Ar or said propellant composition comprising by weight from about 60 to about percent of said oxygen containing ammonium salts, from about 5 to about 20 percent of crosslinkable binder prepolymer and crosslinking agent and from about 0.005 to about 0.05 percent of polyfunctional amine.
2. The composite propellant composition of claim 1 in which the polyfunctional amine is of the general formula (I) wherein X is (NHRI): l l
wherein z is O, l, 2, 3 or 4, and R is hydrogen or lower alkyl having from one to four carbon atoms and R is hydrogen.
3. The propellant composition of claim 1 wherein the polyfunctional amine is triethylenetetramine.
4. The propellant composition of claim 1 wherein the polyfunctional amine is tetraethylenepentamine.
5. The propellant composition of claim 1 wherein the polyfunctional amine is diethylenetriamine.
6. The propellant composition of claim 1 wherein the polyfunctional amine is polyethyleneimine.
7. The propellant composition of claim 1 wherein the polyfunctional amine is B-(4-aminophenyl) ethylam- 8. The composite propellant composition of claim 1 wherein the oxygen containing ammonium salt is ammonium perchlorate, the crosslinkable binder prepolymer is a carboxyl terminated prepolymer, and the crosslinking agent is a mixture of diepoxides and trie poxides.
9. The composite propellant composition of claim 8 wherein the polyfunctional amine is B-(4- aminophenyl) ethylamine.
10. The composite propellant composition of claim 1 wherein the oxygen containing ammonium salt is ammonium perchlorate, the crosslinkable binder prepolymer is a hydroxyl terminated prepolymer, and the crosslinking agent is a polyisocyanate.
11. The composite propellant composition of claim 1 wherein the oxygen containing ammonium salt is ammonium perchlorate, the crosslinkable binder prepolymer is a carboxyl terminated prepolymer, and the crosslinking agent is a polyimine.
Po-ww v UNITED STATES PATENT OFFICE (5/69) CERTIFICATE @F 'CURRECTIGN V Patent No. 3l79ol4l6 Dated February 5; 1974 Inventofla) Henry C- Dehm It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
F a W Column 9 & l0 Table II;
Under Example 5, left hand column labled PEI the Modulas (p.s.i.) determined at 170 F should read 419, not 41.9 and,
The Elongation (percent) determined at 77F should read 36, not 96.
Signed and v sealed this 16th day of July 1974 I L) a .1 a j 2 Attest:
MCCOY M. GIBSON, JR. 0. MARSHALL DANN Attesting Officer Commissioner of Patents Po-ww v UNITED STATES PATENT OFFICE CERTIFICAT F CQECTIN Patent No 317901416 Dated February 5, Inventor) Henry C. Dehm It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
F a W Column 9 & l0 Table II;
Under Example 5, left hand column labled PEI the Modulas (p.s.i.) determined at 170 F should read 419, not 41.9 and,
The Elongation (percent) determined at 77F should read 36, not 96.
Signed and v sealed this 16th day of July 1974 I L) a .1 a j 2 Attest:
MCCOY M. GIBSON, JR. 0. MARSHALL DANN Attesting Officer Commissioner of Patents mg a UNITED STATES PATENT OFFICE t CERTIFICATE OF CORRECTION Patent No. 416 Dated r ary 5, 1974 Henr C. Dehm Inventor-(s) y It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:
Column 9 & l0 Table II;
Under Example 5, left hand column labled PEI the Modulas (p.s.i.) determined at 170 F should read 419, not 41.9 and,
The Elongation (percent) determined at 77F should read 36, not 96. I
Signed andhsealed this 16th day of July l974.'
- 1 I I j a a Attest: 1 1
MCCOY M. GIBSON, JR. C. MARSHALL DANN Attesting Officer I V i Commissioner of Patents
Claims (10)
- 2. The composite propellant composition of claim 1 in which the polyfunctional amine is of the general formula (I) wherein X is
- 3. The propellant composition of claim 1 wherein the polyfunctional amine is triethylenetetramine.
- 4. The propellant composition of claim 1 wherein the polyfunctional amine is tetraethylenepentamine.
- 5. The propellant composition of claim 1 wherein the polyfunctional amine is diethylenetriamine.
- 6. The propellant composition of claim 1 wherein the polyfunctional amine is polyethyleneimine.
- 7. The propellant composition of claim 1 wherein the polyfunctional amine is Beta -(4-aminophenyl) ethylamine.
- 8. The composite propellant composition of claim 1 wherein the oxygen containing ammonium salt is ammonium perchlorate, the crosslinkable binder prepolymer is a carboxyl terminated prepolymer, and the crosslinking agent is a mixture of diepoxides and triepoxides.
- 9. The composite propellant composition of claim 8 wherein the polyfunctional amine is Beta -(4-aminophenyl) ethylamine.
- 10. The composite propellant composition of claim 1 wherein the oxygen containing ammonium salt is ammonium perchlorate, the crosslinkable binder prepolymer is a hydroxyl terminated prepolymer, and the crosslinking agent is a polyisocyanate.
- 11. The composite propellant composition of claim 1 wherein the oxygen containing ammonium salt is ammonium perchlorate, the crosslinkable binder prepolymer is a carboxyl terminated prepolymer, and the crosslinking agent is a polyimine.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US8751370A | 1970-07-22 | 1970-07-22 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3790416A true US3790416A (en) | 1974-02-05 |
Family
ID=22205639
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00087513A Expired - Lifetime US3790416A (en) | 1970-07-22 | 1970-07-22 | Composite propellant including (u) polyfunctional amine |
Country Status (1)
Country | Link |
---|---|
US (1) | US3790416A (en) |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3898111A (en) * | 1968-11-26 | 1975-08-05 | Us Air Force | Quinone inhibitors in organometallic polyurethane propellant compositions |
US4065332A (en) * | 1972-12-19 | 1977-12-27 | Societe Nationale Des Poudres Et Explosifs | Hybrid propellant compositions |
US4120709A (en) * | 1973-04-25 | 1978-10-17 | Thiokol Corporation | Technique for improving processibility of certain composite propellants by calcining the iron oxide burning rate catalyst |
US4158583A (en) * | 1977-12-16 | 1979-06-19 | Nasa | High performance ammonium nitrate propellant |
US4214928A (en) * | 1976-11-29 | 1980-07-29 | The United States Of America As Represented By The Secretary Of The Navy | Dimethyl hydantoin bonding agents in solid propellants |
US4478656A (en) * | 1973-11-14 | 1984-10-23 | Hercules Incorporated | Urethane compounds and CMDB propellants stabilized therewith |
FR2587329A1 (en) * | 1985-09-19 | 1987-03-20 | Poudres & Explosifs Ste Nale | BINDER-LOADING ADHESION AGENT AND PROPULSIVE COMPOSITION CONTAINING THE SAME |
US4670068A (en) * | 1981-02-19 | 1987-06-02 | Hercules Incorporated | Polyfunctional isocyanate crosslinking agents for propellant binders |
US5401341A (en) * | 1993-04-14 | 1995-03-28 | The Lubrizol Corporation | Cross-linked emulsion explosive composition |
US5414123A (en) * | 1992-09-11 | 1995-05-09 | Thiokol Corporation | Polyether compounds having both imine and hydroxyl functionality and methods of synthesis |
US5472532A (en) * | 1993-06-14 | 1995-12-05 | Thiokol Corporation | Ambient temperature mix, cast, and cure composite propellant formulations |
US5847315A (en) * | 1996-11-29 | 1998-12-08 | Ecotech | Solid solution vehicle airbag clean gas generator propellant |
US9181140B1 (en) | 1992-09-16 | 2015-11-10 | Orbital Atk, Inc. | Solid propellant bonding agents and methods for their use |
US20230093642A1 (en) * | 2021-08-23 | 2023-03-23 | Northrop Grumman Systems Corporation | Methods of passivating fuel materials for use in solid propellants, and related solid fuels, ramjet engines, and methods |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3305523A (en) * | 1962-08-30 | 1967-02-21 | North American Aviation Inc | Modification of telechelic-type polymers |
US3454436A (en) * | 1962-07-02 | 1969-07-08 | Monsanto Res Corp | Poly - beta - hydroxyamines propellant compositions prepared with lithium perchlorate |
US3476622A (en) * | 1966-12-20 | 1969-11-04 | Asahi Chemical Ind | Carboxy-terminated composite rocket propellant and process for producing using an amide additive |
US3529042A (en) * | 1959-10-22 | 1970-09-15 | Phillips Petroleum Co | Method for manufacturing cast solid polyurethane propellants |
US3586552A (en) * | 1968-05-23 | 1971-06-22 | Union Carbide Corp | Propellant composition having a curable ethylene interpolymer binder |
-
1970
- 1970-07-22 US US00087513A patent/US3790416A/en not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3529042A (en) * | 1959-10-22 | 1970-09-15 | Phillips Petroleum Co | Method for manufacturing cast solid polyurethane propellants |
US3454436A (en) * | 1962-07-02 | 1969-07-08 | Monsanto Res Corp | Poly - beta - hydroxyamines propellant compositions prepared with lithium perchlorate |
US3305523A (en) * | 1962-08-30 | 1967-02-21 | North American Aviation Inc | Modification of telechelic-type polymers |
US3476622A (en) * | 1966-12-20 | 1969-11-04 | Asahi Chemical Ind | Carboxy-terminated composite rocket propellant and process for producing using an amide additive |
US3586552A (en) * | 1968-05-23 | 1971-06-22 | Union Carbide Corp | Propellant composition having a curable ethylene interpolymer binder |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3898111A (en) * | 1968-11-26 | 1975-08-05 | Us Air Force | Quinone inhibitors in organometallic polyurethane propellant compositions |
US4065332A (en) * | 1972-12-19 | 1977-12-27 | Societe Nationale Des Poudres Et Explosifs | Hybrid propellant compositions |
US4120709A (en) * | 1973-04-25 | 1978-10-17 | Thiokol Corporation | Technique for improving processibility of certain composite propellants by calcining the iron oxide burning rate catalyst |
US4478656A (en) * | 1973-11-14 | 1984-10-23 | Hercules Incorporated | Urethane compounds and CMDB propellants stabilized therewith |
US4214928A (en) * | 1976-11-29 | 1980-07-29 | The United States Of America As Represented By The Secretary Of The Navy | Dimethyl hydantoin bonding agents in solid propellants |
US4158583A (en) * | 1977-12-16 | 1979-06-19 | Nasa | High performance ammonium nitrate propellant |
US4670068A (en) * | 1981-02-19 | 1987-06-02 | Hercules Incorporated | Polyfunctional isocyanate crosslinking agents for propellant binders |
EP0218511A1 (en) * | 1985-09-19 | 1987-04-15 | Societe Nationale Des Poudres Et Explosifs | Binder-charge bonding agent and propellant composition containing it |
FR2587329A1 (en) * | 1985-09-19 | 1987-03-20 | Poudres & Explosifs Ste Nale | BINDER-LOADING ADHESION AGENT AND PROPULSIVE COMPOSITION CONTAINING THE SAME |
US4747891A (en) * | 1985-09-19 | 1988-05-31 | Societe Nationale Des Poudres Et Explosifs | Solid propellant containing an aziridinyl bonding agent |
US5414123A (en) * | 1992-09-11 | 1995-05-09 | Thiokol Corporation | Polyether compounds having both imine and hydroxyl functionality and methods of synthesis |
US9181140B1 (en) | 1992-09-16 | 2015-11-10 | Orbital Atk, Inc. | Solid propellant bonding agents and methods for their use |
US5401341A (en) * | 1993-04-14 | 1995-03-28 | The Lubrizol Corporation | Cross-linked emulsion explosive composition |
US5472532A (en) * | 1993-06-14 | 1995-12-05 | Thiokol Corporation | Ambient temperature mix, cast, and cure composite propellant formulations |
US5847315A (en) * | 1996-11-29 | 1998-12-08 | Ecotech | Solid solution vehicle airbag clean gas generator propellant |
US20230093642A1 (en) * | 2021-08-23 | 2023-03-23 | Northrop Grumman Systems Corporation | Methods of passivating fuel materials for use in solid propellants, and related solid fuels, ramjet engines, and methods |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3790416A (en) | Composite propellant including (u) polyfunctional amine | |
US3948698A (en) | Solid propellant compositions having epoxy cured, carboxy-terminated rubber binder | |
US3476622A (en) | Carboxy-terminated composite rocket propellant and process for producing using an amide additive | |
US3909322A (en) | Solid gas generating and gun propellant compositions containing a nitroaminotetrazole salt | |
CN107867961B (en) | Method for improving mechanical property of butylated hydroxytoluene propellant and butylated hydroxytoluene propellant prepared by same | |
US3734789A (en) | Gas generating solid propellant containing 5-aminotetrazole nitrate | |
US3609115A (en) | Propellant binder | |
US3793099A (en) | Solid propellant with polyurethane binder | |
CN109467495B (en) | Solid propellant with polyether-butyl hydroxyl block polymer as adhesive | |
US4337103A (en) | Composite propellant with differentially cured area at initial burn surface | |
US3984265A (en) | Composite propellants having improved resistance to thermal oxidation | |
US3986906A (en) | Ultrahigh burning rate propellants containing an organic perchlorate oxidizer | |
US3792003A (en) | Hydroxy-terminated polybutadiene,diisocyanate and triol composition | |
US3982975A (en) | Propellants having improved resistance to oxidative hardening | |
US4241661A (en) | Composite propellant with surface having improved strain capacity | |
US3454436A (en) | Poly - beta - hydroxyamines propellant compositions prepared with lithium perchlorate | |
US3177101A (en) | Carboxyl-terminated linear polyester gas-generating composition and method of preparaion | |
US3748199A (en) | Composite propellants containing hydroxylammonium perchlorate | |
US4412875A (en) | Nitramine composite propellant compostion | |
US4416710A (en) | Polynorbornene-based combustible compositions and processes for the fabrication thereof | |
US3804683A (en) | High energy, low burning rate solid propellant compositions based on acrylic prepolymer binders | |
US3745074A (en) | Composite solid propellant with additive to improve the mechanical properties thereof | |
US3762972A (en) | Reaction product of phosphine oxide with carboxylic acids | |
KR101101218B1 (en) | Gap/nitramine-based energetic propellant composition having excellent mechanical properties | |
KR101974125B1 (en) | Solid propellant composition and manufacturing method thereof |