US3027284A - Composite propellants containing a - Google Patents
Composite propellants containing a Download PDFInfo
- Publication number
- US3027284A US3027284A US3027284DA US3027284A US 3027284 A US3027284 A US 3027284A US 3027284D A US3027284D A US 3027284DA US 3027284 A US3027284 A US 3027284A
- Authority
- US
- United States
- Prior art keywords
- weight
- parts
- burning rate
- group
- molybdate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000003380 propellant Substances 0.000 title description 106
- 239000002131 composite material Substances 0.000 title description 14
- 239000000203 mixture Substances 0.000 claims description 120
- 239000007800 oxidant agent Substances 0.000 claims description 58
- 239000011230 binding agent Substances 0.000 claims description 54
- 239000003795 chemical substances by application Substances 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 38
- 230000000881 depressing Effects 0.000 claims description 34
- HHEFNVCDPLQQTP-UHFFFAOYSA-N Ammonium perchlorate Chemical compound [NH4+].[O-]Cl(=O)(=O)=O HHEFNVCDPLQQTP-UHFFFAOYSA-N 0.000 claims description 30
- 239000004449 solid propellant Substances 0.000 claims description 30
- 150000003839 salts Chemical class 0.000 claims description 18
- 239000011780 sodium chloride Substances 0.000 claims description 18
- VLTRZXGMWDSKGL-UHFFFAOYSA-M Perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 16
- DVARTQFDIMZBAA-UHFFFAOYSA-O Ammonium nitrate Chemical compound [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 claims description 14
- 240000008528 Hevea brasiliensis Species 0.000 claims description 12
- 229910001485 alkali metal perchlorate Inorganic materials 0.000 claims description 12
- 229920001194 natural rubber Polymers 0.000 claims description 12
- 230000001590 oxidative Effects 0.000 claims description 12
- 229910001963 alkali metal nitrate Inorganic materials 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims 2
- 229920001971 elastomer Polymers 0.000 description 54
- 239000002585 base Substances 0.000 description 46
- 229920001577 copolymer Polymers 0.000 description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 239000005060 rubber Substances 0.000 description 30
- 150000001993 dienes Chemical class 0.000 description 28
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 26
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 24
- 239000004615 ingredient Substances 0.000 description 20
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 18
- 125000000623 heterocyclic group Chemical group 0.000 description 18
- 125000004432 carbon atoms Chemical group C* 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 125000000217 alkyl group Chemical group 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- -1 i.e. Substances 0.000 description 12
- RRHGJUQNOFWUDK-UHFFFAOYSA-N isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000006229 carbon black Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 239000004014 plasticizer Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 description 10
- VJOWMORERYNYON-UHFFFAOYSA-N 5-ethenyl-2-methylpyridine Chemical compound CC1=CC=C(C=C)C=N1 VJOWMORERYNYON-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000994 depressed Effects 0.000 description 8
- 238000007720 emulsion polymerization reaction Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-Vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 6
- TVFDJXOCXUVLDH-UHFFFAOYSA-N Cesium Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 6
- 241001441571 Hiodontidae Species 0.000 description 6
- VLAPMBHFAWRUQP-UHFFFAOYSA-L Molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 6
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- 230000000111 anti-oxidant Effects 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 229910052792 caesium Inorganic materials 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 230000003247 decreasing Effects 0.000 description 6
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000003801 milling Methods 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 150000003222 pyridines Chemical class 0.000 description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 6
- 230000003014 reinforcing Effects 0.000 description 6
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 6
- 229910052701 rubidium Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- 239000004594 Masterbatch (MB) Substances 0.000 description 4
- WCYWZMWISLQXQU-UHFFFAOYSA-N Methyl radical Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 4
- 239000000020 Nitrocellulose Substances 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N Silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 150000001450 anions Chemical group 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N carbon bisulphide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000006011 modification reaction Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920001220 nitrocellulos Polymers 0.000 description 4
- 239000006069 physical mixture Substances 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 150000003248 quinolines Chemical class 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 239000000080 wetting agent Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- JDUQPSINXKBHEN-UHFFFAOYSA-N (3-ethenylisoquinolin-6-yl)methanol Chemical compound C1=NC(C=C)=CC2=CC(CO)=CC=C21 JDUQPSINXKBHEN-UHFFFAOYSA-N 0.000 description 2
- SNIOPGDIGTZGOP-UHFFFAOYSA-N 1,2,3-propanetrioltrinitrate Chemical compound [O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O SNIOPGDIGTZGOP-UHFFFAOYSA-N 0.000 description 2
- WVICRWJHVDRYSU-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;methyl prop-2-enoate Chemical compound COC(=O)C=C.C=CC1=CC=CC=C1C=C WVICRWJHVDRYSU-UHFFFAOYSA-N 0.000 description 2
- BUSCTLHHPMLZMS-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;prop-2-enoic acid;styrene Chemical compound OC(=O)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C BUSCTLHHPMLZMS-UHFFFAOYSA-N 0.000 description 2
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N 1,3-Diaminopropane Chemical group NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- DKWHHTWSTXZKDW-UHFFFAOYSA-N 1-[2-[2-[2-(2-butoxyethoxy)ethoxymethoxy]ethoxy]ethoxy]butane Chemical compound CCCCOCCOCCOCOCCOCCOCCCC DKWHHTWSTXZKDW-UHFFFAOYSA-N 0.000 description 2
- JLPULHDHAOZNQI-ZTIMHPMXSA-N 1-hexadecanoyl-2-(9Z,12Z-octadecadienoyl)-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCCCCCC\C=C/C\C=C/CCCCC JLPULHDHAOZNQI-ZTIMHPMXSA-N 0.000 description 2
- MUEHGEQAMLEEID-UHFFFAOYSA-N 1-pentyl-2-phenylbenzene Chemical group CCCCCC1=CC=CC=C1C1=CC=CC=C1 MUEHGEQAMLEEID-UHFFFAOYSA-N 0.000 description 2
- FSECWGZNMLROOX-UHFFFAOYSA-N 2,3-dimethylhexa-1,3-diene Chemical compound CCC=C(C)C(C)=C FSECWGZNMLROOX-UHFFFAOYSA-N 0.000 description 2
- SPSSULHKWOKEEL-UHFFFAOYSA-N 2,4,6-trinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O SPSSULHKWOKEEL-UHFFFAOYSA-N 0.000 description 2
- JJVHEIJBQGMBKG-UHFFFAOYSA-N 2-ethenyl-3,4,5,6-tetramethylpyridine Chemical compound CC1=NC(C=C)=C(C)C(C)=C1C JJVHEIJBQGMBKG-UHFFFAOYSA-N 0.000 description 2
- TUPJXKPXLGTGTO-UHFFFAOYSA-N 2-ethenyl-4-ethylquinoline Chemical compound C1=CC=C2C(CC)=CC(C=C)=NC2=C1 TUPJXKPXLGTGTO-UHFFFAOYSA-N 0.000 description 2
- FDAQFOWVXWLSBY-UHFFFAOYSA-N 2-ethenyl-5-ethyl-3-methylpyridine Chemical compound CCC1=CN=C(C=C)C(C)=C1 FDAQFOWVXWLSBY-UHFFFAOYSA-N 0.000 description 2
- YQUDMNIUBTXLSX-UHFFFAOYSA-N 2-ethenyl-5-ethylpyridine Chemical compound CCC1=CC=C(C=C)N=C1 YQUDMNIUBTXLSX-UHFFFAOYSA-N 0.000 description 2
- KQKFXQBWFUHZRY-UHFFFAOYSA-N 2-ethenyl-5-methyl-4-phenoxypyridine Chemical compound CC1=CN=C(C=C)C=C1OC1=CC=CC=C1 KQKFXQBWFUHZRY-UHFFFAOYSA-N 0.000 description 2
- ASKLBJFSWQWZFU-UHFFFAOYSA-N 2-ethenyl-6-ethoxy-7-methylquinoline Chemical compound C1=C(C=C)N=C2C=C(C)C(OCC)=CC2=C1 ASKLBJFSWQWZFU-UHFFFAOYSA-N 0.000 description 2
- XUGNJOCQALIQFG-UHFFFAOYSA-N 2-ethenylquinoline Chemical compound C1=CC=CC2=NC(C=C)=CC=C21 XUGNJOCQALIQFG-UHFFFAOYSA-N 0.000 description 2
- ZSMOKNZAUSNOIG-UHFFFAOYSA-N 2-ethoxy-3-ethylhexa-1,3-diene Chemical compound CCOC(=C)C(CC)=CCC ZSMOKNZAUSNOIG-UHFFFAOYSA-N 0.000 description 2
- JFBZAUXCIFXDGO-UHFFFAOYSA-N 2-methoxy-3-methylidenepent-1-ene Chemical compound CCC(=C)C(=C)OC JFBZAUXCIFXDGO-UHFFFAOYSA-N 0.000 description 2
- LEKIODFWYFCUER-UHFFFAOYSA-N 2-methylidenebut-3-enenitrile Chemical compound C=CC(=C)C#N LEKIODFWYFCUER-UHFFFAOYSA-N 0.000 description 2
- YYDOEOGYWXPPHM-UHFFFAOYSA-N 3-ethenyl-1,6-dimethylisoquinoline Chemical compound CC1=NC(C=C)=CC2=CC(C)=CC=C21 YYDOEOGYWXPPHM-UHFFFAOYSA-N 0.000 description 2
- ISRUHSKWYGWJIX-UHFFFAOYSA-N 3-ethenyl-2,4-dimethyl-5,6-dipentylpyridine Chemical compound CCCCCC1=NC(C)=C(C=C)C(C)=C1CCCCC ISRUHSKWYGWJIX-UHFFFAOYSA-N 0.000 description 2
- IIBPRBOWHWXNCE-UHFFFAOYSA-N 3-ethenyl-2-methyl-5-undecylpyridine Chemical compound CCCCCCCCCCCC1=CN=C(C)C(C=C)=C1 IIBPRBOWHWXNCE-UHFFFAOYSA-N 0.000 description 2
- HXBBCCUEPJTHGZ-UHFFFAOYSA-N 3-ethenyl-4-methyl-2-(4-methylphenyl)pyridine Chemical compound C1=CC(C)=CC=C1C1=NC=CC(C)=C1C=C HXBBCCUEPJTHGZ-UHFFFAOYSA-N 0.000 description 2
- JDAPKVYHFNRFKO-UHFFFAOYSA-N 3-ethenyl-5-phenylpyridine Chemical compound C=CC1=CN=CC(C=2C=CC=CC=2)=C1 JDAPKVYHFNRFKO-UHFFFAOYSA-N 0.000 description 2
- XNNLTDRWOHXVDY-UHFFFAOYSA-N 3-ethenyl-6,7-dipropylquinoline Chemical compound C=CC1=CN=C2C=C(CCC)C(CCC)=CC2=C1 XNNLTDRWOHXVDY-UHFFFAOYSA-N 0.000 description 2
- OJFXABGGUBLZIP-UHFFFAOYSA-N 3-ethenylisoquinoline Chemical compound C1=CC=C2C=NC(C=C)=CC2=C1 OJFXABGGUBLZIP-UHFFFAOYSA-N 0.000 description 2
- UXKQNCDDHDBAPD-UHFFFAOYSA-N 4-N,4-N-diphenylbenzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 UXKQNCDDHDBAPD-UHFFFAOYSA-N 0.000 description 2
- VYIYXBONKWPJSH-UHFFFAOYSA-N 4-benzyl-2-ethenylquinoline Chemical compound C=12C=CC=CC2=NC(C=C)=CC=1CC1=CC=CC=C1 VYIYXBONKWPJSH-UHFFFAOYSA-N 0.000 description 2
- HQPQBUQHYITQAL-UHFFFAOYSA-N 4-chloro-2-ethenyl-6-methoxypyridine Chemical compound COC1=CC(Cl)=CC(C=C)=N1 HQPQBUQHYITQAL-UHFFFAOYSA-N 0.000 description 2
- ZVBVBFGGZJJWHR-UHFFFAOYSA-N 4-ethenyl-2,6-diethylpyridine Chemical compound CCC1=CC(C=C)=CC(CC)=N1 ZVBVBFGGZJJWHR-UHFFFAOYSA-N 0.000 description 2
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 2
- XXNVITSQTYKSLR-UHFFFAOYSA-N 5,6-dichloro-3-ethenylisoquinoline Chemical compound C1=NC(C=C)=CC2=C(Cl)C(Cl)=CC=C21 XXNVITSQTYKSLR-UHFFFAOYSA-N 0.000 description 2
- HLLGUKLXALMPHQ-UHFFFAOYSA-N 5-(2-chloroethyl)-3-ethenylquinoline Chemical compound C1=C(C=C)C=C2C(CCCl)=CC=CC2=N1 HLLGUKLXALMPHQ-UHFFFAOYSA-N 0.000 description 2
- NTFOOQDZAMZVJD-UHFFFAOYSA-N 5-ethenyl-4-nonyl-2-propan-2-ylpyridine Chemical compound CCCCCCCCCC1=CC(C(C)C)=NC=C1C=C NTFOOQDZAMZVJD-UHFFFAOYSA-N 0.000 description 2
- 239000004451 Ballistite Substances 0.000 description 2
- 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 2
- ASKJTFVYQYERBD-UHFFFAOYSA-N C(=C)C1=C(C=CC=C1)C=C.C(C=C)(=O)O.C(C=C)(=O)OC Chemical compound C(=C)C1=C(C=CC=C1)C=C.C(C=C)(=O)O.C(C=C)(=O)OC ASKJTFVYQYERBD-UHFFFAOYSA-N 0.000 description 2
- VNTXUFLTYYQIPQ-UHFFFAOYSA-N C(=C)C1=NC=C(C(=C1)Cl)Cl Chemical compound C(=C)C1=NC=C(C(=C1)Cl)Cl VNTXUFLTYYQIPQ-UHFFFAOYSA-N 0.000 description 2
- COFLMCKZBAAZIM-UHFFFAOYSA-N CC1=NC(=CC(=C1)CCCCCCCCC)C=C Chemical compound CC1=NC(=CC(=C1)CCCCCCCCC)C=C COFLMCKZBAAZIM-UHFFFAOYSA-N 0.000 description 2
- DMUUJYGMAZCEJE-UHFFFAOYSA-N CC=CC1=NC=CC(=C1C)C Chemical compound CC=CC1=NC=CC(=C1C)C DMUUJYGMAZCEJE-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M Dioctyl sodium sulfosuccinate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- 210000002370 ICC Anatomy 0.000 description 2
- 229920000126 Latex Polymers 0.000 description 2
- 229940067606 Lecithin Drugs 0.000 description 2
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 2
- 229940098424 POTASSIUM PYROPHOSPHATE Drugs 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M Rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 2
- 241001168730 Simo Species 0.000 description 2
- PDIOKWSXIIMYCJ-UHFFFAOYSA-I [O-]O.[O-]P([O-])(=O)OP(=O)([O-])[O-].[Fe+5] Chemical compound [O-]O.[O-]P([O-])(=O)OP(=O)([O-])[O-].[Fe+5] PDIOKWSXIIMYCJ-UHFFFAOYSA-I 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- DKVNPHBNOWQYFE-UHFFFAOYSA-M carbamodithioate Chemical compound NC([S-])=S DKVNPHBNOWQYFE-UHFFFAOYSA-M 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000005712 crystallization Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000004659 dithiocarbamates Chemical class 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical group CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N edta Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229960003711 glyceryl trinitrate Drugs 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000005842 heteroatoms Chemical group 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000005027 hydroxyaryl group Chemical group 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 150000002537 isoquinolines Chemical class 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 235000010445 lecithin Nutrition 0.000 description 2
- 239000000787 lecithin Substances 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 239000005078 molybdenum compound Substances 0.000 description 2
- 150000002752 molybdenum compounds Chemical class 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- QUPCNWFFTANZPX-UHFFFAOYSA-M paramenthane hydroperoxide Chemical compound [O-]O.CC(C)C1CCC(C)CC1 QUPCNWFFTANZPX-UHFFFAOYSA-M 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- TVPFLPJBESCUKI-UHFFFAOYSA-M potassium;N,N-dimethylcarbamodithioate Chemical compound [K+].CN(C)C([S-])=S TVPFLPJBESCUKI-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000008036 rubber plasticizer Substances 0.000 description 2
- 239000008549 simo Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- RTVVXRKGQRRXFJ-UHFFFAOYSA-N sodium;2-sulfobutanedioic acid Chemical compound [Na].OC(=O)CC(C(O)=O)S(O)(=O)=O RTVVXRKGQRRXFJ-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000010059 sulfur vulcanization Methods 0.000 description 2
- RZRJACCZWZTYJY-UHFFFAOYSA-N tert-butylsulfanyl N,N-dimethylcarbamodithioate Chemical compound CN(C)C(=S)SSC(C)(C)C RZRJACCZWZTYJY-UHFFFAOYSA-N 0.000 description 2
- AUMOSEQHACNXEW-UHFFFAOYSA-J tetrapotassium;[2-[bis[[hydroxy(oxido)phosphoryl]methyl]amino]ethyl-[[hydroxy(oxido)phosphoryl]methyl]amino]methyl-hydroxyphosphinate Chemical compound [K+].[K+].[K+].[K+].OP([O-])(=O)CN(CP(O)([O-])=O)CCN(CP(O)([O-])=O)CP(O)([O-])=O AUMOSEQHACNXEW-UHFFFAOYSA-J 0.000 description 2
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 2
- 239000000015 trinitrotoluene Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
-
- 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
-
- 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
- C06B33/00—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
- C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids
Definitions
- Solid propellants can be classified with respect to composition as double base type, single base type, and composite type.
- An example of a double base propellant is ballistite which comprises essentially nitroglycerine and nitrocellulose.
- Examples of single base propellants are nitrocellulose and trinitrotoluene.
- Composite type propellants are generally composed of an oxidizer, and a binder or fuel. They may contain other materials to facilitate manufacture or increase ballistic performance such as a burning rate catalyst.
- Jet propulsion motors of the type in which the propellants of this invention are applicable can be employed to aid a heavily loaded plane in take-off. Said motors can also be M Recently, it has been discovered that superior solid propellant materials are obtained comprising a solid oxidant such as ammonium nitrate or ammonium perchlorate, and a rubbery material such as a copolymer of butadiene and a vinylpyridine or other substituted heterocycle nitrogen base compound, which after incorporation is cured by a quarternization reaction or a vulcanization reaction. Solid propellant mixturesof this nature and a process for their production are disclosed and claimed in copending application, Serial No. 284,447, filed April 25, 1952, by W. B. Reynolds and J. E. Pritchard.
- the burning rate of composite type propellants utilizing ammonium perchlorate or an alkali metal perchlorate as -at least a major portion of the oxidiz'e ncomponent can be'decreased by incorporating therein'a small but effective amount of a burning rate depressing agent selected from a group of heteropolymolybdates defined hereinafter.
- a burning rate depressing agent selected from a group of heteropolymolybdates defined hereinafter.
- An object of this invention is to provide an improved solid propellant composition. Another object of this in- 3,027,284 Patented Mar. 27, 1962 ICC vention is to provide a burning rate depressing agent for composite type propellants. Another object of this invention is to provide an improved propellant composition containing ammonium perchlorate or an alkali metal perchlorate as the major portion of the oxidizer-component and having incorporated therein a heteropolymolybdate as a burning rate depressing agent.
- a solid propellant composition suitable for use in a rocket motor for developing thrust, comprised of: a base propellant comprising an oxidizer component selected from the group of solid inorganic oxidizing salts consisting of ammonium perchlorate, the alkali metal perchlorates, ammonium nitrate, the alkali metal nitrates, and mixtures thereof, at least weight percent of said oxidizer component being at least one of said perchlorates, and a binder component comprised of a'rubbery materialselected from the group consisting of natural rubber and synthetic rubbery polymers and mixtures thereof; and from 0.1 to 15 parts by weight per parts by weight of said base propellant of a heteropolymolybdate burning rate depressing agent selected from the group consisting of heteropolymolybdates characterized by the formula n a b c wherein X is selected from the group consisting of ammonium and the alkali metals sodium, potassium, lithium, rubidium, and
- heteropolymolybdates increase the burning rate of solid propellant compositions wherein the major portion of the oxidizer component is a nitrate such as ammonium nitrate or the alkali metal nitrates, whereas in the instant inventionthe burning rate of said perchlorat containing propellants is decreased.
- heteropolymolybdate refers to a complex of molybdic acid with either phosphoric acid or silicic acid.
- Molybdic acid can be represented by the formula I H2 O1 ⁇
- Said heteropolymolybdates used in the practice of the invention are complex ions resulting from the condensation of molybdic acid with either phosphoric acid or silicic acid. The mechanism of said condensation reaction is not fully understood. Many of the salts thus formed have definite crystal structures while others are amorphous.
- the compounds used in the practice of the invention can be classified by the ratio of hetero atoms (phosphorus or silicon) to molybdenum atoms. 1 a T u Y Specific examples of said heteropolymolybdates which are useful in the practice of the invention include, among others, the following:
- Hydrated salts of these compounds are also applicable for use in the practice of the invention.
- An example of such a hydrate is (NH P Mo O -11H O, also written as 3(NH O-P O l8Mo0 11H O.
- the water of crystallization amounts to less than 30 mols of water per mol of heteropolymoly-bdate. If desired the water of hydration can be decreased before or during preparation of the propellant, for example, by the application of heat during the mixing or milling operation, and/or by carrying out said mixing or milling operation at reduced pressures.
- the amount of said heteropolymolybclates utilized as burning rate depressants in the practice of the invention is within the range of 0.1 to 15 parts by weight, preferably 0.2 to 5 parts by weight, per 100 parts by weight of base propellant.
- the term base propellant is defined as the binder component plus the oxidant component.
- the rubbery material employed in the binder component of the propellant compositions of the invention can be a natural rubber, a synthetic rubbery polymer, or a mixture of natural rubber and said rubbery polymer.
- the term rubbery polymer as used herein and in the claims, unless otherwise specified is defined as including all rubbery polymers of olefins and diolefins which are prepared by either mass or emulsion polymerization.
- suitable rubbery polymers are polybutadiene, polyisobutylene, polyisoprene, copolymers of isobutylene and isoprene, copolymers of conjugated dienes with comonomers such as styrene, and copolymers of conjugated dienes with polymerizable heterocyclic nitrogen bases.
- Said copolymers of conjugated dienes with polymerizable heterocyclic bases comprise a preferred class of rubbery polymers for use in the binder component of the propellants of the invention.
- a presently preferred rubbery polymer is a copolymer of 1,3-butadiene with 2-methyl-5-vinylpyridine.
- Said preferred class of rubbery polymers prepared by copolymerizing a conjugated diene with a heterocyclic nitrogen base can vary in consistency from very soft rubbers, i.e., materials which are soft at room temperature but will show retraction when relaxed, to those having a Mooney value (ML-4) up to 100.
- the rubbery copolymers most frequently preferred have Mooney values in the range between 5 and 50. They may be prepared by any polymerization methods known to the art, e.g., mass or emulsion polymerization. One convenient method for preparing these copolymers is by emulsion polymerization at temperatures in the range between 0 and F.
- the conjugated dienes employed are those containing from 4 to 10 carbon atoms per molecule and include 1,3-butadiene, isoprene, 2-methyl-l,3-butadiene, and the like.
- Various alkoxy, such as methoxy and ethoxy and cyano derivatives of these conjugated dienes, are also applicable.
- other dienes such as phenylbutadiene, 2,3-dimethyl-1,3-hexadiene, 2-methoxy-3-ethylbutadiene, 2-ethoxy-3-ethyl-1,3-hexadiene, 2-cyano-1,3-butadiene, are also applicable.
- conjugated diene instead of using a single conjugated diene, a mixture of conjugated dienes can be employed. Thus, a mixture of 1,3-butadiene and isoprene can be employed as the conjugated diene portion of the monomer system.
- the polymerizable heterocyclic nitrogen bases which are applicable for the production of the polymeric materials are those of the pyridine, quinoline, and isoquinoline series which are copolymerizable with a conjugated diene and contain one, and only one,
- R' is either hydrogen or a methyl group. That is, the substituent is either a vinyl or an alpha-methylvinyl (isopropenyl) group.
- R' is either hydrogen or a methyl group. That is, the substituent is either a vinyl or an alpha-methylvinyl (isopropenyl) group.
- the compounds of the pyridine series are of the greatest interest commercially at present.
- Various substituted derivatives are also applicable but the total number of carbon atoms in the groups attached to the carbon atoms of the heterocyclic nucleus should not be greater than 15 because the polymerization rate decreases somewhat with increasing size of the alkyl group.
- Compounds where the alkyl substituents are methyl and/or ethyl are available commercially.
- R R R R R R R R R R R R N N R R N where R is selected from the group consisting of hydrogen, alkyl, vinyl, alpha-methylvinyl, alkoxy, halo, hydroxy, cyano, aryloxy, aryl, and combinations of these groups such as haloalkyl, alkylaryl, hydroxyaryl, and the like; one and only one of said groups being selected from the group consisting of vinyl and alpha-methylvinyl; and the total number of carbon atoms in the nuclear substituted groups being not greater than 15.
- Examples of such compounds are 2-vinylpyridine; 2-vinyl-5-ethylpyridine; 2-methyl-5-vinylpyridine; 4-vinylpyridine; 2,3,4-trimethyl- -vinylpyridine; 3,4,5,6-tetramethyl 2 vinylpyridine; 3- ethyl-S-vinylpyridine; 2,6-diethyl-4-vinylpyridine; 2-isopropyl-4-nonyl-5-vinylpyridine; 2-methyl 5 undecyl-3- vinylpyridine; 2,4-dimethyl-5,6-dipentyl-3-vinylpyridine; 2- decyl-S-(alpha-methylvinyl) pyridine; 2-vinyl-3-methyl-5- ethylpyridine; 2-methoxy-4-chloro-6-vinylpyridine; 3- vinyl-S-ethoxypyridine; 2-vinyl-4,5-dichloropyridine; 2- (alpha-methylvinyl)-4-hydroxy-6-cyanopyr
- Another rubbery polymer which can be employed in the binder of the solid propellant composition of this invention is a copolymer of 1,3-butadiene with styrene.
- Such copolymers are commonly known in the art as GR-S rubbers.
- Said GR-S rubbers can be prepared by any of the well known methods employing well known recipes. Any of the well known GR-S rubbers containing from 1 to 2 and up to about 25 parts of styrene can be used in the practice of the invention.
- the GR-S rubber designated as 1505 is one preferred copolymer for use in the practice of the invention.
- GR-S 1505 can be prepared by copolymerizing 1,3-butadiene with styrene at 41 F.
- the binder contains rubbery polymers of the type hereinbefore described and, in addition, there can be present one or more reinforcing agents, plasticizers, wetting agents, and antioxidants.
- Other ingredients which are employed for sulfur vulcanization include a vulcanization accelerator, a vulcanizing agent, such as sulfur, and an accelerator activator, such as zinc oxide.
- the finished binder usually contains various compounding ingredients.
- binder is employed generically and includes various conventional compounding ingredients.
- the binder content of the propellant composition will usually range from 5 to 75 percent by weight.
- a general formulation for the binder component of the propellant compositions of the invention is as follows:
- Reinforcing agents which can be employed include carbon black, wood flour, lignin, and various reinforcing resins such as styrene-divinylbenzene, methyl acrylatedivinylbenzene, acrylic acid-styrene-divinylbenzene, and methyl acrylate-acrylic acid-divinylbenzene resins.
- any rubber plasticizer can be employed in the binder compositions.
- Materials such as Pentaryl A (amylbiphenyl), Paraflux (saturated polymerized hydrocarbon), Circosol-ZHX (petroleum hydrocarbon softener having a specific gravity of 0.940 and a Saybolt Universal viscosity at 100 F. of about 2000 seconds), di(l,4,7-trioxaundecyl) methane, and dioctyl phthalate are suitable plasticizers. Materials which provide a rubber having good low temperature properties are preferred. It is also frequently preferred that the plasticizers be oxygen-containing materials.
- Aerosol OT dioctyl ester of sodium sulfosuccinic acid
- lecithin a compound which is selected from the group consisting of sulfosuccinic acid, lecithin, and Duomeen C diacetate (the diacetate of trimethylenediamine substituted by a coconut oil product) are among the materials which are applicable.
- Antioxidants which can be employed include Flexamine (physical mixture containing 65 percent of a complex diarylamine-ketone reaction product and 35 percent of N,N-diphenyl-p-phenylenediamine, phenyl-beta-naphthylamine, 2,2-methylene-bis(4-methy1-6-tertbutylphenol), and the like. Rubber antioxidants, in general, can be employed or if desired can be omitted.
- vulcanization accelerators are those of the carbamate type, such as N,N-dimethyl-S-tert-butylsulfenyl dithiocarbamate and Butyl-Eight.
- Butyl-Eight is a rubber accelerator of the dithiocarbamate type supplied by the 'R. F. Vanderbilt Company and described in Handbook of Material Trade Names, by Zimmerman and Lavine, 1953 edition, as a brown liquid; specific gravity 1.01; partially soluble in water and gasoline; and soluble in acetone, alcohol, benzol, carbon disulfide and chloroform.
- each of the various types of compounding ingredients can be used single or mixtures of various ingredients performing a certain function can be employed. It is sometimes preferred, for example, to use mixtures of plasticizers rather than a single material.
- Oxidizers which are applicable in the solid propellant compositions of the invention are ammonium perchlorate, the alkali metal perchlorates, ammonium nitrate, and the alkali metal nitrates.
- alkali metal includes sodium, potassium, lithium, cesium, and rubidium.
- Ammonium perchlorate is the presently preferred oxidizer. Mixtures of said oxidizers are also applicable. However, when mixtures of said oxidizers are utilized, one of said perchlorates preferably ammonium perchlorate, should be at least 75 percent by weight of the mixture.
- the oxidizer is ground to a particle size preferably within the range between 20 and 200 microns average particle size.
- the most preferred particle size is from about 40 to about 60 microns.
- the amount of oxidizer used is a major amount of the total composition and is usually within the range of about 75 to about weight percent of the base propellant, i.e., binder plus oxidizer.
- the various ingredients in the propellant composition can be mixed on a roll mill or an internal mixer such as a Banbury or a Baker-Perkins dispersion mixer can be employed.
- the binder forms a continuous phase with the oxidizer being a discontinuous phase.
- One procedure for blending the propellant ingredients utilizes a stepwise addition of the oxidizer ingredient.
- the binder ingredients are first mixed to form a binder mixture and the oxidizer ingredient, having the burning rate depressant dry blended therewith, is then added to said binder mixture in increments, usually 3 to 5, but a greater or smaller number of increments can be used if desired or necessary.
- rocket grains can be formed by extrusion, or compression molding, utilizing techniques known to those skilled in the art.
- the formulated grains are usually cured before use.
- the curing temperature would generally be in the range between 70 and 250 F., preferably between 150 and 250 F.
- the curing time must be long enough to give the required creep resistance and other mechanical properties in the propellant. Said curing time will generally range from around 2 hours, when the higher curing temperatures are employed, to 7 days when the lower curing temperatures are employed.
- Example A rubbery copolymer was prepared by emulsion polymerization of 1,3-butadiene and 2-methyl-5-vinylpyridine at 41 F.
- the polymerization recipe was as follows:
- the polymerization was short-stopped with 0.15 part by weight per 100 parts by weight of rubber of potassium dimethyl dithiocarbamate, and 1.75 parts by weight per 100 parts by weight of rubber of phenyl-beta-naphthylamine was added as a stabilizer.
- the latex was masterbatched with 19.5 parts by weight of low abrasion furnace carbon black per 100 parts by weight of rubber. The black masterbatch was then coagulated with acid, the crumb was washed with water, and then dried.
- the carbon black content of the above-described blend was increased to 22 parts by weight per 100 parts by weight of rubber by milling an additional 2.5 par-ts of said carbon black into said copolymer.
- the thus prepared rubber masterbatch was used to prepare a binder having the composition: Parts by weight 90/10 copolymer 100 Carbon black 22 Butarez 25 1 20 Butyl-Eight 2 2 Sulfur 1.75 Zinc oxide 3 Magnesium oxide 5 Flexamine 3 3 Phenyl-beta-naphthylamine 1.75
- This binder was used to prepare base propellant compositions containing 15 parts by weight of said binder for each 85 parts by weight of ammonium perchlorate.
- the perchlorate was a mixture of two batches of the ground salt. Thirty parts by weight of one batch having a weight average size of 40 microns was mixed with parts by weight of another batch having a weight average size of 200 microns. Both batches were substantially free of particles larger than 140 mesh (105 micron screen opening).
- the base propellants were prepared by first mixing equal parts by weight of the binder and the oxidizer. This uniform blend or materbatch was divided into portions. Each portion was then admixed with additional oxidizer, so as to provide a base propellant containing parts of oxidizer for each 15 parts of binder.
- the desired candidate burning rate depressants in amounts of 2 parts by weight per parts by weight of base propellant was then blended into said base propellants.
- the propellant compositions were then extruded to form cylindrical strands having a diameter of inch.
- the strands were cured for 24 hours at a temperature of about 200 F.
- the cured strands were cut into strand sections approximately 7 inches long and all surfaces of said sections, except one end, were restricted to prevent burning except on said end.
- the strand sections were then mounted in a bomb to determine the burning rate.
- the bomb was maintained at a temperature of 70 F., and was pressured with nitrogen to the desired pressure (300, 600 or 1000 p.s.i.).
- the strands were ignited, and the time required for the propellant to burn between two fusible wires spaced 5 inches apart was recorded.
- the burning rate in inches per second was computed from the results obtained.
- Table I At a pressure of 300 p.s.i. the tetrasodium silico-12-molybdate effected a 36 percent depression of the burning rate.
- a solid propellant composition comprised of: from 75 to 95 weight percent of an oxidizer component selected from the group of solid inorganic oxidizing salts consisting of ammonium perchlorate, the alkali metal perchlorates, ammonium nitrate, the alkali metal nitrates, and mixtures thereof, at least 75 weight percent of said oxidizer component being at least one of said perchlorates, and from 25 to weight percent of a binder component comprised of a rubbery material selected from the group consisting of natural rubber and synthetic rubbery polymers and mixtures thereof; and from 0.1 to 15 parts by weight per 100 parts by weight of the total amount of said oxidizer component plus said binder component of a heteropolymolybdate burning rate depressing agent selected from the group consisting of heteropolymolybdates characterized by the formula x z Mo o,
- X is selected from the group consisting of ammonium and the alkali metals sodium, potassium, lithium, rubidium, and cesium
- n is the valence of the anion group (Z Mo O and is a positive whole integer of from 2 to 8
- Z is selected from the group consisting of phosphorus and silicon
- a is a positive whole integer of from 1 to 2
- b is a positive whole integer of from 6 to 18
- c is a positive whole integer of from 24 to 62.
- a propellant composition according to claim 1 wherein said rubbery material is a copolymer prepared by copolymerizing a conjugated diene containing from 4 to 10 carbon atoms with at least one B! CH O substituted heterocyclic nitrogen base selected from the group consisting of pyridine, quinoline, alkyl substituted pyridine, and alkyl substituted quinoline wherein the total number of carbon atoms in the nuclear alkyl substituents is not more than and wherein R is selected from the group consisting of a hydrogen atom and a methyl radical.
- a propellant composition according to claim 1 wherein said burning rate depressing agent is triammonium phospho-lZ-molybdate.
- a propellant composition according to claim 1 wherein said burning rate depressing agent is tripotassium phospho-12-molybdate.
- a propellant composition according to claim 1 wherein said burning rate depressing agent is tetrarubidium silico-l2-molybdate.
- a propellant composition according to claim 1 wherein said burning rate depressing agent is tetracesium silico-12-molybdate.
- a propellant composition according to claim 1 wherein said burning rate depressing agent is hexasodium 2-phospho-18-molybdate.
- a propellant composition according to claim 1 wherein said burning rate depressing agent is tetrasodium silico-12-molybdate.
- said RI CHFC/ substituted heterocyclic nitrogen base selected from the group consisting of pyridine, quinoline, alkyl substituted pyridine, and alkyl substituted quinoline wherein the total number of carbon atoms in the nuclear alkyl substituents is not more than 15 and
- a propellant composition according to claim 14 wherein said rubbery material is a coplymer of 1,3- butadiene with 2-methyl-5-vinylpyridine.
- a propellant composition according to claim 14 wherein said burning rate depressing agent is tetr-asodium silico-12-molybdate.
Description
United States Patent 3,027,284 COMPOSITE PROPELLANTS CONTAINING A BURNING RATE DEPRESSANT George D. Sammons, Bartlesville, 0kla., assignor to Phillips Petroleum Company, a corporation of Delaware No Drawing. Filed Dec. 29, 1958, Ser. No. 783,619 16 Claims. (Cl. 149-19) This invention relates to solid propellant compositions. In another aspect this invention relates to solid propellant compositions containing a burning rate depressing agent.
Solid propellants can be classified with respect to composition as double base type, single base type, and composite type. An example of a double base propellant is ballistite which comprises essentially nitroglycerine and nitrocellulose. Examples of single base propellants are nitrocellulose and trinitrotoluene. Composite type propellants are generally composed of an oxidizer, and a binder or fuel. They may contain other materials to facilitate manufacture or increase ballistic performance such as a burning rate catalyst.
Rocket propellants have achieved considerable commercial importance as well as military importance. Jet propulsion motors of the type in which the propellants of this invention are applicable can be employed to aid a heavily loaded plane in take-off. Said motors can also be M Recently, it has been discovered that superior solid propellant materials are obtained comprising a solid oxidant such as ammonium nitrate or ammonium perchlorate, and a rubbery material such as a copolymer of butadiene and a vinylpyridine or other substituted heterocycle nitrogen base compound, which after incorporation is cured by a quarternization reaction or a vulcanization reaction. Solid propellant mixturesof this nature and a process for their production are disclosed and claimed in copending application, Serial No. 284,447, filed April 25, 1952, by W. B. Reynolds and J. E. Pritchard.
In the utilization of solid propellant compositions, it is important to control the burning rate and thus be able to control the amount of thrust developed per unit of time for a given charge of propellant. In many instances, burning rate catalysts are utilized to increase the burning rate. However, with some oxidizers, e.g., ammonium perchlorate, it is desirable in many instances to decrease the burning rate; ltfreqiiently happens that composite solid propellants utilizing ammonium perchlorate as the major portion of the oxidizer component are satisfactory from the standpoint of other performance characteristics, such as specific impulse, but possess too high a burning rate.
I have discovered that the burning rate of composite type propellants utilizing ammonium perchlorate or an alkali metal perchlorate as -at least a major portion of the oxidiz'e ncomponent can be'decreased by incorporating therein'a small but effective amount of a burning rate depressing agent selected from a group of heteropolymolybdates defined hereinafter. Thus, broadly speaking, the present invention resides in a solid propellant composition comprising an oxidizer component, a binder component, and said burning rate depressing agent.
An object of this invention is to provide an improved solid propellant composition. Another object of this in- 3,027,284 Patented Mar. 27, 1962 ICC vention is to provide a burning rate depressing agent for composite type propellants. Another object of this invention is to provide an improved propellant composition containing ammonium perchlorate or an alkali metal perchlorate as the major portion of the oxidizer-component and having incorporated therein a heteropolymolybdate as a burning rate depressing agent. Other aspects, objects, and advantages of the invention will be apparent to those skilled in the art in view'of this disclosure.
Thus, according to the invention there is provided a solid propellant composition, suitable for use in a rocket motor for developing thrust, comprised of: a base propellant comprising an oxidizer component selected from the group of solid inorganic oxidizing salts consisting of ammonium perchlorate, the alkali metal perchlorates, ammonium nitrate, the alkali metal nitrates, and mixtures thereof, at least weight percent of said oxidizer component being at least one of said perchlorates, and a binder component comprised of a'rubbery materialselected from the group consisting of natural rubber and synthetic rubbery polymers and mixtures thereof; and from 0.1 to 15 parts by weight per parts by weight of said base propellant of a heteropolymolybdate burning rate depressing agent selected from the group consisting of heteropolymolybdates characterized by the formula n a b c wherein X is selected from the group consisting of ammonium and the alkali metals sodium, potassium, lithium, rubidium, and cesium; n is the valence of the anion group (Z Mo O and is a positive whole integer of from 2 to 8; Z is selected from the group consisting of phosphorus and silicon; a is a positive whole integer of from 1 to 2; b is a positive whole integer of from 6 to 18; and c is a positive whole integer of from 24 to 62. I
The results obtained using the above-identified heteropolymolybdates are believed unique for said perchlorate containing propellants becauseas disclosed and claimed in my copending application, Serial No. 783,615, filed De- .cember 29, 1958, said heteropolymolybdates increase the burning rate of solid propellant compositions wherein the major portion of the oxidizer component is a nitrate such as ammonium nitrate or the alkali metal nitrates, whereas in the instant inventionthe burning rate of said perchlorat containing propellants is decreased.
As used herein, the term heteropolymolybdate refers to a complex of molybdic acid with either phosphoric acid or silicic acid. Molybdic acid can be represented by the formula I H2 O1\|40O) 0 and as hydrated complexes of the oxide M00 Said heteropolymolybdates used in the practice of the invention are complex ions resulting from the condensation of molybdic acid with either phosphoric acid or silicic acid. The mechanism of said condensation reaction is not fully understood. Many of the salts thus formed have definite crystal structures while others are amorphous. The compounds used in the practice of the invention can be classified by the ratio of hetero atoms (phosphorus or silicon) to molybdenum atoms. 1 a T u Y Specific examples of said heteropolymolybdates which are useful in the practice of the invention include, among others, the following:
K SiMo O Tetrapotassium silico-lZ-molybdate Triammonium phospho-lZ-molybdate Trisodium phospho-lZ-molybdate K3PMOIZO4O Tripotassium phospho-lZ-molybdate Ll4SiMO1 O4u Tetralithium silico-lZ-molybdate Na4SlMO O4g Tetrasodium silico-lZ-molybdate Rb4SiMO O4o Tetrarubidium silico-lZ-molybdate CS4SlMO O40 Tetracesium silico-lZ-molybdate 4)4 1z 40 Tetraammonium silico-l2-molybdate G Z IS GZ Hexasodium 2-phospho-l8-molybdate 4)2 2 12 42 Diammonium 2-phospho-l2-molybdate Na3SlMO1 O4 Octasodium silico-12-molybdate 7 11 a9 Heptapotassium phospho-l l-molybdate 4)5 9 s2 Pentaammonium phosphate-9-molybdate CS5SlMO9O32 Hexacesium silico-9-molybdate (NH4) 7 6 24 Heptaammonium phospho-6-molybdate t) 6 2 1s e2 Hexaammonium 2-phospho-l8-molybdate The formulas as given above are for the anhydrous salts. Hydrated salts of these compounds are also applicable for use in the practice of the invention. An example of such a hydrate is (NH P Mo O -11H O, also written as 3(NH O-P O l8Mo0 11H O. For many of the hydrates the water of crystallization amounts to less than 30 mols of water per mol of heteropolymoly-bdate. If desired the water of hydration can be decreased before or during preparation of the propellant, for example, by the application of heat during the mixing or milling operation, and/or by carrying out said mixing or milling operation at reduced pressures.
A review on the structure, properties and the preparation of heteropolymolybdates is given by Killeffer and Linz, Molybdenum Compounds, chapter 8, pages 87-94, Interscience Publishers, New York (1952).
The amount of said heteropolymolybclates utilized as burning rate depressants in the practice of the invention is within the range of 0.1 to 15 parts by weight, preferably 0.2 to 5 parts by weight, per 100 parts by weight of base propellant.
As used herein and in the claims, unless otherwise specified, the term base propellant is defined as the binder component plus the oxidant component. The rubbery material employed in the binder component of the propellant compositions of the invention can be a natural rubber, a synthetic rubbery polymer, or a mixture of natural rubber and said rubbery polymer. The term rubbery polymer as used herein and in the claims, unless otherwise specified is defined as including all rubbery polymers of olefins and diolefins which are prepared by either mass or emulsion polymerization. Some examples of suitable rubbery polymers are polybutadiene, polyisobutylene, polyisoprene, copolymers of isobutylene and isoprene, copolymers of conjugated dienes with comonomers such as styrene, and copolymers of conjugated dienes with polymerizable heterocyclic nitrogen bases. Said copolymers of conjugated dienes with polymerizable heterocyclic bases comprise a preferred class of rubbery polymers for use in the binder component of the propellants of the invention. A presently preferred rubbery polymer is a copolymer of 1,3-butadiene with 2-methyl-5-vinylpyridine.
Said preferred class of rubbery polymers prepared by copolymerizing a conjugated diene with a heterocyclic nitrogen base can vary in consistency from very soft rubbers, i.e., materials which are soft at room temperature but will show retraction when relaxed, to those having a Mooney value (ML-4) up to 100. The rubbery copolymers most frequently preferred have Mooney values in the range between 5 and 50. They may be prepared by any polymerization methods known to the art, e.g., mass or emulsion polymerization. One convenient method for preparing these copolymers is by emulsion polymerization at temperatures in the range between 0 and F. Recipes such as the iron pyrophosphate-hydroperoxide, either sugar-free or containing sugar, the sulfoxylate, and the persulfate recipes are among those which are applicable. It is advantageous to polymerize to high conversion as the unreacted vinylpyridine monomer is difiicult to remove by stripping.
The conjugated dienes employed are those containing from 4 to 10 carbon atoms per molecule and include 1,3-butadiene, isoprene, 2-methyl-l,3-butadiene, and the like. Various alkoxy, such as methoxy and ethoxy and cyano derivatives of these conjugated dienes, are also applicable. Thus, other dienes, such as phenylbutadiene, 2,3-dimethyl-1,3-hexadiene, 2-methoxy-3-ethylbutadiene, 2-ethoxy-3-ethyl-1,3-hexadiene, 2-cyano-1,3-butadiene, are also applicable.
Instead of using a single conjugated diene, a mixture of conjugated dienes can be employed. Thus, a mixture of 1,3-butadiene and isoprene can be employed as the conjugated diene portion of the monomer system.
The polymerizable heterocyclic nitrogen bases which are applicable for the production of the polymeric materials are those of the pyridine, quinoline, and isoquinoline series which are copolymerizable with a conjugated diene and contain one, and only one,
substituent wherein R' is either hydrogen or a methyl group. That is, the substituent is either a vinyl or an alpha-methylvinyl (isopropenyl) group. Of these, the compounds of the pyridine series are of the greatest interest commercially at present. Various substituted derivatives are also applicable but the total number of carbon atoms in the groups attached to the carbon atoms of the heterocyclic nucleus should not be greater than 15 because the polymerization rate decreases somewhat with increasing size of the alkyl group. Compounds where the alkyl substituents are methyl and/or ethyl are available commercially.
These heterocyclic nitrogen bases have the formula R R R R R R R R R R R N N R R N where R is selected from the group consisting of hydrogen, alkyl, vinyl, alpha-methylvinyl, alkoxy, halo, hydroxy, cyano, aryloxy, aryl, and combinations of these groups such as haloalkyl, alkylaryl, hydroxyaryl, and the like; one and only one of said groups being selected from the group consisting of vinyl and alpha-methylvinyl; and the total number of carbon atoms in the nuclear substituted groups being not greater than 15. Examples of such compounds are 2-vinylpyridine; 2-vinyl-5-ethylpyridine; 2-methyl-5-vinylpyridine; 4-vinylpyridine; 2,3,4-trimethyl- -vinylpyridine; 3,4,5,6-tetramethyl 2 vinylpyridine; 3- ethyl-S-vinylpyridine; 2,6-diethyl-4-vinylpyridine; 2-isopropyl-4-nonyl-5-vinylpyridine; 2-methyl 5 undecyl-3- vinylpyridine; 2,4-dimethyl-5,6-dipentyl-3-vinylpyridine; 2- decyl-S-(alpha-methylvinyl) pyridine; 2-vinyl-3-methyl-5- ethylpyridine; 2-methoxy-4-chloro-6-vinylpyridine; 3- vinyl-S-ethoxypyridine; 2-vinyl-4,5-dichloropyridine; 2- (alpha-methylvinyl)-4-hydroxy-6-cyanopyridine; 2-vinyl- 4-phenoxy-5-methylpyridine; Z-cyano 5 (alpha-methylvinyl) pyridine; 3-vinyl-5-phenylpyridine; 2-(para-methylphenyl)-3-vinyl-4-methylpyridine; 3 vinyl 5 (hydroxyphenyD-pyridine; 2-vinylquinoline; 2-vinyl-4-ethylquinoline; 3-vinyl-6,7-di-n-propylquinoline; 2-methyl-4-nonyl-6- vinylpyridine; 4(alpha-methylviny1)-8-dodecylquinoline; 3-vinylisoquinoline; 1,6-dimethyl-3-vinylisoquinoline; 2- vinyl-4-benzylquinoline; 3-vinyl-5-chloroethylquinoline; 3- vinyl-5,6-dichloroisoquinoline; 2-vinyl-6-ethoxy-7-methylquinoline; 3-vinyl-6-hydroxymethylisoquinoline; and the like.
Another rubbery polymer which can be employed in the binder of the solid propellant composition of this invention is a copolymer of 1,3-butadiene with styrene. Such copolymers are commonly known in the art as GR-S rubbers. Said GR-S rubbers can be prepared by any of the well known methods employing well known recipes. Any of the well known GR-S rubbers containing from 1 to 2 and up to about 25 parts of styrene can be used in the practice of the invention. The GR-S rubber designated as 1505 is one preferred copolymer for use in the practice of the invention. GR-S 1505 can be prepared by copolymerizing 1,3-butadiene with styrene at 41 F. using a sugar free, iron activated, rosinacid emulsified system. A charge weight ratio of butadiene to styrene is 90/10 and the polymerization is allowed to go to approximately 52 percent completion. The copolymer is then salt acid coagulated and usually has a mean raw Mooney value (ML-4) of about 40. Said copolymers usually have a bound styrene content of about 8 weight percent. Further details regarding the preparation of GR-S rubbers can be found in Industrial and Engineering Chemistry, 40, pages 769-777 (1948) and United States Patents 2,583,277; 2,595,892; 2,609,362; 2,614,100; 2,647,109; and 2,665,269.
The binder contains rubbery polymers of the type hereinbefore described and, in addition, there can be present one or more reinforcing agents, plasticizers, wetting agents, and antioxidants. Other ingredients which are employed for sulfur vulcanization include a vulcanization accelerator, a vulcanizing agent, such as sulfur, and an accelerator activator, such as zinc oxide. The finished binder usually contains various compounding ingredients. Thus, it will be understood that herein and in the claims, unless otherwise specified, the term binder is employed generically and includes various conventional compounding ingredients. The binder content of the propellant composition will usually range from 5 to 75 percent by weight.
A general formulation for the binder component of the propellant compositions of the invention is as follows:
Reinforcing agents which can be employed include carbon black, wood flour, lignin, and various reinforcing resins such as styrene-divinylbenzene, methyl acrylatedivinylbenzene, acrylic acid-styrene-divinylbenzene, and methyl acrylate-acrylic acid-divinylbenzene resins.
In general, any rubber plasticizer can be employed in the binder compositions. Materials such as Pentaryl A (amylbiphenyl), Paraflux (saturated polymerized hydrocarbon), Circosol-ZHX (petroleum hydrocarbon softener having a specific gravity of 0.940 and a Saybolt Universal viscosity at 100 F. of about 2000 seconds), di(l,4,7-trioxaundecyl) methane, and dioctyl phthalate are suitable plasticizers. Materials which provide a rubber having good low temperature properties are preferred. It is also frequently preferred that the plasticizers be oxygen-containing materials.
Wetting agents aid in deflocculating or dispersing the oxidizer. Aerosol OT (dioctyl ester of sodium sulfosuccinic acid), lecithin, and Duomeen C diacetate (the diacetate of trimethylenediamine substituted by a coconut oil product) are among the materials which are applicable.
Antioxidants which can be employed include Flexamine (physical mixture containing 65 percent of a complex diarylamine-ketone reaction product and 35 percent of N,N-diphenyl-p-phenylenediamine, phenyl-beta-naphthylamine, 2,2-methylene-bis(4-methy1-6-tertbutylphenol), and the like. Rubber antioxidants, in general, can be employed or if desired can be omitted.
Examples of vulcanization accelerators are those of the carbamate type, such as N,N-dimethyl-S-tert-butylsulfenyl dithiocarbamate and Butyl-Eight. Butyl-Eight is a rubber accelerator of the dithiocarbamate type supplied by the 'R. F. Vanderbilt Company and described in Handbook of Material Trade Names, by Zimmerman and Lavine, 1953 edition, as a brown liquid; specific gravity 1.01; partially soluble in water and gasoline; and soluble in acetone, alcohol, benzol, carbon disulfide and chloroform.
It is to be understood that each of the various types of compounding ingredients can be used single or mixtures of various ingredients performing a certain function can be employed. It is sometimes preferred, for example, to use mixtures of plasticizers rather than a single material.
Oxidizers which are applicable in the solid propellant compositions of the invention are ammonium perchlorate, the alkali metal perchlorates, ammonium nitrate, and the alkali metal nitrates. As used herein, the term alkali metal includes sodium, potassium, lithium, cesium, and rubidium. Ammonium perchlorate is the presently preferred oxidizer. Mixtures of said oxidizers are also applicable. However, when mixtures of said oxidizers are utilized, one of said perchlorates preferably ammonium perchlorate, should be at least 75 percent by weight of the mixture. In the preparation of the solid rocket propellant compositions, the oxidizer is ground to a particle size preferably within the range between 20 and 200 microns average particle size. The most preferred particle size is from about 40 to about 60 microns. The amount of oxidizer used is a major amount of the total composition and is usually within the range of about 75 to about weight percent of the base propellant, i.e., binder plus oxidizer.
The various ingredients in the propellant composition can be mixed on a roll mill or an internal mixer such as a Banbury or a Baker-Perkins dispersion mixer can be employed. In the finished propellant the binder forms a continuous phase with the oxidizer being a discontinuous phase. One procedure for blending the propellant ingredients utilizes a stepwise addition of the oxidizer ingredient. The binder ingredients are first mixed to form a binder mixture and the oxidizer ingredient, having the burning rate depressant dry blended therewith, is then added to said binder mixture in increments, usually 3 to 5, but a greater or smaller number of increments can be used if desired or necessary.
After the propellant composition has been formulated as indicated above, or by any other suitable mixing technique, rocket grains can be formed by extrusion, or compression molding, utilizing techniques known to those skilled in the art.
The formulated grains are usually cured before use. The curing temperature would generally be in the range between 70 and 250 F., preferably between 150 and 250 F. The curing time must be long enough to give the required creep resistance and other mechanical properties in the propellant. Said curing time will generally range from around 2 hours, when the higher curing temperatures are employed, to 7 days when the lower curing temperatures are employed.
The following examples will serve to further illustrate the invention. Example A rubbery copolymer was prepared by emulsion polymerization of 1,3-butadiene and 2-methyl-5-vinylpyridine at 41 F. The polymerization recipe was as follows:
Sodium salt of condensed alkylaryl sulfonic acid 0.3 Tetrasodium salt of ethylenediaminetetraacetic acid 0.005
Tertiary dodecyl mercaptan 0.6-0.8
Ferrous sulfate heptahydrate 0.2 Potassium pyrophosphate 0.253 Para-menthane hydroperoxide 0.135
A total of 55 runs were made using the above recipe. The average conversion for these runs was 85 percent in 17.0 hours. The polymerization was short-stopped with 0.15 part by weight per 100 parts by weight of rubber of potassium dimethyl dithiocarbamate, and 1.75 parts by weight per 100 parts by weight of rubber of phenyl-beta-naphthylamine was added as a stabilizer. The latex was masterbatched with 19.5 parts by weight of low abrasion furnace carbon black per 100 parts by weight of rubber. The black masterbatch was then coagulated with acid, the crumb was washed with water, and then dried.
The carbon black content of the above-described blend was increased to 22 parts by weight per 100 parts by weight of rubber by milling an additional 2.5 par-ts of said carbon black into said copolymer. Three parts by weight per 100 parts by weight of rubber of Flexamine, a physical mixture containing 65 percent of a complex diaryla-mine-ketone reaction product and 35 percent of N,N'-diphenyl-p-phenylenediamine, was also milled into said copolymer.
The thus prepared rubber masterbatch was used to prepare a binder having the composition: Parts by weight 90/10 copolymer 100 Carbon black 22 Butarez 25 1 20 Butyl-Eight 2 2 Sulfur 1.75 Zinc oxide 3 Magnesium oxide 5 Flexamine 3 3 Phenyl-beta-naphthylamine 1.75
1 Liquid polybutadiene plasticizer.
2 Activated dithiocarbamate.
percent diarylamine-ketone reaction product and 35 percent N,N'-dlphenyl-p-phenylenedlamine.
This binder was used to prepare base propellant compositions containing 15 parts by weight of said binder for each 85 parts by weight of ammonium perchlorate. The perchlorate was a mixture of two batches of the ground salt. Thirty parts by weight of one batch having a weight average size of 40 microns was mixed with parts by weight of another batch having a weight average size of 200 microns. Both batches were substantially free of particles larger than 140 mesh (105 micron screen opening).
The base propellants were prepared by first mixing equal parts by weight of the binder and the oxidizer. This uniform blend or materbatch was divided into portions. Each portion was then admixed with additional oxidizer, so as to provide a base propellant containing parts of oxidizer for each 15 parts of binder. The desired candidate burning rate depressants in amounts of 2 parts by weight per parts by weight of base propellant was then blended into said base propellants. The propellant compositions were then extruded to form cylindrical strands having a diameter of inch. The strands were cured for 24 hours at a temperature of about 200 F. The cured strands were cut into strand sections approximately 7 inches long and all surfaces of said sections, except one end, were restricted to prevent burning except on said end. The strand sections were then mounted in a bomb to determine the burning rate. The bomb was maintained at a temperature of 70 F., and was pressured with nitrogen to the desired pressure (300, 600 or 1000 p.s.i.). The strands were ignited, and the time required for the propellant to burn between two fusible wires spaced 5 inches apart was recorded. The burning rate in inches per second was computed from the results obtained. The resulting data are presented in Table I below. At a pressure of 300 p.s.i. the tetrasodium silico-12-molybdate effected a 36 percent depression of the burning rate. At pressures of 600 and 1000 p.s.i., the tetrasodium silico-l2-molybdate efiected a 44 and a 45 percent depression in burning rate, respectively. At a pressure of 300 p.s.i. the trisodium phospho-12-mo1ybdate effected a 4 percent depression of the burning rate. At pressures of 600 and 1000 p.s.i., the trisodium phospho-12-molybdate efiected 11 and 9 percent depressions in burning rate, respectively.
TABLE I.DEPRESSIO(I5THI()F BURNING RATE OF AMMONIUM PER- ORATE PROPELLANTS l The moisture content (based on loss in weight on drying at 89.5 C. at a pressure of less than 2 mm. Hg for 39 hours) of the tetrasodium silico-lz-molybdate was 6.2 weight percent, and for the trisodium phospho-12-molybdate was 7.1 weight percent. At least some of said moisture content was water of hydration. The above tests were run using uudrled materials.
Parts by weight per 100 parts of base propellant.
While certain examples have been set forth above for purposes of illustration, the invention is not limited thereto. Various other modifications will be apparent to those skilled in the art in view of this disclosure. Such modifications are within the spirit and scope of the invention.
I claim:
1. A solid propellant composition, comprised of: from 75 to 95 weight percent of an oxidizer component selected from the group of solid inorganic oxidizing salts consisting of ammonium perchlorate, the alkali metal perchlorates, ammonium nitrate, the alkali metal nitrates, and mixtures thereof, at least 75 weight percent of said oxidizer component being at least one of said perchlorates, and from 25 to weight percent of a binder component comprised of a rubbery material selected from the group consisting of natural rubber and synthetic rubbery polymers and mixtures thereof; and from 0.1 to 15 parts by weight per 100 parts by weight of the total amount of said oxidizer component plus said binder component of a heteropolymolybdate burning rate depressing agent selected from the group consisting of heteropolymolybdates characterized by the formula x z Mo o,
wherein: X is selected from the group consisting of ammonium and the alkali metals sodium, potassium, lithium, rubidium, and cesium, n is the valence of the anion group (Z Mo O and is a positive whole integer of from 2 to 8; Z is selected from the group consisting of phosphorus and silicon; a is a positive whole integer of from 1 to 2; b is a positive whole integer of from 6 to 18; and c is a positive whole integer of from 24 to 62.
2. A propellant composition according to claim 1 wherein said oxidizer component is ammonium perchlorate. v
3. A propellant composition according to claim 1 wherein said oxidizer component is at least about 75 weight percent ammonium perchlorate and up to about 25 weight percent ammonium nitrate.
4. A propellant composition according to claim 1 wherein said rubbery material is natural rubber.
5. A propellant composition according to claim 1 wherein said rubbery material is a copolymer prepared by copolymerizing a conjugated diene containing from 4 to 10 carbon atoms with at least one B! CH O substituted heterocyclic nitrogen base selected from the group consisting of pyridine, quinoline, alkyl substituted pyridine, and alkyl substituted quinoline wherein the total number of carbon atoms in the nuclear alkyl substituents is not more than and wherein R is selected from the group consisting of a hydrogen atom and a methyl radical.
6. A propellant composition according to claim 1 wherein said burning rate depressing agent is triammonium phospho-lZ-molybdate.
7. A propellant composition according to claim 1 10 wherein said burning ratedepressing agent is trisodium phospho-lZ-molybdate.
8. A propellant composition according to claim 1 wherein said burning rate depressing agent is tripotassium phospho-12-molybdate.
9. A propellant composition according to claim 1 wherein said burning rate depressing agent is tetrarubidium silico-l2-molybdate.
10. A propellant composition according to claim 1 wherein said burning rate depressing agent is tetracesium silico-12-molybdate.
11. A propellant composition according to claim 1 wherein said burning rate depressing agent is hexasodium 2-phospho-18-molybdate.
12. A propellant composition according to claim 1 wherein said burning rate depressing agent is tetrasodium silico-12-molybdate.
13. A propellant composition according to claim 1 wherein the amount of said burning rate depressing agent is within the range of 0.2 to 5 parts by weight per parts by weight of the total amount of said oxidizer component plus said binder component.
14. A propellant composition according to claim 1 wherein said oxidant component is ammonium perchlorate, said rubbery material is a copolymer prepared by copolymerizing a conjugated diene containing from 4 to 10 carbon atoms with at least one RI CHFC/ substituted heterocyclic nitrogen base selected from the group consisting of pyridine, quinoline, alkyl substituted pyridine, and alkyl substituted quinoline wherein the total number of carbon atoms in the nuclear alkyl substituents is not more than 15 and wherein R is selected from the group consisting of a hydrogen atom and a methyl radical, and said burning rate depressing agent is tetrasodium silico-12-molybdate.
15. A propellant composition according to claim 14 wherein said rubbery material is a coplymer of 1,3- butadiene with 2-methyl-5-vinylpyridine.
16. A propellant composition according to claim 14 wherein said burning rate depressing agent is tetr-asodium silico-12-molybdate.
References Cited in the file of this patent UNITED STATES PATENTS 2,637,274 Taylor et a1 May 5, 1953 2,682,461 Hutchison June 29, 1954 2,744,816 Hutchison May 8, \1956 2,877,504 Fox Mar. 17, 1959 FOREIGN PATENTS 655,585 Great Britain July 25, 1951 OTHER REFERENCES 6zgllaemical and Engineering News, Oct. 7, 1957, pp
Claims (1)
1. A SOLID PROPELLANT COMPOSITION, COMPRISED OF: FROM 75 TO 95 WEIGHT PERCENT OF AN OXIDIZER COMPONENT SELECTED FROM THE GROUP OF SOLID INORGANIC OXIDIZING SALTS CONSISTING OF AMMONIUM PERCHLORATE, THE ALKALI METAL PERCHLORATES, AMMONIUM NITRATE, THE ALKALI METAL NITRATES, AND MIXTURES THEREOF, AT LEAST 75 WEIGHT PERCENT OF SAID OXIDIZER COMPONENT BEING AT LEAST ONE OF SAID PERCHLORATES, AND FROM 25 TO 5 WEIGHT PERCENT OF A BINDER COMPONENT COMPRISED OF A RUBBERY MATERIAL SELECTED FROM THE GROUP CONSISTING OF NATURAL RUBBER AND SYNTHETIC RUBBERY POLYMERS AND MIXTURES THEREOF; AND FROM 0.1 TO 15 PARTS BY WEIGHT PER 100 PARTS BY WEIGHT OF THE TOTAL AMOUNT OF SAID OXIDIZER COMPONENT PLUS SAID BINDER COMPONENT OF A HETEROPOLYMOLYBDATE BURNING RATE DEPRESSING AGENT SELECTED FROM THE GROUP CONSISTING OF HETEROPOLYMOLYBDATES CHARACTERIZED BY THE FORMULA
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US3220898A (en) * | 1962-12-20 | 1965-11-30 | Standard Oil Co | Solid gas generating compositions containing phosphate burning rate suppressants |
US3632458A (en) * | 1968-05-02 | 1972-01-04 | Dow Ch Mical Co The | Self-extinguishing solid propellant formulations |
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GB655585A (en) * | 1947-09-29 | 1951-07-25 | Frans Tore Baltzar Bonell | Improvements in or relating to methods for producing propellent charges for rockets and the like |
US2637274A (en) * | 1946-11-29 | 1953-05-05 | Ici Ltd | Power-gas generating device |
US2682461A (en) * | 1949-01-12 | 1954-06-29 | Ici Ltd | Solid gas generating charge |
US2744816A (en) * | 1947-10-10 | 1956-05-08 | Ici Ltd | Solid gas-generating charges |
US2877504A (en) * | 1954-08-02 | 1959-03-17 | Phillips Petroleum Co | Method of bonding propellant grain to metal case |
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Publication number | Priority date | Publication date | Assignee | Title |
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US2637274A (en) * | 1946-11-29 | 1953-05-05 | Ici Ltd | Power-gas generating device |
GB655585A (en) * | 1947-09-29 | 1951-07-25 | Frans Tore Baltzar Bonell | Improvements in or relating to methods for producing propellent charges for rockets and the like |
US2744816A (en) * | 1947-10-10 | 1956-05-08 | Ici Ltd | Solid gas-generating charges |
US2682461A (en) * | 1949-01-12 | 1954-06-29 | Ici Ltd | Solid gas generating charge |
US2877504A (en) * | 1954-08-02 | 1959-03-17 | Phillips Petroleum Co | Method of bonding propellant grain to metal case |
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US3220898A (en) * | 1962-12-20 | 1965-11-30 | Standard Oil Co | Solid gas generating compositions containing phosphate burning rate suppressants |
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