US3896865A - Propellant with polymer containing nitramine moieties as binder - Google Patents
Propellant with polymer containing nitramine moieties as binder Download PDFInfo
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- US3896865A US3896865A US435073A US43507374A US3896865A US 3896865 A US3896865 A US 3896865A US 435073 A US435073 A US 435073A US 43507374 A US43507374 A US 43507374A US 3896865 A US3896865 A US 3896865A
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- 239000003380 propellant Substances 0.000 title claims abstract description 66
- 229920000642 polymer Polymers 0.000 title claims abstract description 51
- 239000011230 binding agent Substances 0.000 title abstract description 30
- POCJOGNVFHPZNS-ZJUUUORDSA-N (6S,7R)-2-azaspiro[5.5]undecan-7-ol Chemical group O[C@@H]1CCCC[C@]11CNCCC1 POCJOGNVFHPZNS-ZJUUUORDSA-N 0.000 title 1
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 239000002131 composite material Substances 0.000 claims description 31
- 239000000020 Nitrocellulose Substances 0.000 claims description 22
- 229920001220 nitrocellulos Polymers 0.000 claims description 22
- 239000007800 oxidant agent Substances 0.000 claims description 16
- 239000004449 solid propellant Substances 0.000 claims description 16
- 239000000446 fuel Substances 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- SNIOPGDIGTZGOP-UHFFFAOYSA-N Nitroglycerin Chemical compound [O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O SNIOPGDIGTZGOP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002360 explosive Substances 0.000 claims description 5
- 229960003711 glyceryl trinitrate Drugs 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- LYAGTVMJGHTIDH-UHFFFAOYSA-N diethylene glycol dinitrate Chemical compound [O-][N+](=O)OCCOCCO[N+]([O-])=O LYAGTVMJGHTIDH-UHFFFAOYSA-N 0.000 claims description 4
- HJXJFWKJCUQSFM-UHFFFAOYSA-N 2-(hydroxymethyl)-2-methylpropane-1,3-diol nitric acid Chemical compound O[N+]([O-])=O.O[N+]([O-])=O.O[N+]([O-])=O.CC(CO)(CO)CO HJXJFWKJCUQSFM-UHFFFAOYSA-N 0.000 claims description 3
- 239000000006 Nitroglycerin Substances 0.000 claims description 3
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000002585 base Substances 0.000 description 14
- 238000009472 formulation Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- UZGLIIJVICEWHF-UHFFFAOYSA-N octogen Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)CN([N+]([O-])=O)C1 UZGLIIJVICEWHF-UHFFFAOYSA-N 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- -1 lithium aluminum hydride Chemical compound 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- RUKISNQKOIKZGT-UHFFFAOYSA-N 2-nitrodiphenylamine Chemical compound [O-][N+](=O)C1=CC=CC=C1NC1=CC=CC=C1 RUKISNQKOIKZGT-UHFFFAOYSA-N 0.000 description 1
- BJEMXPVDXFSROA-UHFFFAOYSA-N 3-butylbenzene-1,2-diol Chemical group CCCCC1=CC=CC(O)=C1O BJEMXPVDXFSROA-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- AGUIVNYEYSCPNI-UHFFFAOYSA-N N-methyl-N-picrylnitramine Chemical group [O-][N+](=O)N(C)C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O AGUIVNYEYSCPNI-UHFFFAOYSA-N 0.000 description 1
- KYIMHWNKQXQBDG-UHFFFAOYSA-N N=C=O.N=C=O.CCCCCC Chemical compound N=C=O.N=C=O.CCCCCC KYIMHWNKQXQBDG-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- 229910001485 alkali metal perchlorate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 235000017168 chlorine Nutrition 0.000 description 1
- 125000001309 chloro group Chemical class Cl* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000001087 glyceryl triacetate Substances 0.000 description 1
- 235000013773 glyceryl triacetate Nutrition 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QCOXCILKVHKOGO-UHFFFAOYSA-N n-(2-nitramidoethyl)nitramide Chemical compound [O-][N+](=O)NCCN[N+]([O-])=O QCOXCILKVHKOGO-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical class [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- 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
- C06B45/105—The resin being a polymer bearing energetic groups or containing a soluble organic explosive
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
Definitions
- Solid propellants are usually made of the three basic ingredients: (1) oxidizer, (2) fuel, and (3) binder. Two or even three of these may be contained in the same material.
- a convenient way to divide solid propellants into classes is according to physical state, i.e., homogeneous (single-base or double-base) and composite.
- a single-base propellant contains nitrocellulose as the main ingredient with a stabilizer such as diphenylamine added, as well as other conventional additives depending on the application.
- Single-base propellants are used primarily in gun applications and cartridge-actuated devices.
- Double-base propellants have two principal ingredients nitrocellulose and nitroglycerine, and may have various conventional ingredients as stabilizers, burning rate modifiers, extrusion lubricants and flash suppressors. When additional oxidizers are added to the double-base propellant, one has a composite modified double-base propellant.
- Composite propellants are generally composed of an oxidizer and a fuel and/or binder. Well-known oxidizers and fuels are used.
- the binder material in composite propellants usually is a polymeric material and nitrocellulose is the most commonly known and used binder component.
- nitrocellulose finds wide use in all types of propellant formulations.
- the use of nitrocellulose as a binder in gun propellants results in a high flame temperature and low gas output, both of which are undesirable features.
- the replacement of nitrocellulose in gun propellants with a rubber binder gives better flame temperature and gas output, it requires large amounts of output for efficient propellant combustion.
- nitrocellulose offers high energy it generally gives poor low temperature mechanical properties and relatively high sensitivity.
- the use of a rubber binder for these composite propellants improves the low temperature mechanical properties and sensitivity but such propellants are less energetic and less efficient than those based on nitrocellulose.
- Still another object of the instant invention is to produce a binder for propellant compositions which is compatible with other propellant ingredients.
- novel binder polymer of the instant invention is a-hydro-w-hydroxy poly (oxymethylenenitramino),
- EDNAP EDNAP
- any molecular weight polymer will suffice so long as the polymer is operable for binder purposes, it is preferred to use a polymer of a molecular weight of from about 750 to about 3,000, or more preferably from about 1,000 to about 2,500.
- This type of polymer is synthesized by reacting l,6-dichloro-2,5-dinitrazahexane (DCDNH) with a polyhydroxy alcohol, exemplified by ethylene glycol.
- DCDNH l,6-dichloro-2,5-dinitrazahexane
- the polymer is thermally stable and can be crosslinked with hexane diisocyanate to form a rubbery gumstock.
- the DCDNH which reacts with the polyfunctional alcohol, is prepared by reacting ethylene dinitramine with formaldehyde and hydrogen chloride in acetic acid at about 0 C.
- the DCDNH is usually recrystallized from benzene before preparing the polymer.
- the bulk reaction between DCDNH and the polyol may be carried out between room temperature and C., but the range of 4060 C. is preferred.
- the ratio of hydroxyls to chlorines in the respective reactants may be 1.0 to 1.3. Operation under reduced pressure is desirable so as to rapidly remove the hydrogen chloride generated by the reaction and thereby prevent its reaction with the poly-ol.
- the prepolymer Prior to use in propellant formulations, the prepolymer should be thoroughly washed with base.
- EDNAP when crosslinked, will form a high energy, low glass transition temperature binder which is nearly oxygen balanced and will form low molecular weight products upon combustion.
- the properties of EDNAP are compared to nitrocellulose and butarez II (a rubber binder) in Table I, below.
- Butare1 is not a monopropcllant
- the low flame temperature and high gas output of EDNAP is ideal for gun propellant applications.
- propellants with about 20 percent EDNAP as a binder with other well-characterized compounds have a calculated impetus of up to 420,000 ft-lb/lb at 2,70 OK. This is a 25 percent gain over Olin ball powder which is presently used for many gun propellant applications.
- EDNAP solid rocket propellants
- Table 11 shows two formulations which are comparable to composite modified doublebase (CMDB) propellants in impulse.
- CMDB composite modified doublebase
- the advantages of the EDNAP binder rocket propellants are their expected good low temperature mechanical properties and lower sensitivity compared to the CMDB propellants.
- the cured polymer is generally used.
- the polymer can be cured with any conventional curing agent such as any of the crosslinking polyfunctional isocyanates. Exemplary are toluene diisocyanate and hexan'e diisocyanate, to name just a few of the many conventional crosslinking agents readily available.
- a wide variety of propellant compositions can be made using the cured prepolymer as the binder. It is preferred to use the EDNAP in double-base and composite type propellants, rather than in single-base propellants. In a composite propellant the amount of EDNAP present is about 10 25 percent by weight of the propellant composition.
- conventional fuels such as aluminum, beryllium, zirconium, magnesium, boron, and their corresponding hydrides, as well as lithium, and lithium aluminum hydride
- conventional fuels such as aluminum, beryllium, zirconium, magnesium, boron, and their corresponding hydrides, as well as lithium, and lithium aluminum hydride
- Conventional oxidizers such as cyclotetramethylenetetranitramine (RDX), and ammonium and alkali metal nitrates or perchlorates may be present in amounts ranging from about 55 to 90 percent. With respect to the latter, it would be preferable to have from 55 to 80 percent of oxidizer because it is desired to have at least 10 percent of fuel present in the composition, although the propellants would be operative in the absence of the fuels.
- RDX cyclotetramethylenetetranitramine
- ammonium and alkali metal nitrates or perchlorates may be present in amounts ranging from about 55 to 90
- any of the conventional additives such as plasticizers, curing agents, stabilizers, burning rate additives, catalysts, etc.
- plasticizers any of the conventional additives such as plasticizers, curing agents, stabilizers, burning rate additives, catalysts, etc.
- the amount of curing agent necessary to crosslink the polymer is not critical and generally conventional amounts of about 1 to about 6 percent will suffice.
- the EDNAP usually the EDNAP may be plasticized with up to twice its weight with energetic materials like nitroglycerine or diethylene glycol dinitrate.
- a satisfactory propellant can be obtained by replacing up to about one half of the nitrocellulose with EDNAP.
- the typical double-base propellant will contain about 30-50 percent by weight of a high energy explosive such as nitroglycerin, diethylene glycol dinitrate, methyl trimethylolmethane trinitrate or others, and about 40 to about 60 percent of nitrocellulose
- the propellant compositions of the instant invention will con tain from about 1 to about 30 percent of EDNAP, replacing up to about one half of said nitrocellulose, usu' ally present in the'conventional type.
- the resulting propellant will have the polymer present in an amount equal to or less than the amount of nitrocellulose pres ent.
- plasticizers pthalates, triacetin, etc.
- stabilizers (2 -nitrodiphenylamine, tertiary butyl catechol, etc.
- burning rate modifiers lead salts, etc.
- extrusion lubricants stearates, soaps, etc.
- flash suppressors potassium salts, etc.
- EXAMPLE I 0.6 moles of DCDNI-I, 0.56 moles of ethylene glycol, and 0.1 1 moles of glycerol were reacted at 5060 C. for 24 hours at the low pressure level produced by a water aspirator. The cooled reaction mixture was dissolved in methylene chloride and washed successively with water, sodium bicarbonate solution, and finally sodium hydroxide solution. For drying, benzene was added to the solution and the total solvent was distilled. Last traces of solvent were removed by sparging with dry nitrogen at 60 C. The product, on analysis, was found to contain 0.19 percent water and to have an hydroxyl equivalent weight of 572.
- This composition has a calculated specific impulse of 265 seconds and a density of 0.065 lbs/in Its burning rate at 1,000 psi was 0.21 in/sec. 1
- a solid propellant composition which contains a cured polymer as a binder component therefor, said polymer being of the formula:
- composition of claim 1 wherein said composition is a composite type solid propellant comprising a propellant oxidizer and said polymer.
- the composite type solid propellant of claim 2 comprising an oxidizer, a fuel, and said polymer.
- the composite type solid propellant of claim 3 comprising from about 55-80 percent by weight of said oxidizer, from about to about percent by weight of said fuel, and from about 10 to about 25 percent by weight of said polymer.
- the composite type propellant of claim 4 comprising 12 percent of aluminum, 65 percent of HMX oxidizer and 19.2 percent of said polymer.
- the composite type propellant of claim 4 comprising 25 percent of said polymer, 50 percent of ammonium perchlorate oxidizer, and 25 percent of aluminum fuel.
- the composite type propellant of claim 4 comprising 20 percent of said polymer, 15 percent of aluminum fuel, and 65 percent of HMX oxidizer.
- the double-base type propellant of claim 10 comprising from about 30 to about 50 percent by weight of said high energy explosive, from about 10 to about 59 percent by weight of nitrocellulose and from about 1 to about 30 percent by weight of said polymer such that the amount of said polymer is equal to or less than the amount of nitrocellulose present.
Abstract
A novel binder for propellant compositions, and its method of preparation, said binder being a polymer of the formula:
and novel propellant compositions thereof.
and novel propellant compositions thereof.
Description
ite
ttes atet 1 Comfort et al.
1 July 29, 1975 The United States of America as represented by the Secretary of the Navy, Washington, DC.
Filed: Jan. 21, 1974 Appl. No.: 435,073
Related U.S. Application Data Division of Ser. No. 219,183, Jan. 19, 1972, Pat. No. 3,808,276.
Assignee:
U.S. Cl. 149/19.4; 149/19.6; l49/l9.8; 149/20; 149/92; 149/96; 149/97 Int. Cl. C06D 5/06 Field of Search 149/96, 97, 92, 20, 19.6, l49/l9.4, 19.8
References Cited UNITED STATES PATENTS 2/1964 Gey et a1. 149/92 X 3,151,164 9/1964 Sammons 149/92 X 3,609,115 9/1971 Sammons et al.... 149/92 X 3,711,344 1/1973 Pierce 149/19.8 3,726,729 4/1973 Pierce 149/19.8 3,756,874 9/1973 Chang ct al l49/l9.4 3,793,099 2/1974 Duerksen et a1 l49/19.4
Primary Examiner-Benjamin R. Padgett Assistant Examiner-E. A. Miller Attorney, Agent, or FirmR. S. Sciascia; .l. A. Cooke 5 7 ABSTRACT A novel binder for propellant compositions, and its method of preparation, said binder being a polymer of the formula:
H (001,1 1 cH,cH,1 1 c11 0 ctnci-nipn.
and novel propellant compositions thereof.
13 Claims, No Drawings PROPELLANT WITH POLYMER CONTAINING NITRAMINE MOIETIES AS BINDER This is a division of application Ser. No. 219,183, filed Jan. 19, 1972, now US. Pat. No. 3,808,276.
BACKGROUND OF THE INVENTION Solid propellants are usually made of the three basic ingredients: (1) oxidizer, (2) fuel, and (3) binder. Two or even three of these may be contained in the same material. A convenient way to divide solid propellants into classes is according to physical state, i.e., homogeneous (single-base or double-base) and composite. A single-base propellant contains nitrocellulose as the main ingredient with a stabilizer such as diphenylamine added, as well as other conventional additives depending on the application. Single-base propellants are used primarily in gun applications and cartridge-actuated devices. Double-base propellants have two principal ingredients nitrocellulose and nitroglycerine, and may have various conventional ingredients as stabilizers, burning rate modifiers, extrusion lubricants and flash suppressors. When additional oxidizers are added to the double-base propellant, one has a composite modified double-base propellant. Composite propellants are generally composed of an oxidizer and a fuel and/or binder. Well-known oxidizers and fuels are used.
The binder material in composite propellants usually is a polymeric material and nitrocellulose is the most commonly known and used binder component. Thus, nitrocellulose finds wide use in all types of propellant formulations. However, the use of nitrocellulose as a binder in gun propellants results in a high flame temperature and low gas output, both of which are undesirable features. While the replacement of nitrocellulose in gun propellants with a rubber binder gives better flame temperature and gas output, it requires large amounts of output for efficient propellant combustion. Moreover, in solid rocket propellants and other composite propellants, while nitrocellulose offers high energy it generally gives poor low temperature mechanical properties and relatively high sensitivity. The use of a rubber binder for these composite propellants improves the low temperature mechanical properties and sensitivity but such propellants are less energetic and less efficient than those based on nitrocellulose.
SUMMARY OF THE INVENTION It is an object of this invention to obtain a new binder for propellant compositions, and a method of preparing such a binder.
It is an additional object of the instant invention to obtain a new binder for propellant compositions which has a low flame temperature.
It is a further object of the present invention to obtain a new binder for propellant compositions with a high gas output.
It is still another object of the instant invention to produce propellant compositions which have good low temperature mechanical properties.
It is yet another object of the instant invention to produce a propellant having low sensitivity.
It is still another object of the invention to produce a binder for propellant compositions which is thermally stable.
Still another object of the instant invention is to produce a binder for propellant compositions which is compatible with other propellant ingredients.
It is an additional object of the present invention to produce a binder for propellant compositions which can be used as a replacement for or additive to a nitrocellulose binder.
These and other objects are accomplished by the use of a new polymer binder which offers the desirable advantages of both nitrocellulose and rubber binders, in solid propellants such as gun propellants and rocket propellants.
The objects, advantages, and novel features of the invention will become apparent from the following detailed description.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The novel binder polymer of the instant invention is a-hydro-w-hydroxy poly (oxymethylenenitramino),
and is designated as EDNAP. While any molecular weight polymer will suffice so long as the polymer is operable for binder purposes, it is preferred to use a polymer of a molecular weight of from about 750 to about 3,000, or more preferably from about 1,000 to about 2,500. This type of polymer is synthesized by reacting l,6-dichloro-2,5-dinitrazahexane (DCDNH) with a polyhydroxy alcohol, exemplified by ethylene glycol. The polymer is thermally stable and can be crosslinked with hexane diisocyanate to form a rubbery gumstock.
A more detailed description of the preparation is as follows. The DCDNH, which reacts with the polyfunctional alcohol, is prepared by reacting ethylene dinitramine with formaldehyde and hydrogen chloride in acetic acid at about 0 C. The DCDNH is usually recrystallized from benzene before preparing the polymer. The bulk reaction between DCDNH and the polyol may be carried out between room temperature and C., but the range of 4060 C. is preferred. The ratio of hydroxyls to chlorines in the respective reactants may be 1.0 to 1.3. Operation under reduced pressure is desirable so as to rapidly remove the hydrogen chloride generated by the reaction and thereby prevent its reaction with the poly-ol. Prior to use in propellant formulations, the prepolymer should be thoroughly washed with base.
EDNAP, when crosslinked, will form a high energy, low glass transition temperature binder which is nearly oxygen balanced and will form low molecular weight products upon combustion. The properties of EDNAP are compared to nitrocellulose and butarez II (a rubber binder) in Table I, below.
Table l-Continued Nitrocellulose Butarcz EDNAP (12.67:) 11
Flame Tcmp. 1.800 3.435
(K) Gas Output 5.4 4.0
mo1es/l00,gms Density. gm/cc 1.36 1.66 0.90
Butare1 is not a monopropcllant The low flame temperature and high gas output of EDNAP is ideal for gun propellant applications. For example, propellants with about 20 percent EDNAP as a binder with other well-characterized compounds have a calculated impetus of up to 420,000 ft-lb/lb at 2,70 OK. This is a 25 percent gain over Olin ball powder which is presently used for many gun propellant applications.
1n solid rocket propellants EDNAP also calculates well. For example, Table 11 shows two formulations which are comparable to composite modified doublebase (CMDB) propellants in impulse. The advantages of the EDNAP binder rocket propellants are their expected good low temperature mechanical properties and lower sensitivity compared to the CMDB propellants.
"In use in solid propellants, the cured polymer is generally used. The polymer can be cured with any conventional curing agent such as any of the crosslinking polyfunctional isocyanates. Exemplary are toluene diisocyanate and hexan'e diisocyanate, to name just a few of the many conventional crosslinking agents readily available. A wide variety of propellant compositions can be made using the cured prepolymer as the binder. It is preferred to use the EDNAP in double-base and composite type propellants, rather than in single-base propellants. In a composite propellant the amount of EDNAP present is about 10 25 percent by weight of the propellant composition. In these composite types, conventional fuels, such as aluminum, beryllium, zirconium, magnesium, boron, and their corresponding hydrides, as well as lithium, and lithium aluminum hydride, may be used in amounts varying from to 25 percent by weight, preferably at least about percent by weight. Conventional oxidizers, such as cyclotetramethylenetetranitramine (RDX), and ammonium and alkali metal nitrates or perchlorates may be present in amounts ranging from about 55 to 90 percent. With respect to the latter, it would be preferable to have from 55 to 80 percent of oxidizer because it is desired to have at least 10 percent of fuel present in the composition, although the propellants would be operative in the absence of the fuels. In addition to the oxidizer, EDNAP and fuel, any of the conventional additives such as plasticizers, curing agents, stabilizers, burning rate additives, catalysts, etc., are also possible components of the composite formulation The amount of curing agent necessary to crosslink the polymer is not critical and generally conventional amounts of about 1 to about 6 percent will suffice. With respect to the amount of plasticizer present, usually the EDNAP may be plasticized with up to twice its weight with energetic materials like nitroglycerine or diethylene glycol dinitrate.
In a double-base type propellant, a satisfactory propellant can be obtained by replacing up to about one half of the nitrocellulose with EDNAP. Thus, while the typical double-base propellant will contain about 30-50 percent by weight of a high energy explosive such as nitroglycerin, diethylene glycol dinitrate, methyl trimethylolmethane trinitrate or others, and about 40 to about 60 percent of nitrocellulose, the propellant compositions of the instant invention will con tain from about 1 to about 30 percent of EDNAP, replacing up to about one half of said nitrocellulose, usu' ally present in the'conventional type. The resulting propellant will have the polymer present in an amount equal to or less than the amount of nitrocellulose pres ent. Conventional additives, such as plasticizers (pthalates, triacetin, etc.), stabilizers (2 -nitrodiphenylamine, tertiary butyl catechol, etc.), burning rate modifiers (lead salts, etc.), extrusion lubricants (stearates, soaps, etc.), and flash suppressors (potassium salts, etc.) may also be added. g
The following examples illustrate the method of obtaining the novel polymer as well as some propellant formulations utilizing the novel polymer.
EXAMPLE I 0.6 moles of DCDNI-I, 0.56 moles of ethylene glycol, and 0.1 1 moles of glycerol were reacted at 5060 C. for 24 hours at the low pressure level produced by a water aspirator. The cooled reaction mixture was dissolved in methylene chloride and washed successively with water, sodium bicarbonate solution, and finally sodium hydroxide solution. For drying, benzene was added to the solution and the total solvent was distilled. Last traces of solvent were removed by sparging with dry nitrogen at 60 C. The product, on analysis, was found to contain 0.19 percent water and to have an hydroxyl equivalent weight of 572.
EXAMPLE II A propellant formulation was prepared in the laboratory of the following composition:
This composition has a calculated specific impulse of 265 seconds and a density of 0.065 lbs/in Its burning rate at 1,000 psi was 0.21 in/sec. 1
EXAMPLES Il1lV The two formulations set forth at Table I1, supra, are additional examples of propellant compositions in which EDNAP is incorporated.
Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims the invention may be practiced otherwise than as specifically described herein.
What is claimed as new and desired to be secured by Letters Patent of the United States is:
l. A solid propellant composition which contains a cured polymer as a binder component therefor, said polymer being of the formula:
2. The solid propellant composition of claim 1, wherein said composition is a composite type solid propellant comprising a propellant oxidizer and said polymer.
3. The composite type solid propellant of claim 2 comprising an oxidizer, a fuel, and said polymer.
4. The composite type solid propellant of claim 3 comprising from about 55-80 percent by weight of said oxidizer, from about to about percent by weight of said fuel, and from about 10 to about 25 percent by weight of said polymer.
5. The composite type propellant of claim 4 comprising 12 percent of aluminum, 65 percent of HMX oxidizer and 19.2 percent of said polymer.
6. The composite type propellant of claim 4 comprising 25 percent of said polymer, 50 percent of ammonium perchlorate oxidizer, and 25 percent of aluminum fuel.
7. The composite type propellant of claim 4 comprising 20 percent of said polymer, 15 percent of aluminum fuel, and 65 percent of HMX oxidizer.
8. The composite type polymer of claim 4 wherein said polymer is cured with a difunctional isocyanate.
9. The composite type polymer of claim 4 wherein the molecular weight of said polymer varies from about 750 to about 3,000.
10. A solid propellant composition according to claim 1 wherein said composition is a double-base type propellant containing said polymer, nitrocellulose, and a high energy explosive selected from the group consisting of nitroglycerin, diethylene glycol dinitrate, and methyl trimethylolmethane trinitrate.
11. The double-base type propellant of claim 10 comprising from about 30 to about 50 percent by weight of said high energy explosive, from about 10 to about 59 percent by weight of nitrocellulose and from about 1 to about 30 percent by weight of said polymer such that the amount of said polymer is equal to or less than the amount of nitrocellulose present.
12. The composite type composition of claim 11 wherein said polymer is cured with a difunctional isocyanate.
13. The composite type composition of claim 11 wherein the molecular weight of said polymer varies from about L000 to about 2,500.
Claims (13)
1. A SOLID PROPELLANT COMPOSITION WHICH CONTAINS A CURED POLYMER AS A BINDER COMPONENT THEREFOR, SAID POLYMER BEING OF THE FORMULA:
2. The solid propellant composition of claim 1, wherein said composition is a composite type solid propellant comprising a propellant oxidizer and said polymer.
3. The composite type solid propellant of claim 2 comprising an oxidizer, a fuel, and said polymer.
4. The composite type solid propellant of claim 3 comprising from about 55-80 percent by weight of said oxidizer, from about 10 to about 25 percent by weight of said fuel, and from about 10 to about 25 percent by weight of said polymer.
5. The composite type propellant of claim 4 comprising 12 percent of aluminum, 65 percent of HMX oxidizer and 19.2 percent of said polymer.
6. The composite type propellant of claim 4 comprising 25 percent of said polymer, 50 percent of ammonium perchlorate oxidizer, and 25 percent of aluminum fuel.
7. The composite type propellant of claim 4 comprising 20 percent of said polymer, 15 percent of aluminum fuel, and 65 percent of HMX oxidizer.
8. The composite type polymer of claim 4 wherein said polymer is cured with a difunctional isocyanate.
9. The composite type polymer of claim 4 wherein the molecular weight of said polymer varies from about 750 to about 3,000.
10. A solid propellant composition according to claim 1 wherein said composition is a double-base type propellant containing said polymer, nitrocellulose, and a high energy explosive selected from the group consisting of nitroglycerin, diethylene glycol dinitrate, and methyl trimethylolmethane trinitrate.
11. The double-base type propellant of claim 10 comprising from about 30 to about 50 percent by weight of said high energy explosive, from about 10 to about 59 percent by weight of nitrocelluLose and from about 1 to about 30 percent by weight of said polymer such that the amount of said polymer is equal to or less than the amount of nitrocellulose present.
12. The composite type composition of claim 11 wherein said polymer is cured with a difunctional isocyanate.
13. The composite type composition of claim 11 wherein the molecular weight of said polymer varies from about 1,000 to about 2,500.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US435073A US3896865A (en) | 1972-01-19 | 1974-01-21 | Propellant with polymer containing nitramine moieties as binder |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00219183A US3808276A (en) | 1972-01-19 | 1972-01-19 | Alpha-hydro-gamma-hydroxy poly(oxymethylenenitroamino)polymer |
US435073A US3896865A (en) | 1972-01-19 | 1974-01-21 | Propellant with polymer containing nitramine moieties as binder |
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US3896865A true US3896865A (en) | 1975-07-29 |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5028343A (en) * | 1989-02-09 | 1991-07-02 | Atochem North America, Inc. | Stabilized sulfur dissolving compositions |
US10415938B2 (en) | 2017-01-16 | 2019-09-17 | Spectre Enterprises, Inc. | Propellant |
US11112222B2 (en) | 2019-01-21 | 2021-09-07 | Spectre Materials Sciences, Inc. | Propellant with pattern-controlled burn rate |
US11650037B2 (en) | 2021-02-16 | 2023-05-16 | Spectre Materials Sciences, Inc. | Primer for firearms and other munitions |
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US3121748A (en) * | 1959-06-23 | 1964-02-18 | William A Gey | Long chain nitramine diols |
US3151164A (en) * | 1960-01-25 | 1964-09-29 | Phillips Petroleum Co | Nitraza thia polymer compositions |
US3609115A (en) * | 1963-09-30 | 1971-09-28 | North American Rockwell | Propellant binder |
US3711344A (en) * | 1970-09-23 | 1973-01-16 | Us Army | Processing of crosslinked nitrocellulose propellants |
US3726729A (en) * | 1965-06-30 | 1973-04-10 | Us Army | Solid propellant compositions having a nitrocellulose-hydroxyl-terminated polybutadiene binder and method of preparing the same |
US3756874A (en) * | 1969-07-01 | 1973-09-04 | Us Navy | Temperature resistant propellants containing cyclotetramethylenetetranitramine |
US3793099A (en) * | 1960-05-31 | 1974-02-19 | Aerojet General Co | Solid propellant with polyurethane binder |
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1974
- 1974-01-21 US US435073A patent/US3896865A/en not_active Expired - Lifetime
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
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US3121748A (en) * | 1959-06-23 | 1964-02-18 | William A Gey | Long chain nitramine diols |
US3151164A (en) * | 1960-01-25 | 1964-09-29 | Phillips Petroleum Co | Nitraza thia polymer compositions |
US3793099A (en) * | 1960-05-31 | 1974-02-19 | Aerojet General Co | Solid propellant with polyurethane binder |
US3609115A (en) * | 1963-09-30 | 1971-09-28 | North American Rockwell | Propellant binder |
US3726729A (en) * | 1965-06-30 | 1973-04-10 | Us Army | Solid propellant compositions having a nitrocellulose-hydroxyl-terminated polybutadiene binder and method of preparing the same |
US3756874A (en) * | 1969-07-01 | 1973-09-04 | Us Navy | Temperature resistant propellants containing cyclotetramethylenetetranitramine |
US3711344A (en) * | 1970-09-23 | 1973-01-16 | Us Army | Processing of crosslinked nitrocellulose propellants |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5028343A (en) * | 1989-02-09 | 1991-07-02 | Atochem North America, Inc. | Stabilized sulfur dissolving compositions |
US10415938B2 (en) | 2017-01-16 | 2019-09-17 | Spectre Enterprises, Inc. | Propellant |
US11112222B2 (en) | 2019-01-21 | 2021-09-07 | Spectre Materials Sciences, Inc. | Propellant with pattern-controlled burn rate |
US11650037B2 (en) | 2021-02-16 | 2023-05-16 | Spectre Materials Sciences, Inc. | Primer for firearms and other munitions |
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