US3625782A - Solid propellants containing burning rate depressants - Google Patents
Solid propellants containing burning rate depressants Download PDFInfo
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- US3625782A US3625782A US726649A US3625782DA US3625782A US 3625782 A US3625782 A US 3625782A US 726649 A US726649 A US 726649A US 3625782D A US3625782D A US 3625782DA US 3625782 A US3625782 A US 3625782A
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- propellant
- potential base
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- 239000004449 solid propellant Substances 0.000 title description 7
- 239000003380 propellant Substances 0.000 claims abstract description 59
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 26
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002585 base Substances 0.000 claims description 32
- 150000001412 amines Chemical class 0.000 claims description 30
- 239000011230 binding agent Substances 0.000 claims description 29
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 150000002897 organic nitrogen compounds Chemical class 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 238000002485 combustion reaction Methods 0.000 claims description 4
- 230000000881 depressing effect Effects 0.000 claims description 4
- 239000012458 free base Substances 0.000 claims description 4
- 150000001541 aziridines Chemical class 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 2
- 230000000994 depressogenic effect Effects 0.000 claims description 2
- 239000000446 fuel Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 238000001723 curing Methods 0.000 abstract description 7
- 230000002411 adverse Effects 0.000 abstract description 4
- 230000000704 physical effect Effects 0.000 abstract description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 150000002430 hydrocarbons Chemical group 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 235000013877 carbamide Nutrition 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 8
- -1 that is Chemical class 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 150000003672 ureas Chemical class 0.000 description 4
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical group NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- VFFDVELHRCMPLY-UHFFFAOYSA-N dimethyldodecyl amine Natural products CC(C)CCCCCCCCCCCN VFFDVELHRCMPLY-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical class C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000001734 carboxylic acid salts Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 229940117986 sulfobetaine Drugs 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UKXSKSHDVLQNKG-UHFFFAOYSA-N benzilic acid Chemical compound C=1C=CC=CC=1C(O)(C(=O)O)C1=CC=CC=C1 UKXSKSHDVLQNKG-UHFFFAOYSA-N 0.000 description 1
- 229940087675 benzilic acid Drugs 0.000 description 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical class NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- PYRZPBDTPRQYKG-UHFFFAOYSA-N cyclopentene-1-carboxylic acid Chemical compound OC(=O)C1=CCCC1 PYRZPBDTPRQYKG-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- NAPSCFZYZVSQHF-UHFFFAOYSA-N dimantine Chemical compound CCCCCCCCCCCCCCCCCCN(C)C NAPSCFZYZVSQHF-UHFFFAOYSA-N 0.000 description 1
- 229950010007 dimantine Drugs 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- LGPJVNLAZILZGQ-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;iodide Chemical compound [I-].CCCCCCCCCCCCCCCC[N+](C)(C)C LGPJVNLAZILZGQ-UHFFFAOYSA-M 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 235000012907 honey Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- RBLWMQWAHONKNC-UHFFFAOYSA-N hydroxyazanium Chemical compound O[NH3+] RBLWMQWAHONKNC-UHFFFAOYSA-N 0.000 description 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 125000001905 inorganic group Chemical group 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
- NHLUVTZJQOJKCC-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCN(C)C NHLUVTZJQOJKCC-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019983 sodium metaphosphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/007—Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B29/00—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate
- C06B29/22—Compositions containing an inorganic oxygen-halogen salt, e.g. chlorate, perchlorate the salt being ammonium perchlorate
-
- 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
- Solid rocket propellants employing ammonium perchlorate as an oxidizing agent are well known.
- propellants based upon ammonium perchlorate have a high burning rate.
- Typical of such known bumingrate depressants is calcium oxalate.
- calcium oxalate does not contribute to the energy of the propellant and hence, when used in effective buming-rate depressing amounts, reduces the specific impulse of the propellant.
- the present invention comprises novel solid ammonium perchlorate containing rocket propellants containing therein potential bases which are stable under conventional solid propellant curing conditions but which yield at least some free base upon propellant combustion.
- the amine precursors reduce the burning rate of the propellant without adversely affecting the specific impulse or the physical properties thereof.
- the invention further comprises the formulation of novel propellants containing the burning-rate depressants referred to above.
- the precursors are used in an effective burning rate reducing amount, normally from about 0.0l percent to about 5 percent by weight of the propellant.
- the optimum amount for any propellant is dependent upon the propellant formulation and performance desired.
- the novel burning-rate depressants of the present invention act as sources of free nonvolatile bases such as amines, that is, compounds which release bases upon thermal decomposition only. It has been found that nonvolatile free organic amines in a propellant binder drastically reduce the burning rate, apparently due either to the generation of ammonia or to the prevention of the buildup of a hydrogen-perchlorate-rich surface on the NH,CIO, particles. However, the incorporation of strongly basic free amines in a propellant is impractical, since it was found that the ordinary binder systems used in the solid propellants will not satisfactorily cure in their presence.
- the precursor compounds of the present invention are believed to generate the free nonvolatile amines in situ, and therefore permit the curing of the propellant and at the same time yield, upon decomposition, the free nonvolatile amines which suppress the buildup of perchloric-acid-rich surfaces on the NH,C10, particles.
- the control of the ammonia generation and perchloric acid buildup is believed to be significant for the following reasons. It is well known that in an ammonia atmosphere, the decomposition of ammonium perchlorate is considerably slowed down. It is believed that the decomposition of ammonium perchlorate is preceded by a dissociation into ammonia and hydrogen perchlorate, followed by desorption where ammonia, because of its lower molecular weight, diffuses away faster, leaving a hydrogen-perchlorate-rich surface. In the present invention, it is believed that the burning-rate depressants of this invention prevent temporarily the buildup of a hydrogen-perchlorate-rich surface.
- the compounds of the present invention are very beneficial in controlling the burning rate of ammonium perchlorate propellants. In addition, the compounds of the present invention are fully compatible with the binder system and do not interfere with curing. These compounds are also sufficiently soluble in the binder to allow themselves to be adsorbed onto the ammonium perchlorate.
- Yet another object of the present invention is to provide the means for controlling the burning rate of ammonium perchlorate propellants without adversely affecting the specific impulse.
- Still another object of the present invention is the provision of buming-rate modifier compounds which are effective in ammonium perchlorate propellants and do not interfere with the cure system or the physical properties of the cured propellant.
- New classes of buming-rate modifiers within the scope of the present invention are those compounds derived from amines which will yield free amines upon thermal decomposition or those which are capable of exchanging the amine constituent.
- the present invention is not limited to amine derivatives, however, but extends to compounds which are potential bases, that is, compounds or compositions which, at elevated temperatures, are converted into or release free bases and are readily adsorbed or coated onto the oxidizer (ammonium perchlorate or other ammonium salts with an oxidizing anion like NO included are also salts of ammonium derivatives, such as hydroxyl-ammonium
- the amine derivatives within the scope of the present invention include ammonium salts of organic amines having the formula:
- R, and R are either alkyl groups or hydrogen, and R; is preferably a hydrocarbon chain containing from eight to 30 carbon atoms. Any of the R-groups may contain one or more functional groups such as hydroxyl, etc.
- acid used to prepare the salts from the above amines include hydrochloric, sulfuric, nitric, perchloric, hydrogen borofluoride and perfluoroaeetic.
- the invention also includes quaternary ammonium salts having the formula:
- R, R,, R and R are alkyl groups, preferably where at least one R group is a hydrocarbon chain containing from about eight to about 30 carbon atoms. Any of the R-groups may contain one or more functional groups such as hydroxyl,
- X is any of the stable inorganic or organic anions, i.e., chloride, nitrate, sulfate, phosphate, etc. Included are also quaternary ammonium salts which are derived from oligoand polyamines.
- quaternary ammonium salts are trimethyldodecylammonium toluenesulfonate wherein l0 g. dimethyldodecylamine are dissolved in about 50 ml. methylethylketone and 9.3 g. methyl p-toluenesulfonate added under stirring.
- the quaternary ammonium salt starts to crystallize out already at room temperature.
- the solution is heated to the b.p. of MEK and just enough isopropanol added to completely dissolve any precipitate.
- the desired compound crystallizes out on cooling to room temperature. It is filtered off, washed with MEK and dried under vacuum. White, crystalline solid; yield nearly quantitative.
- a still further example of the preparation of quaternary ammonium salts is trimethyldodecylammonium metaphosphate wherein a cold solution of L2 g. water-soluble sodium metaphosphate in 100 ml. water, a hot solution of 4 g. trimethyldodecylammonium toluenesulfonate in about 30 ml. 35
- quaternary ammonium salts useful in this Invention and containing hydroxyl groups include:
- NCCH2CHF 'CIhCIIflOH -CH1CHaOH Do. -CH; --CII; CH;.CHOH.CH;OH Do. --ClhClIOlI CH; -CH .CH0H.CH, "'CllQ-(IIIOIIXJH; D0. H; C IzClh0H --CH1CII2OH Do. CH3 -C H3 (1121175 D0. 015F131 *CHsC 20H ACHQCIIIOI D0. CH: Cla aT lE JT 0- Polymeric quaternary ammonium salts with OH groups are also included, and are illustrated by:
- R,, R and R are alkyl groups; R, is any linear or branched hydrocarbon group, normally alkylene; and Y may be any of the stable inorganic or organic groups such as OBF,, S and COO.
- the R,-group can be omitted in which case the Y-group (BF,, 0, etc.) is attached directly to the nitrogen.
- any of the R-groups may comprise a hydrocarbon structure from eight to 30 carbon atoms.
- any of the R-groups may contain one or more functional groups such as hydroxyl, carboxyl, etc. Included also are structures which contain more than one functional group such as hydroxyl, carboxyl, etc. Included also are structures which contain more than one anionic Y-group.
- R is a hydrocarbon group
- R R and R are hydrogen or hydrocarbon groups, preferably with one or more of the R-groups consisting of hydrocarbon chains from about eight to about 30 carbon atoms. Any of the R-groups may contain one or more functional groups such as hydroxyl, carboxyl, etc. Also included are derivatives of biuret, guanidine and similar compounds.
- the invention includes any of the metal salts which form stable complexes with amines.
- the amino nitrogen can carry at least one hydrocarbon group with or without other functional or complexing groups.
- the hydrocarbon group contains from about eight to 30 carbon atoms.
- An example of such a compound is the zinc complex:
- Amine precursor compounds were evaluated, by incorporation at an 0.3 percent level into a propellant consisting of 86 percent solids [76 percent ammonium perchlorate, and I0 percent powdered aluminum).
- the additive replaced an equivalent amount of the binder.
- Direct addition of the respective amine precursor compound to the binder is preferred, though in special cases the oxidizer was precoated with the material. Processing was done at ll5-l25" F.
- the propellants were cured at I35 F. in bulk for preparation of solid strands. Since the response of a propellant towards such bumingrate modifiers depends strongly on the binder, two representative binders were used for testing.
- Polypropylene ether diol 28.435 Polypropylene ether triol 4
- FIGS. 5-8 The results are shown in FIGS. 5-8. In both systems. Binder No. I (FIGS. 5 and 6) and Binder No. 2 (FIGS. 7 and 8), it is seen that these compounds indeed are burning rate modifiers though not as effective as the previous ones.
- oxamide One of the most eflective burning-rate depressants reported in the prior art is oxamide.
- Oxamide was incorporated into standard propellants at a l.5 level and compared with the ad ditives of this invention at an 0.3 percent level. The results are shown in FIGS. 9 (Binder No. 2) and 10 (Binder No. I).
- the quaternary ammonium salt is more than five times as effective as the oxamide.
- the sulfobetaine shown is even more effective.
- amine derivatives any potential base as defined there will be effective although the most powerful burning-rate depressants are derived from amines.
- depressants derived from carboxylic acid salts preferably from such which are relatively strong acids (e.g., by a-substitution with electron withdrawing groups):
- R alkyl or aryl preferably long hydrocarbon chains, e.g., C I-I, and longer
- R, I'I or aryl
- Y preferably cations of the alkali or alkaline earth metals, like Li, Na, K, Mg, Ca Sr and Ba.
- a example for the preparation of a carboxylic acid salt is Libenzilate wherein 0.05 moles of benu'lic acid are dissolved in warm methanol and a solution of 1.2 g. LiOH (in just enough methanol to dissolve it) is added. The Li-salt crystallizes out at room temperature and can be recrystallized from isopropanol.
- Benzilic acid can be either purchased or made according to "Organic Synthesis" Collective Vol. I, p. 89 (1958 publ. John Wiley & Sons, Inc., New York.
- potential base means that free bases will not only be released from real chemical compounds, but also from adsorbates, clathrates (inclusion compounds) etc.
- An example for the latter are amine/urea inclusion compounds, where the amine is contained in channel structures formed by the urea crystal lattice. At the m.p. of the urea (about 130 C.), the amine is released and is free to difl'use through the binder to the NI-LC I 0, particles.
- an alkylamine ureaclathrate is where 40 g. of urea are dissolved in I00 ml. 10.4 methanol, then I04 3. dimethyloctadecylamine are added under stirring; the clathrate crystallizes out on cooling under continued stirring. It is filtered off at room temperature, washed with ice cold methanol and dried under vacuum at room temperature. Titration of the clathrate showed that it contained 75 moles amine per g. clathrate or 22.3 g. amine per 100 g. clathrate.
- the present invention is applicable to all types of ammonium perchlorate containing solid propellants including those having polymeric binders derived from polyether-diols, -trio
- the propellants may contain fuels such as aluminum, plasticizers, stabilizers and the like. Many propellant formulations and their processing techniques are disclosed in assignees prior patents including US. Pat. Nos. 3,245,849 and 3,340,] l l the disclosure of which are expressly incorporated herein by reference.
- solid rocket propellants comprising a cross-linked high molecular weight polymeric binder and an ammonium perchlorate oxidizing agent
- said propellant contains an effective burning-rate depressing amount of a potential base which is stable under the normal curing conditions for solid rocket propellants but which is capable upon combustion of said propellant of conversion to form at least some free base
- said potential base being an organic nitrogen compound and present in an amount from about 0.01 percent to about percent by weight of the propelan ammonium salt of an organic amine.
- composition of claim I wherein the potential base is a quaternary ammonium salt.
- composition of claim 1 wherein the potential base is a zwitterionic betaine-type compound.
- composition of claim 1 wherein the potential base comprises a substituted organic urea.
- a method of fonning a novel solid rocket propellant comprises forming a castabie mixture of a curable polymeric binder, ammonium perchlorate, and a potential base, and thereafter casting the mixture and permitting it to set to form a solid rocket propellant having a depressed burning rate, said potential base being an organic nitrogen compound and present in an amount from about 0.01 percent to about 5 percent by weight of the propellant.
Abstract
This patent described novel solid ammonium perchlorate containing propellant compositions containing powerful burningrate depressants which are potential bases, that is, compounds which are capable of releasing free bases. The burning-rate depressants of this invention do not reduce the specific impulse of the propellant, nor do they interfere with cure reactions or adversely affect the physical properties of the cured propellant.
Description
United States Patent Inventors Adolf E. Oherth Fair Oaks; Roll 8. Bruenner, Orangevnle, both of Calif. Appl. No. 726,649 Filed May 2,1968 Patented Dec. 7, 1971 Assignee Aerojet-General Corporation El Monte, Calif.
SOLID PROPELLANTS CONTAINING BURNING RATE DEPRESSANTS 12 Claims, 10 Drawing Figs.
U.S. Cl 149/19, 149/20 Int. Cl C06d 5/06 Field of Search 149/19, 20
References Cited UNITED STATES PATENTS 3/1962 Sammons 149/76 X Primary Examiner-Benjamin R. Padgett Atrorneys- Edward O, Ansell, D1 Gordon Angus and Reid Anderson ABSTRACT: This patent described novel solid ammonium perchlorate containing propellant compositions containing powerful burning-rate depressants which are potential bases. that is. compounds which are capable of releasing free bases. The burning-rate depressants of this invention do not reduce the specific impulse of the propellant, nor do they interfere with cure reactions or adversely affect the physical properties of the cured propellant.
SOLID PROPELLANTS CONTAINING BURNING RATE DEPRESSANTS BACKGROUND OF THE INVENTION The field of the present invention pertains to novel solid rocket propellants and their preparation.
Solid rocket propellants employing ammonium perchlorate as an oxidizing agent are well known. In general, propellants based upon ammonium perchlorate have a high burning rate. In many solid rocket applications, it is desirable to have a propellant which will provide a slower burning rate than normally can be had with ammonium perchlorate propellants. Therefore, it has been proposed to use various burning-rate depressants to control and reduce the burning rate of ammonium perchlorate propellants. Typical of such known bumingrate depressants is calcium oxalate. However, it is necessary to use calcium oxalate in rather substantial quantities if the desired burning-rate suppression is to be obtained. Moreover, calcium oxalate does not contribute to the energy of the propellant and hence, when used in effective buming-rate depressing amounts, reduces the specific impulse of the propellant.
According to the present invention there has now been found potential bases which are uniquely adapted to the reduction of the burning rate of ammonium perchlorate containing propellants. These additives are substantially more ef fective than calcium oxalate in that they require only about one-tenth or less of the concentration of calcium oxalate in order to provide the same degree of buming-rate suppression. In addition, the buming-rate additives of the present invention do not decrease the propellant's specific impulse.
SUMMARY OF THE INVENTION Briefly, the present invention comprises novel solid ammonium perchlorate containing rocket propellants containing therein potential bases which are stable under conventional solid propellant curing conditions but which yield at least some free base upon propellant combustion. The amine precursors reduce the burning rate of the propellant without adversely affecting the specific impulse or the physical properties thereof. The invention further comprises the formulation of novel propellants containing the burning-rate depressants referred to above.
The precursors are used in an effective burning rate reducing amount, normally from about 0.0l percent to about 5 percent by weight of the propellant. The optimum amount for any propellant is dependent upon the propellant formulation and performance desired.
While not bound by any theory, it is believed that the novel burning-rate depressants of the present invention act as sources of free nonvolatile bases such as amines, that is, compounds which release bases upon thermal decomposition only. It has been found that nonvolatile free organic amines in a propellant binder drastically reduce the burning rate, apparently due either to the generation of ammonia or to the prevention of the buildup of a hydrogen-perchlorate-rich surface on the NH,CIO, particles. However, the incorporation of strongly basic free amines in a propellant is impractical, since it was found that the ordinary binder systems used in the solid propellants will not satisfactorily cure in their presence. The precursor compounds of the present invention are believed to generate the free nonvolatile amines in situ, and therefore permit the curing of the propellant and at the same time yield, upon decomposition, the free nonvolatile amines which suppress the buildup of perchloric-acid-rich surfaces on the NH,C10, particles.
The control of the ammonia generation and perchloric acid buildup is believed to be significant for the following reasons. It is well known that in an ammonia atmosphere, the decomposition of ammonium perchlorate is considerably slowed down. It is believed that the decomposition of ammonium perchlorate is preceded by a dissociation into ammonia and hydrogen perchlorate, followed by desorption where ammonia, because of its lower molecular weight, diffuses away faster, leaving a hydrogen-perchlorate-rich surface. In the present invention, it is believed that the burning-rate depressants of this invention prevent temporarily the buildup of a hydrogen-perchlorate-rich surface. The compounds of the present invention are very beneficial in controlling the burning rate of ammonium perchlorate propellants. In addition, the compounds of the present invention are fully compatible with the binder system and do not interfere with curing. These compounds are also sufficiently soluble in the binder to allow themselves to be adsorbed onto the ammonium perchlorate.
Accordingly, it is an object of the present invention to provide a novel class of solid rocket propellants.
More particularly, it is an object of the present invention to provide a novel class of solid rocket propellants having a decreased burning rate and containing precursors of free organic amines.
Yet another object of the present invention is to provide the means for controlling the burning rate of ammonium perchlorate propellants without adversely affecting the specific impulse.
Still another object of the present invention is the provision of buming-rate modifier compounds which are effective in ammonium perchlorate propellants and do not interfere with the cure system or the physical properties of the cured propellant.
These and other objects and advantages of the present invention will become apparent from the detailed description which follows.
DESCRIPTION OF THE PREFERRED EMBODIMENTS New classes of buming-rate modifiers within the scope of the present invention are those compounds derived from amines which will yield free amines upon thermal decomposition or those which are capable of exchanging the amine constituent. The present invention is not limited to amine derivatives, however, but extends to compounds which are potential bases, that is, compounds or compositions which, at elevated temperatures, are converted into or release free bases and are readily adsorbed or coated onto the oxidizer (ammonium perchlorate or other ammonium salts with an oxidizing anion like NO included are also salts of ammonium derivatives, such as hydroxyl-ammonium The amine derivatives within the scope of the present invention include ammonium salts of organic amines having the formula:
wherein R, and R, are either alkyl groups or hydrogen, and R; is preferably a hydrocarbon chain containing from eight to 30 carbon atoms. Any of the R-groups may contain one or more functional groups such as hydroxyl, etc. Examples of acid used to prepare the salts from the above amines include hydrochloric, sulfuric, nitric, perchloric, hydrogen borofluoride and perfluoroaeetic.
The invention also includes quaternary ammonium salts having the formula:
Iitl Rr-N-Rr wherein R,, R,, R and R, are alkyl groups, preferably where at least one R group is a hydrocarbon chain containing from about eight to about 30 carbon atoms. Any of the R-groups may contain one or more functional groups such as hydroxyl,
carboxyl, etc. X is any of the stable inorganic or organic anions, i.e., chloride, nitrate, sulfate, phosphate, etc. Included are also quaternary ammonium salts which are derived from oligoand polyamines.
An example of the preparation of quaternary ammonium salts 1936) trimethylhexadecylammonium iodide wherein 13.5 g. dimethylhexadecylamine are dissolved in approximately 100 ml. methylethylketone (MEK) and then 7 g. methyliodide added under stirring. This mixture is heated to the boiling point of MEK and isopropanol is added until all of the precipitated quaternary ammonium salt has dissolved. The clear solution is allowed to cool to room temperature whereupon the salt crystallizes out. After washing with MEK the compound was dried under vacuum. White crystalline solid, melting point close to that reported in the literature (247 C.) (Macroski, Bulletin de la Societe Chimique de France (5) 3 I936) 500); yield is nearly quantitative.
Another example of the preparation of quaternary ammonium salts is trimethyldodecylammonium toluenesulfonate wherein l0 g. dimethyldodecylamine are dissolved in about 50 ml. methylethylketone and 9.3 g. methyl p-toluenesulfonate added under stirring. The quaternary ammonium salt starts to crystallize out already at room temperature. To complete the reaction the solution is heated to the b.p. of MEK and just enough isopropanol added to completely dissolve any precipitate. The desired compound crystallizes out on cooling to room temperature. It is filtered off, washed with MEK and dried under vacuum. White, crystalline solid; yield nearly quantitative. 30
A still further example of the preparation of quaternary ammonium salts is trimethyldodecylammonium metaphosphate wherein a cold solution of L2 g. water-soluble sodium metaphosphate in 100 ml. water, a hot solution of 4 g. trimethyldodecylammonium toluenesulfonate in about 30 ml. 35
water is added under rapid stirring, whereupon the quaternary ammonium metaphosphate precipitates immediately. It is filtered off, washed with plenty of cold water and dried under vacuum. White solid, soluble inorganic solvents like Cl-lCl, and others.
The following quaternary ammonium halide compounds have also been found to be useful in this invention.
Other quaternary ammonium salts useful in this Invention and containing hydroxyl groups include:
a lit e R0 R1 X (11).. lliUlhUll (llhClhOll *GIIsClliOil CU; I (11).... blamensnbovuuuflhn. lnmnasnbovondflnfl CH; CH; 1 (c) (Ill; "(1H CH; Clh PH Cll; Cull Cll, 0 80(311,
(d) "Cl iClI'CH' -C|5Hn -CIII -CIX; Cl
0 ll ll (0) Same as above CH:CH:0II CII;CHOH CnH;1 C] (i) -CH1CH20H C 2Hzs *CH; 01 Same as above CuHn CH| Cl .do .d0 Same as above -C|5H Br *CII --CH-CH; CH:7-CH*-C1{3 0 SOCH;
H OH
(j) *CHz-CII-CHI CH:CH:OH *CHzCHgOH C1 H;1 Cl
H II
Same as above -C1sHn CH: CH; Cl -CH2CH1OH CH:CH2OH "CH; CH: I Same as above "do CHzCIhOH CH; I "CHHH --C2Ii5 CII3 CH3 H;C v S O;
(o) Same as above *CH; CH; -CH! Same as above. (9)" (10 CH; *Clla CH; DD. i H; -CH2CHOH -CH2CH2OH Do. (r) *CHICIIECN Same as above Same as above Do. CH; Cli -CH1-CHCH, Do.
NCCH2CHF 'CIhCIIflOH -CH1CHaOH Do. -CH; --CII; CH;.CHOH.CH;OH Do. --ClhClIOlI CH; -CH .CH0H.CH, "'CllQ-(IIIOIIXJH; D0. H; C IzClh0H --CH1CII2OH Do. CH3 -C H3 (1121175 D0. 015F131 *CHsC 20H ACHQCIIIOI D0. CH: Cla aT lE JT 0- Polymeric quaternary ammonium salts with OH groups are also included, and are illustrated by:
wherein R,, R and R are alkyl groups; R, is any linear or branched hydrocarbon group, normally alkylene; and Y may be any of the stable inorganic or organic groups such as OBF,, S and COO. In the above fonnula, the R,-group can be omitted in which case the Y-group (BF,, 0, etc.) is attached directly to the nitrogen. In the above fonnula, any of the R-groups may comprise a hydrocarbon structure from eight to 30 carbon atoms. Also, any of the R-groups may contain one or more functional groups such as hydroxyl, carboxyl, etc. Included also are structures which contain more than one functional group such as hydroxyl, carboxyl, etc. Included also are structures which contain more than one anionic Y-group.
An example for the preparation of a Betaine Analogue having the formula:
(according to T. L. Gresham et al., J.A.C.S. 73, 3,168, I95 1 To a solution of 2| .3 g. dimethyldodecylamin in 125 ml. ether and 38 ml. H,CCN 7.2 g. B-propiolactone were added under stirring, whereupon a white solid formed. After standing for 16 hours, the solid was filtered off and washed with ether. The compound was dried under vacuum and kept over I50 yield 24 g. (81 percent).
An example for the preparation of a tertiary amine-BF, adduct having the formula:
wherein 0.8 moles of dry ether were placed in a three-neck flask and BF, was passed in through a glass-fritted tube until vapors of BF, could be detected above the solution; some more ether was then added to convert all excess BF, to the BF etherate. To this solution 0.8 moles of dimethyldodecylamine were added under stirring. The ether was then removed under aspirator vacuum. After this, all remaining BF -etherate was distilled off under oil pump vacuum at 80 C. The residue crystallized at room temperature and was recrystallized from heptane; white flakes.
An example for the preparation of an oxyfluoborobetaine having the formula:
(according to H. Meerwein et al., J. Prakt. Chem. (2) 154,83 (i940)), wherein 0.25 moles of and 0.25 moles of dodeceneoxide were heated under stirring in a C. oil bath. At 70-75 C. the reaction starts with an exothenn, which takes the mixture of about llS-l20 C. At the same time the color changes from a pale yellow to the color of honey. The compound is a rather viscous liquid at 90 C. and vaselinelike at room temperature.
An example for the preparation of a sulfobetaine (according to J. H. Helberger, Ann. 588, H (1954)) wherein 6. I07 g. y-propanesultone and 10.65 g. dimethyldodecylamine are heated in about 50 ml. xylene. At -9$C. an exothermic reaction starts under precipitation of the desired compound. The mixture is taken to ca. C. and held there for 10 mins. to complete the reaction. After cooling to room temperature the solvent is removed by filtering; The residue is stirred with acetone (Which facilitates filtering), filtered and washed several times with acetone. The compound is then dried under vacuum at about 60-70 C.; white solid.
Another class of compounds within the scope of the present invention are the substituted ureas having the formula:
wherein R is a hydrocarbon group, and R R and R are hydrogen or hydrocarbon groups, preferably with one or more of the R-groups consisting of hydrocarbon chains from about eight to about 30 carbon atoms. Any of the R-groups may contain one or more functional groups such as hydroxyl, carboxyl, etc. Also included are derivatives of biuret, guanidine and similar compounds.
The following is an example for the preparation of a substituted urea having the formula [(-CH1)NH-CO-NH- C.-,Hz:,]2:l8.5 g. dodecylamine and 8.4 g. hexamethylene diisocyanate are dissolved separately in heptane and then the isocyanate solution is added to the amine solution with good stirring. The product precipitates out immediately. It is filtered off and washed thoroughly with heptane; white solid.
Still further, the invention includes any of the metal salts which form stable complexes with amines. The amino nitrogen can carry at least one hydrocarbon group with or without other functional or complexing groups. Preferably the hydrocarbon group contains from about eight to 30 carbon atoms. An example of such a compound is the zinc complex:
The preparation of the potential base compounds is not new, and the general methods can be found in e.g., Houben Weyl, Methoden der organischen Chemie, Vol. XI/Z, Stuttgart Georg Thieme Verlag, 1958, pp. 59l-6l3 (for quaternary ammonium compo including betaines and betaine unds analogues), Vol. VIII (1952), pp. l57-l58 (for substituted ureas), pp. 180-l83 (for substituted guanidinium salts), Vol. III (1958 pp. 39l-4 ID (for urea clathrates The synthesis of sulfobetaines can be found in: R. F. Fischer, Ind. & Eng. Chem. Vol. 56, No. 3, p. 44 I964) etc.
The following examples are presented solely to illustrate the invention and should not be regarded as limiting in any way. In the examples, the parts and percentages are by weight unless otherwise indicated.
Amine precursor compounds were evaluated, by incorporation at an 0.3 percent level into a propellant consisting of 86 percent solids [76 percent ammonium perchlorate, and I0 percent powdered aluminum). The additive replaced an equivalent amount of the binder. Direct addition of the respective amine precursor compound to the binder is preferred, though in special cases the oxidizer was precoated with the material. Processing was done at ll5-l25" F. The propellants were cured at I35 F. in bulk for preparation of solid strands. Since the response of a propellant towards such bumingrate modifiers depends strongly on the binder, two representative binders were used for testing.
Binder No. l
Polypropylene ether diol 28.435 Polypropylene ether triol 4| 10% llodecylpelsrgonst: 25 00% Hes-methylene diisocyannte (I07 eqsIlOOeqs ON) 5475 N-phenyl belannphtliylsmine 011i Catalyst is either FeAA (0.015-003 percent) or dibutyltindilaurate (0.05 percent).
Binder No. 2
Carbosy-terminated polybutadiene (IOOeqs) sans Trimethyllziridine phosphine oxide (I20 eql] 2.07% lsodecylpelargonate 30.0%
The following compounds are a few examples of those synthesized and tested:
In the Binder No. 1 system (FIG. I) it is seen that the 3) (f) is more effective than the iodide (3) of an identical cation. If compared with the iodide series [RN(CII,),] I when R I) C,,H, and (2) C H then compound (e) R=C,,,l-I, is the least effective, whereas (2) R==C,,l-l is the most effective. The mole concentrations of these compounds are 2.82, 2.43 and L48 respectively. The effectiveness passes through a maximum. The bromides (b) and (c) (FIG. 2) (Binder No. l)compare favorably with any of the other compounds.
Sulfobetaines of the following formula were used in Binder No. l (FIG. 3), and Binder No. 12 (FIG. 4):
In addition to the two compounds with R,=C,,I-I,,, and R,=C,,,H and R,=R,=-CH;,R,( CH, a compound with R,=C,,,H was prepared, which proved to be the most effective one in both systems (FIGS. 3 and 4).
Ureas of the formula:
WITH R and R hydrocarbon was used.
The following compounds were prepared and tested:
The results are shown in FIGS. 5-8. In both systems. Binder No. I (FIGS. 5 and 6) and Binder No. 2 (FIGS. 7 and 8), it is seen that these compounds indeed are burning rate modifiers though not as effective as the previous ones.
The following compound was prepared according to Ralston et al. .I. AM. Oil Chemists Soc., 24, page 307:
Mixtures of the above compound with AP (CD-blend) showed final decomposition DTA exotherm at 355 C.
One of the most eflective burning-rate depressants reported in the prior art is oxamide. Oxamide was incorporated into standard propellants at a l.5 level and compared with the ad ditives of this invention at an 0.3 percent level. The results are shown in FIGS. 9 (Binder No. 2) and 10 (Binder No. I). For the Binder No. 2 system the quaternary ammonium salt is more than five times as effective as the oxamide. In the Binder No. 1 system, the sulfobetaine shown is even more effective.
The scope of the invention is not limited to amine derivatives; actually any potential base as defined there will be effective although the most powerful burning-rate depressants are derived from amines. An example for this are depressants derived from carboxylic acid salts, preferably from such which are relatively strong acids (e.g., by a-substitution with electron withdrawing groups):
wherein R alkyl or aryl (preferably long hydrocarbon chains, e.g., C I-I, and longer); R, preferably -OH; R,=I'I or aryl and Y preferably cations of the alkali or alkaline earth metals, like Li, Na, K, Mg, Ca Sr and Ba.
A example for the preparation of a carboxylic acid salt is Libenzilate wherein 0.05 moles of benu'lic acid are dissolved in warm methanol and a solution of 1.2 g. LiOH (in just enough methanol to dissolve it) is added. The Li-salt crystallizes out at room temperature and can be recrystallized from isopropanol. (Benzilic acid can be either purchased or made according to "Organic Synthesis" Collective Vol. I, p. 89 (1958 publ. John Wiley & Sons, Inc., New York.
As used herein, potential base means that free bases will not only be released from real chemical compounds, but also from adsorbates, clathrates (inclusion compounds) etc. An example for the latter are amine/urea inclusion compounds, where the amine is contained in channel structures formed by the urea crystal lattice. At the m.p. of the urea (about 130 C.), the amine is released and is free to difl'use through the binder to the NI-LC I 0, particles.
An example for the preparation of an alkylamine ureaclathrate is where 40 g. of urea are dissolved in I00 ml. 10.4 methanol, then I04 3. dimethyloctadecylamine are added under stirring; the clathrate crystallizes out on cooling under continued stirring. It is filtered off at room temperature, washed with ice cold methanol and dried under vacuum at room temperature. Titration of the clathrate showed that it contained 75 moles amine per g. clathrate or 22.3 g. amine per 100 g. clathrate.
The present invention is applicable to all types of ammonium perchlorate containing solid propellants including those having polymeric binders derived from polyether-diols, -trio|s etc., and polybutadiene-diols, -triols etc. with isocyanates as curatives (polyurethanes), or derived from polybutadienedicarboxylic acids and aziridines or aziridine derivatives as curatives. The propellants may contain fuels such as aluminum, plasticizers, stabilizers and the like. Many propellant formulations and their processing techniques are disclosed in assignees prior patents including US. Pat. Nos. 3,245,849 and 3,340,] l l the disclosure of which are expressly incorporated herein by reference.
Having fully described the invention, it is intended that it be limited only by the lawful scope of the appended claims.
We claim:
I. A novel solid ammonium perchlorate containing rocket propellant composition containing a polymeric organic binder and an effective buming-rate depressing amount of a potential base which is stable under normal solid propellant curing conditions but which upon combustion of the propellant undergoes conversion to form at least some free base, said potential base being an organic nitrogen compound and present in an amount from about 0.0l percent to about 5 percent by weight of the propellant.
2. In solid rocket propellants comprising a cross-linked high molecular weight polymeric binder and an ammonium perchlorate oxidizing agent, the improvement wherein said propellant contains an effective burning-rate depressing amount of a potential base which is stable under the normal curing conditions for solid rocket propellants but which is capable upon combustion of said propellant of conversion to form at least some free base, said potential base being an organic nitrogen compound and present in an amount from about 0.01 percent to about percent by weight of the propelan ammonium salt of an organic amine.
8. The composition of claim I wherein the potential base is a quaternary ammonium salt.
9. The composition of claim 1 wherein the potential base is a zwitterionic betaine-type compound.
10. The composition of claim 1 wherein the potential base comprises a substituted organic urea.
IL A method of fonning a novel solid rocket propellant comprises forming a castabie mixture of a curable polymeric binder, ammonium perchlorate, and a potential base, and thereafter casting the mixture and permitting it to set to form a solid rocket propellant having a depressed burning rate, said potential base being an organic nitrogen compound and present in an amount from about 0.01 percent to about 5 percent by weight of the propellant.
12. The method of claim ll wherein the potential base is an organic amine precursor.
Claims (11)
- 2. In solid rocket propellants comprising a cross-linked high molecular weight polymeric binder and an ammonium perchlorate oxidizing agent, the improvement wherein said propellant contains an effective burning-rate depressing amount of a potential base which is stable under the normal curing conditions for solid rocket propellants but which is capable upon combustion of said propellant of conversion to form at least some free base, said potential base being an organic nitrogen compound and present in an amount from about 0.01 pErcent to about 5 percent by weight of the propellant.
- 3. The composition of claim 1 wherein the propellant additionally contains a finely divided metal fuel.
- 4. The composition of claim 1 wherein the propellant contains a polyurethane binder.
- 5. The composition of claim 1 wherein the propellant contains a binder comprising a carboxy-terminated polydiolefin cross-linked with aziridines or their derivatives respectively.
- 6. The composition of claim 1 wherein the potential base is an organic amine precursor.
- 7. The composition of claim 1 wherein the potential base is an ammonium salt of an organic amine.
- 8. The composition of claim 1 wherein the potential base is a quaternary ammonium salt.
- 9. The composition of claim 1 wherein the potential base is a zwitterionic betaine-type compound.
- 10. The composition of claim 1 wherein the potential base comprises a substituted organic urea.
- 11. A method of forming a novel solid rocket propellant comprises forming a castable mixture of a curable polymeric binder, ammonium perchlorate, and a potential base, and thereafter casting the mixture and permitting it to set to form a solid rocket propellant having a depressed burning rate, said potential base being an organic nitrogen compound and present in an amount from about 0.01 percent to about 5 percent by weight of the propellant.
- 12. The method of claim 11 wherein the potential base is an organic amine precursor.
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US5942720A (en) * | 1993-04-29 | 1999-08-24 | Cordant Technologies Inc. | Processing and curing aid for composite propellants |
US6004466A (en) * | 1997-09-25 | 1999-12-21 | Rhodia Inc. | Recovery and reuse of sugar-derived nonionic surfactants from aqueous solutions |
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US3024144A (en) * | 1958-12-29 | 1962-03-06 | Phillips Petroleum Co | Solid composite propellants containing diamine dinitrates |
US3291660A (en) * | 1963-01-24 | 1966-12-13 | Aerojet General Co | Polyurethane propellant formulations and process |
US3214304A (en) * | 1963-03-20 | 1965-10-26 | Thiokol Chemical Corp | Gas-generating compositions containing coolants and methods for their use |
US3340111A (en) * | 1963-03-26 | 1967-09-05 | Aerojet General Co | Solid propellant catalyzed with copper-chromium complex |
US3266959A (en) * | 1965-05-05 | 1966-08-16 | Avery W Ackley | Stabilized polyurethane propellants containing aluminum |
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US5942720A (en) * | 1993-04-29 | 1999-08-24 | Cordant Technologies Inc. | Processing and curing aid for composite propellants |
US5654480A (en) * | 1995-05-19 | 1997-08-05 | Rhone-Poulenc Surfactants & Specialties, L.P. | Recovery and reuse of surfactants from aqueous solutions |
US5919980A (en) * | 1995-05-19 | 1999-07-06 | Rhodia Inc. | Recovery and reuse of amphoteric surfactants from aqueous solutions |
US6004466A (en) * | 1997-09-25 | 1999-12-21 | Rhodia Inc. | Recovery and reuse of sugar-derived nonionic surfactants from aqueous solutions |
US6013185A (en) * | 1997-09-25 | 2000-01-11 | Rhodia Inc. | Recovery and reuse of nonionic surfactants from aqueous solutions |
US6361630B2 (en) * | 1999-08-17 | 2002-03-26 | Trw Inc. | Cool burning gas generating composition |
CN111440073A (en) * | 2020-04-24 | 2020-07-24 | 湖北航天化学技术研究所 | Synthetic method and application of combustion speed regulator |
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