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US3914139A - Propellant with very high burning rate acrylate polymer binder and NF plasticizer - Google Patents

Propellant with very high burning rate acrylate polymer binder and NF plasticizer Download PDF

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US3914139A
US3914139A US287164A US28716472A US3914139A US 3914139 A US3914139 A US 3914139A US 287164 A US287164 A US 287164A US 28716472 A US28716472 A US 28716472A US 3914139 A US3914139 A US 3914139A
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propellant composition
difluoramino
bis
propellant
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US287164A
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Marvin L Jones
David W Booth
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United States Department of the Army
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United States Department of the Army
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
    • C07D303/44—Esterified with oxirane-containing hydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
    • C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
    • C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides

Definitions

  • Difluoramino compounds belong to a class of compounds which are known to be useful as propellant ingredients for obtaining high density and high impulse.
  • Derivatives of carborane belong to a class of compounds which are known to be effective ballistic modifiers for obtaining high burning rates.
  • most derivatives of carborane are not miscible with the standard NF binder constituted of 1,2,3-tris-( 1,2-bisdifluoroamino) ethoxy propane (TVOPA) and 2,3- bis(difluoramino) propyl acrylate (NFPA).
  • the object of this invention is to provide a combination binder having carborane derivatives which are miscible with NF compounds which are also compatible with other propellant ingredients.
  • Another object is to provide composite propellants having the characteristic features of high'impulse, high density, and high burning rates while employing conventional ammonium perchlorate oxidizer grinds.
  • One representative propellant of this invention is constituted of a binder comprised of a blend of TVOPA and NFPA-carboranyl methyl acrylate (CMA)-acrylic acid (AA) terpolymer, an inorganic oxidizer of ammonium perchlorate, a curing agent and optionally, aluminum metal fuel.
  • a binder comprised of a blend of TVOPA and NFPA-carboranyl methyl acrylate (CMA)-acrylic acid (AA) terpolymer, an inorganic oxidizer of ammonium perchlorate, a curing agent and optionally, aluminum metal fuel.
  • Another representative propellant of this invention is constituted of a binder comprised of ethyl acrylate (EA)-acrylic acid (AA) copolymer (designated EA-AA), and a mixed plasticizer comprised of a blend of TVOPA and l-isopropenyl-carboranyl-acetone (IPCA), an inorganic oxidizer of ammonium perchlorate, a curing agent, and optionally, aluminum metal fuel.
  • EA ethyl acrylate
  • AA acrylic acid copolymer
  • IPCA l-isopropenyl-carboranyl-acetone
  • NF refers to NitrogemFluorine
  • NF propellants are those propellants containing the difluoramino group NF
  • TVOPA, IPCA, and NFPA resulting from research efforts in the NF and Carborane Chemistry fields, may be prepared by procedures set forth below.
  • TVOPA l,2,3-tris[ l ,2-bis(difluoramino)ethoxy] propane, is prepared by reacting tris(vinoxy)propane 2 with tetrafluorohydrazine.
  • TVOPA contains two high energy difluoramino groups, NF in each of the three vinoxy groups of the starting compound, tris(vinoxy)- propane.
  • the reaction of tetrafluorohydrazine with 5 tris(vinoxy)propane to form TVOPA is conducted under pressure in the range of 500 mm of mercury up to about 600 psig and temperature range of about 0 to 120C.
  • the reaction is conducted in the presence of an inert volatile organic solvent, preferably one that is a suitable solvent for both the TVOPA as well as the reactant.
  • an inert volatile organic solvent preferably one that is a suitable solvent for both the TVOPA as well as the reactant.
  • Aromatic and aliphatic hydrocarbons, chlorinated hydrocarbons, ethers and ketones may be employed as the solvent.
  • Typical solvents include diethyl ether, dipropyl ether, pentane, hexane, chloroform, carbon tetrachloride, methylene chloride, benzene, toluene, xylene, and acetone.
  • IPCA Hsopropenyl-carboranyl-acetone
  • Preparative procedure for IPCA is as follows: after flushing the reaction flask and accessory equipment, with dry nitrogen, 50 grams of isopropenylcarborane and 300 milliliters of anhydrous ethyl ether are combined in a three necked flask equipped with two addition funnels, cooling and heating accessory equipment, and accessory equipment for reflux procedure. Butyl lithium (171 milliliters of 1.60 molar) is placed into one addition funnel, and 40 milliliters of propylene oxide is placed in the other one.
  • the flask is cooled to 0C, and the butyl lithium is added dropwise. After the butyl lithium is added, the flask is heated to reflux and the propylene oxide is added dropwise. After the addition is complete, the flask is refluxed for an additional 1 )6 hours. Contents of the flask are then poured into a separatory funnel and washed with an equal portion of water. The water layer is drained off and discarded and the ether layer is washed with two ZOO-ml portions of 10% HCl in water. The acid layers are discarded and the ether layer dried over magnesium sulfate. The ether is removed on a rotary evaporator.
  • H C C C C-CHgCiCHg
  • Additional characteristics of IPCA are revealed by the NMR spectrum which consists of four absorptions centered at 1.95, 2.18, 3.07, and 5.57 ppm.
  • the 5.57 ppm absorption, due to the vinylic protons, has the gross appearance of a quartet (J 1 cps) and a singlet superimposed on one another.
  • the 3.07 and 2.18 ppm absorptions, due to the CH and CH of the acetone group are singlets while the 1.95 ppm peak assigned to isopropenyl CI-I group has the appearance ofa doublet (J 1 cps).
  • the difiuoramino groups in the specified reactant are positioned within the alcohol moiety of the compound and paired on vicinal carbon atoms.
  • the reactant is prepared by reacting propenyla,B-dibromopropionate with tetrafluorohydrazine at a temperature of about 50C to 120C.
  • a slightly exothermic heat of reaction 23C to 27C
  • an immediate precipitate of triphenylphosphine dibromide are noted.
  • the addition is completed within a -minute period.
  • the reaction is continued for a period of 24 hours.
  • the solids are removed by filtration, and the ether is removed at reduced pressure on a rotary evaporator.
  • the residue containing a small quantity of solids, is treated with 100 ml. of pentane and filtered again.
  • the pentane is removed and the residue first examined by gas chromatography and then distilled.
  • the gas chromatogram showed the product to be approximately 95% pure.
  • the product (b.p. 52C. 1.1 mm. of mercury) is obtained in a yield of 4.22 parts(67%).
  • the infrared spectrum of the product is identical in every respect to that of known 2,3-bis(difiuoramino)- propyl acrylate.
  • the product gives the following analysis:
  • IPCA ethyl acrylateacrylic acid
  • IPCA l-isopropenyl-carboranyI-acetone
  • Propellants with high ammonium perchlorate oxidizer concentrations are illustrated in Table III below. Increasing the oxidizer loading usually increases the density of propellant. Addition of aluminum will increase both density and impulse. Table III also illustrates that the density and impulse of a propellant can be increased with only a small loss in burning rate when NF compounds and aluminum are added to a carborane propellant.
  • the procedure for propellant mixing as conventionally used in the propellant manufacturing art is employed in making the propellant grains of this invention.
  • the propellant formulation ingredients are blended together under vacuum until a homogeneous mixture is obtained and then the propellant grain is formed and cured.
  • the metal powder is usually mixed with the binder or prepolymer [e.g., copolymers (EA-AA) or terpolymer (NFPA/CMA/AA)] and the mass mixed until the metal powder is wetted.
  • the inorganic oxidizing salt and additives are next added, and the mixture is mixed under vacuum until a homogeneous mixture is obtained.
  • the resulting mixture is cast into a suitable mold or rocket motor to form the propellant grain and to cure.
  • the grain is cured for several days at about 60C until a cured grain is obtained. The curing may vary somewhat, but generally in about 3 days the grain is properly cured.
  • the inorganic oxidizing salts which are useful in the solid propellant compositions of this invention are those oxygen containing salts which readily give up oxygen.
  • These oxidizing salts include ammonium, alkali metal, and alkaline earth metal salts of nitric, perchloric, and chloric acids, and mixtures thereof.
  • Representative of the oxidizing salts referred to are ammonium perchlorate, ammonium nitrate, sodium nitrate, potassium perchlorate, potassium chlorate, lithium perchlorate, lithium chlorate, calcium nitrate, calcium chlorate, barium perchlorate, strontium chlorate, and strontium perchlorate.
  • Ammonium perchlorate is preferred since less smoke results from lower solids present in exhaust gases from a rocket motor wherein used. Lower smoke solids is required for military purposes of concealment. Ammonium perchlorate of particle size from the range of about 8 microns to the range of about 55 microns is suitable for use in the propellant compositions of this invention to achieve the burning rates and special properties as disclosed in the Tables listed hereinabove.
  • Powdered metals, as additive, useful in the propellant compositions of this invention include in addition to aluminum, magnesium, titanium, zirconium, boron, and beryllium. Alloys and mixtures of the aforesaid metals may also be employed.
  • Aluminum metal powder is the preferred metal additive.
  • the ingredients of the propellants of this invention may be varied to provide propellants having a wide range of high densities, high impulses, and high burning rates. Satisfactory ranges for the ingredients are inorganic oxidizing salts from about 45 to about 76 weight percent, metal additive up to about 20 weight percent, ethyl acrylate from about 2 to about 7 weight percent, acrylic acid from about 0.20 to about 7 weight percent, TVOPA from about 4 to about 36 weight percent, carborane derivatives (e.g., lPCA and CMA) from about 3 to about 22 weight percent, NFPA up to about 10 weight percent, and curing agent in the range of about 1 to 2 parts per 100 parts of the total propellant ingredients.
  • inorganic oxidizing salts from about 45 to about 76 weight percent
  • metal additive up to about 20 weight percent
  • ethyl acrylate from about 2 to about 7 weight percent
  • acrylic acid from about 0.20 to about 7 weight percent
  • TVOPA from about 4 to about 36 weight percent
  • the binder is conveniently formulated of a mixture of about 2 parts of TVOPA to one part of terpolymer constituted of 7 IPCA is used at a ratio of about 1 part to about 6 parts for each part of copolymer used.
  • a number of dicyclo diepoxy carboxylates are suitable for use as the curing agent for the propellants of this invention.
  • One procedure for preparation is given hereinbelow.
  • This type curing agent is also sold under brand names of UNOX 221 and ERL 4221.
  • the dicyclo diepoxy carboxylate curing agent used in compositions A-H is more extensively identified under UNOX 221 in The Condensed Chemical Dictionary, Seventh Edition, Copyright 1966 by Reinhold Publishing Corporation.
  • the dicyclo diepoxy carboxylate which is sold under Union Carbide Corporations trademark UNOX 221 has the following properties: Sp. gr. 1.1750 (20/20C); b.p. 354C (760mm); vapor pressure 0.01 mm hg. at 20C; f.p. -20C (sets to glass below this temperature); at 20C, 0.03% by wt. soluble in water; water in, 2.8% by wt; wt/gal 9.76 at 20C; flash point 400F.
  • reaction mixture has a tendency to become warm, but the temperature should be maintained somewhat below 50-60, by cooling, if necessary. A pasty, gelatinous mass results. After about one-half hour, the temperature of the mixture no longer rises; it is then warmed on a water bath for 1-2 hours with occasional shaking.
  • the cooled reaction product is treated with water (200 ml.); the layer of oil is separated; washed once with a second portion of water, and subjected to distillation under reduced pressure.
  • the first fraction of the distillate contains recovered epoxycyclohexylmethyl alcohol together with unchanged epoxycyclohexaldehyde, as well as a small quantity of water.
  • the temperature then rises rapidly to the boiling point of the epoxycyclohexylmethyl epoxycyclohexylcarboxylate.
  • the product boils at 184-185/5mm or in the range of about 350-360C/760mm.
  • the yield is 410-420g (75-80% of the theoretical amount).
  • the resulting product has a viscosity of 350-450 centipoise at 25C;-a specific gravity of 1.16-1.18; its color on the Gardner Color Comparator is less than 1.
  • a solid propellant composition comprising: a mixture of an inorganic oxidizing salt selected from ammonium, alkali metal, and alkaline earth metal salts of nitric, perchloric, and chloric acids and mixtures thereof; an NF binder comprised of the plasticizer 1,2,3- tris(1,2-bis-difluoramino) ethoxy propane in combination with a material selected from a terpolymer of 2,3- bis(difluoramino) propyl acrylate, carboranyl methyl acrylate, and acrylic acid, or a copolymer of ethyl acrylate and acrylic acid with the added plasticizer, l-isopropenylcarboranyl-acetone; and a dicyclo diepoxy carboxylate curing agent.
  • an inorganic oxidizing salt selected from ammonium, alkali metal, and alkaline earth metal salts of nitric, perchloric, and chloric acids and mixtures thereof
  • ammonium perchlorate has particle size in the range from about 8 micron to about 55 micron; and wherein said terpolymer is comprised of about 71 parts 2,3-bis(difluoramino) propyl acrylate, of about 25 parts carboranyl methyl acrylate, and of about 4 parts acrylic acid, said terpolymer being present in an amount of about 1 part to about 2 parts of said 1,2,3- tris( l,2,-bis-difluoramino) ethoxy propane.
  • the propellant composition of claim 1 and wherein said inorganic oxidizing salt is ammonium perchlorate present in an amount from about 45 to about 76 weight percent; said NF binder is comprised of 1,2,3-tris(1,2-bis-difluoramino) ethoxy propane from 6.
  • said ammonium perchlorate has particle size in the range from about 8 micron to about 55 micron, and said l-isopropenyl-carboranyl-acetone being used in a ratio of from about 1 part to about 6 parts to each part of copolymer used.
  • composition H is the composition in Table III headed by the component where EA equals 3.4.
  • Composition H is the composition in Table III headed by the component where EA equals 3.4.

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Abstract

Composite propellant compositions having NF binders selected from a mixture comprised of the plasticizer 1,2,3-tris(1,2bis(difluoroamino) ethoxy) propane in combination with a terpolymer constituted of 2,3-bis(difluoramino) propyl acrylate, carboranyl methyl acrylate, and acrylic acid, or a copolymer constituted of ethyl acrylate and acrylic acid with added plasticizer, 1-isopropenyl-carboranyl-acetone, are disclosed which have high impulses, high densities, high burning rates, and which employ conventional ammonium perchlorate oxidizer grinds.

Description

United States Patent [191 Jones et al.
[4 1 Oct. 21, 1975 1 PROPELLANT WITH VERY HIGH BURNING RATE ACRYLATE POLYMER BINDER AND NF PLASTICIZER [75] Inventors: Marvin L. Jones, Cumberland, Md.;
David W. Booth, Gurley, Ala.
[73] Assignee: The United States of America as represented by the Secretary of the Army, Washington, DC.
22 Filed: Sept. 12, 1972 21 Appl. No.: 287,164
[44] Published under the Trial Voluntary Protest Program on January 28, 1975 as document no. B 287,164.
Related US. Application Data [63] Continuation-in-part of Ser. No. 866,067, Sept. 30,
1969, abandoned.
[52] US. 149/l9.2; 149/19.3; 149/44; 149/76; 149/19.9l; 149/22 [51] Int. Cl. C061) 5/06 [58] Field of Search 149/19, 22, 44, 76, 109, 149/19.2, 19.3, 19.91; 260/583 NH, 606.5 B
[56] References Cited UNITED STATES PATENTS 5/1965 Cohen et al. 260/835 5/1966 Dupont et al 149/19 X 3,346,546 10/1967 Beach et al. 149/19 X 3,376,318 4/1968 Bieber fit al. 260/347] 3,406,203 10/1968 Morrow et al. 260/583 3,419,445 12/1968 Markels 149/19 3,439,039 4/1969 Petry 6i Ell. 260/584 3,441,550 4/1969 Zimmerman 260/895 3,476,622 11/1969 Harada et al.
3,549,707 12/1970 Stogryn 149/19 X OTHER PUBLICATIONS Zakharkin et al., Zhurnal Obshchei Khimii," 36, (No. 7), l,285l,290, (1966) (translation).
Primary ExaminerBenjamin R. Padgett Assistant Examiner-E. 'A. Miller Attorney, Agent, or Firm-Nathan Edelberg; Robert P. Gibson; Jack W. Voigt 7 Claims, No Drawings CROSS-REFERENCE TO RELATED APPLICATION This is a continuation-in-part of application Ser. No. 866,067, filed Sept. 30, 1969, now abandoned.
BACKGROUND OF THE INVENTION Current high burning rate composite propellants (with burning rates of about 15 inches/second at 10,000 psi) employ fine ammonium perchlorate (AP) (e.g., 2 to 4 microns, diameter) along with derivatives of dicarbaclovododecaborane (carborane) as plasticizers. Carborane plasticizers generally have a high specific volume resulting in a propellant with low density.
Difluoramino compounds belong to a class of compounds which are known to be useful as propellant ingredients for obtaining high density and high impulse. Derivatives of carborane belong to a class of compounds which are known to be effective ballistic modifiers for obtaining high burning rates. However, most derivatives of carborane are not miscible with the standard NF binder constituted of 1,2,3-tris-( 1,2-bisdifluoroamino) ethoxy propane (TVOPA) and 2,3- bis(difluoramino) propyl acrylate (NFPA).
Thus, a need exists for a high impulse, high density, high burning rate propellant employing conventional ammonium perchlorate oxidizer grinds and carborane derivatives which are miscible with NF compounds.
The object of this invention is to provide a combination binder having carborane derivatives which are miscible with NF compounds which are also compatible with other propellant ingredients.
Another object is to provide composite propellants having the characteristic features of high'impulse, high density, and high burning rates while employing conventional ammonium perchlorate oxidizer grinds.
SUMMARY OF THE INVENTION One representative propellant of this invention is constituted of a binder comprised of a blend of TVOPA and NFPA-carboranyl methyl acrylate (CMA)-acrylic acid (AA) terpolymer, an inorganic oxidizer of ammonium perchlorate, a curing agent and optionally, aluminum metal fuel. Another representative propellant of this invention is constituted of a binder comprised of ethyl acrylate (EA)-acrylic acid (AA) copolymer (designated EA-AA), and a mixed plasticizer comprised of a blend of TVOPA and l-isopropenyl-carboranyl-acetone (IPCA), an inorganic oxidizer of ammonium perchlorate, a curing agent, and optionally, aluminum metal fuel.
A number of new compounds used in the propellant formulations of this invention have resulted from research in the fields of NF and carborane chemistry. NF refers to NitrogemFluorine and NF propellants are those propellants containing the difluoramino group NF The new compounds: TVOPA, IPCA, and NFPA, resulting from research efforts in the NF and Carborane Chemistry fields, may be prepared by procedures set forth below.
PREPARATION OF TVOPA TVOPA, l,2,3-tris[ l ,2-bis(difluoramino)ethoxy] propane, is prepared by reacting tris(vinoxy)propane 2 with tetrafluorohydrazine. TVOPA contains two high energy difluoramino groups, NF in each of the three vinoxy groups of the starting compound, tris(vinoxy)- propane. The reaction of tetrafluorohydrazine with 5 tris(vinoxy)propane to form TVOPA is conducted under pressure in the range of 500 mm of mercury up to about 600 psig and temperature range of about 0 to 120C. The reaction is conducted in the presence of an inert volatile organic solvent, preferably one that is a suitable solvent for both the TVOPA as well as the reactant. Aromatic and aliphatic hydrocarbons, chlorinated hydrocarbons, ethers and ketones may be employed as the solvent. Typical solvents include diethyl ether, dipropyl ether, pentane, hexane, chloroform, carbon tetrachloride, methylene chloride, benzene, toluene, xylene, and acetone.
For further information about the preparation of TVOPA refer to US Pat. application Ser. No. 363,680, filed Apr. 27, 1964.
PREPARATION OF IPCA The derivative of carborane, l-isopropenyl-carborane, is further modified to form Hsopropenyl-carboranyl-acetone which is referred to as IPCA. Preparative procedure for IPCA is as follows: after flushing the reaction flask and accessory equipment, with dry nitrogen, 50 grams of isopropenylcarborane and 300 milliliters of anhydrous ethyl ether are combined in a three necked flask equipped with two addition funnels, cooling and heating accessory equipment, and accessory equipment for reflux procedure. Butyl lithium (171 milliliters of 1.60 molar) is placed into one addition funnel, and 40 milliliters of propylene oxide is placed in the other one. The flask is cooled to 0C, and the butyl lithium is added dropwise. After the butyl lithium is added, the flask is heated to reflux and the propylene oxide is added dropwise. After the addition is complete, the flask is refluxed for an additional 1 )6 hours. Contents of the flask are then poured into a separatory funnel and washed with an equal portion of water. The water layer is drained off and discarded and the ether layer is washed with two ZOO-ml portions of 10% HCl in water. The acid layers are discarded and the ether layer dried over magnesium sulfate. The ether is removed on a rotary evaporator. The remaining oil is washed into another three-neck flask with -ml of ether and treated dropwise with a chromic acid solution of 95.6 grams K Cr O 42.6 ml conc. H 80 and ml water after the flask is cooled to 0C. Throughout the addition the ice bath should remain around the flask as heat is generated in this reaction. After the addition of the chromic acid, the ice bath is removed and the reaction stirred at room temperature over night.
The reaction mixture is poured into a separatory funnel and washed with water. The water layer is discarded. The ether layer is then washed with saturated sodium bicarbonate-water solutions. The water layer is discarded and the ether layer dried over magnesium sulfate. The ether is removed on an evaporator and the remaining oil distilled to give IPCA l bp C at 0.025 mm, 35 grams yield. 1
(1) H C=C C C-CHgCiCHg Additional characteristics of IPCA are revealed by the NMR spectrum which consists of four absorptions centered at 1.95, 2.18, 3.07, and 5.57 ppm. the 5.57 ppm absorption, due to the vinylic protons, has the gross appearance of a quartet (J 1 cps) and a singlet superimposed on one another. The 3.07 and 2.18 ppm absorptions, due to the CH and CH of the acetone group are singlets while the 1.95 ppm peak assigned to isopropenyl CI-I group has the appearance ofa doublet (J 1 cps).
PREPARATION OF 2,3-BIS(DIFLUORAMINO)PROPYL ACRYLATE (NFPA) To a 200 ml. three-necked flask fitted with mechanical stirrer, condenser, thermometer and dropping funnel (all outlets covered with Drierite drying tubes) is introduced 7.72 parts (0.029 mole) of triphenylphosphine and 100 ml. anhydrous diethyl ether (commercial grade). To this solution is added 1 1.0 parts (0.029 mole) of a reactant 2,3-bis(difluoramino)propyl-a,[3- dibromopropionate. (The difiuoramino groups in the specified reactant are positioned within the alcohol moiety of the compound and paired on vicinal carbon atoms. The reactant is prepared by reacting propenyla,B-dibromopropionate with tetrafluorohydrazine at a temperature of about 50C to 120C.) A slightly exothermic heat of reaction (23C to 27C) and an immediate precipitate of triphenylphosphine dibromide are noted. The addition is completed within a -minute period. The reaction is continued for a period of 24 hours. The solids are removed by filtration, and the ether is removed at reduced pressure on a rotary evaporator. The residue, containing a small quantity of solids, is treated with 100 ml. of pentane and filtered again. The pentane is removed and the residue first examined by gas chromatography and then distilled. The gas chromatogram showed the product to be approximately 95% pure. The product (b.p. 52C. 1.1 mm. of mercury) is obtained in a yield of 4.22 parts(67%). The infrared spectrum of the product is identical in every respect to that of known 2,3-bis(difiuoramino)- propyl acrylate. The product gives the following analysis:
Calculated for C H F N O (NFPA): %C, 33.33; %H, 3.70;
Found: 71C, 33.25; %HH. 4.42; %F, 35.1; %N, 14.35.
DESCRIPTION OF THE PREFERRED EMBODIMENT NFPA 4% acrylic acid (AA) copolymer modified by adding carboranyl methyl acrylate (CMA) to the copolymer, is utilized in the formulation. The modified binder contains 2 parts TVOPA and one part NFPA/C- MA/AA 71/25/4 terpolymer. The composition, burning rate, density, and calculated specific impulse for the modified and control propellants are listed in Table 1 below.
Fast burning NF propellants result when IPCA is formulated with TVOPA along with moderate'or high amounts of ammonium perchlorate to provide control of the final density and impulse of the propellant composition. Propellant samples based on an ethyl acrylateacrylic acid (EA-AA) copolymer and a mixed plasticizer comprised of a blend of TVOPA and l-isopropenyl-carboranyI-acetone (IPCA) and containing only ammonium perchlorate in the solids phase are illustrated in Table 11 below. The formulations illustrate the trade-off of density and impulse for higher burning rates while utilizing a moderate amount of ammonium perchlorate.
Propellants with high ammonium perchlorate oxidizer concentrations are illustrated in Table III below. Increasing the oxidizer loading usually increases the density of propellant. Addition of aluminum will increase both density and impulse. Table III also illustrates that the density and impulse of a propellant can be increased with only a small loss in burning rate when NF compounds and aluminum are added to a carborane propellant.
BURNING RATES, DENSITIES, AND SPECIFIC IMPULSE FOR NF PROPELLANT CONTAINING CMA MODIFIER Control Modified Propellant Propellant Component Composition A Composition B NFPA 12.5 9.2 CMA None 3.3 AA 05 0.5 TVOPA 26.0 26.0 AP 46.0 46.0 A1 15.0 15.0 Additive: UNOX 221 (dicyclo diepoxy carboxylate curing agent) 1.5 1.5 Density (Ib./in 0.0662 0.0652 1 (lb./-secllbm)" 268.8 266.0 Burning Rate (in/sec) micron oxidizer 20,000 psia 12.8 21.0 15.000 psia 10.0 16.2 10,000 psia 7.0 11.1 5.000 psia 3.8 5.9 Burning Rate (in/sec) 8 micron oxidizer 20.000 psia 14.2 28.5 15,000 psia l 1.5 19.9 10.000 psia 8.5 14.2 5,000 psia 5.0 9.2
" 1000 psia L r conditions.
BURNING RATES, DENSITIES, AND SPECIFIC IMPULSES FOR ETHYL ACRYLATE PROPELLANTS CONTAINING IPCA MODIFIER Control Propellant Modified Propellants Component Composition C Composition D Composition E EA 6.6 6.6 6.6 AA 0.5 0.5 0.5 TVOPA 42.9 35.75 21.45 IPCA None 7.15 21.45 AP (8 micron) 50.0 50.0 50.0 Additive: UNOX 221 (dicyclo diepoxy carboxylate curing agent) 1.7 1.7 1.7
Density (lb/in") 0.0608 0.0590 0.0556
1sps (lbfsec/lbm) 258.7 253.1 249.9
TABLE 11 -continued BURNING RATES, DENSITIES, AND SPECIFIC IMPULSES FOR ETHYL ACRYLATE PROPELLANTS CONTAINING IPCA MODIFIER Control Propellant Component Composition C Modified Propellants Composition D Composition E Burning Rate (in/sec) "Calculated impulse, 1000 psia chamber pressure, standard conditions.
BURNING RATES, DENSITIES, AND SPECIFIC IMPULSES FOR ETHYL ACRYLATE PROPELLANTS CONTAINING TVOPA MODIFIER Modified Propellants Control Propellant Component Composition F Composition G Composition EA 2.67 2.67 3.4 AA 0.20 0.20 0.2 TVOPA None 4.89 18.3 IPCA 2148 16.59 3.1 AP (8 micron) 75.65 75.65 70.0 Al 5.0 Additive: UNOX 221 (dicyclo diepoxy carboxylate curing agent) 0.5 0.5 0.5 Density (lbm/in) 0.0594 0.0607 0.0653 Isps (lbf-sec/lbm)" 256.9 254.0 263.7 Burning Rate (in/sec) 20,000 psia 24.2 23.2
15,000 psia 20.0 18.9
10,000 psia 14.9 13.8 13.0
8,000 psia 12.8 11.5 11.3
"Calculated impulse, 1000 psia chamber pressure, standard conditions.
The procedure for propellant mixing as conventionally used in the propellant manufacturing art is employed in making the propellant grains of this invention. For example, the propellant formulation ingredients are blended together under vacuum until a homogeneous mixture is obtained and then the propellant grain is formed and cured. The metal powder is usually mixed with the binder or prepolymer [e.g., copolymers (EA-AA) or terpolymer (NFPA/CMA/AA)] and the mass mixed until the metal powder is wetted. The inorganic oxidizing salt and additives are next added, and the mixture is mixed under vacuum until a homogeneous mixture is obtained. The resulting mixture is cast into a suitable mold or rocket motor to form the propellant grain and to cure. The grain is cured for several days at about 60C until a cured grain is obtained. The curing may vary somewhat, but generally in about 3 days the grain is properly cured.
The inorganic oxidizing salts which are useful in the solid propellant compositions of this invention are those oxygen containing salts which readily give up oxygen. These oxidizing salts include ammonium, alkali metal, and alkaline earth metal salts of nitric, perchloric, and chloric acids, and mixtures thereof. Representative of the oxidizing salts referred to are ammonium perchlorate, ammonium nitrate, sodium nitrate, potassium perchlorate, potassium chlorate, lithium perchlorate, lithium chlorate, calcium nitrate, calcium chlorate, barium perchlorate, strontium chlorate, and strontium perchlorate. Ammonium perchlorate is preferred since less smoke results from lower solids present in exhaust gases from a rocket motor wherein used. Lower smoke solids is required for military purposes of concealment. Ammonium perchlorate of particle size from the range of about 8 microns to the range of about 55 microns is suitable for use in the propellant compositions of this invention to achieve the burning rates and special properties as disclosed in the Tables listed hereinabove.
Powdered metals, as additive, useful in the propellant compositions of this invention include in addition to aluminum, magnesium, titanium, zirconium, boron, and beryllium. Alloys and mixtures of the aforesaid metals may also be employed. Aluminum metal powder is the preferred metal additive.
The ingredients of the propellants of this invention may be varied to provide propellants having a wide range of high densities, high impulses, and high burning rates. Satisfactory ranges for the ingredients are inorganic oxidizing salts from about 45 to about 76 weight percent, metal additive up to about 20 weight percent, ethyl acrylate from about 2 to about 7 weight percent, acrylic acid from about 0.20 to about 7 weight percent, TVOPA from about 4 to about 36 weight percent, carborane derivatives (e.g., lPCA and CMA) from about 3 to about 22 weight percent, NFPA up to about 10 weight percent, and curing agent in the range of about 1 to 2 parts per 100 parts of the total propellant ingredients. Although, the ingredients are specified in weight percent of the total propellant mix, the binder is conveniently formulated of a mixture of about 2 parts of TVOPA to one part of terpolymer constituted of 7 IPCA is used at a ratio of about 1 part to about 6 parts for each part of copolymer used.
A number of dicyclo diepoxy carboxylates are suitable for use as the curing agent for the propellants of this invention. One procedure for preparation is given hereinbelow. This type curing agent is also sold under brand names of UNOX 221 and ERL 4221.
The dicyclo diepoxy carboxylate curing agent used in compositions A-H is more extensively identified under UNOX 221 in The Condensed Chemical Dictionary, Seventh Edition, Copyright 1966 by Reinhold Publishing Corporation. The dicyclo diepoxy carboxylate which is sold under Union Carbide Corporations trademark UNOX 221 has the following properties: Sp. gr. 1.1750 (20/20C); b.p. 354C (760mm); vapor pressure 0.01 mm hg. at 20C; f.p. -20C (sets to glass below this temperature); at 20C, 0.03% by wt. soluble in water; water in, 2.8% by wt; wt/gal 9.76 at 20C; flash point 400F.
The disproportionation of two molecules of an aldehyde (usually aromatic) brought about by the action of sodium or potassium hydroxide to yield the corresponding alcohol and acid is known as the Cannizzaro reaction. A review of the Cannizzaro reaction is given by T. A. Geissman, in Organic Reactions" (R Adams, ed.), Vol. ll, p. 94, Wiley, New York, 1944.
One method of synthesis to produce a dicyclo diepoxy carboxylate curing agent of the type sold under trademark UNOX 221 employs a Cannizzaro-type redox reaction which is a reaction between an aldehyde and an alcoholate. The reaction is summarized by the chemical equation which follows the Procedure for the Synthesis of 4,5-Epoxycyclohexylmethyl 4,5- epoxycyclohexylcarboxylate set forth hereinbelow.
PROCEDURE FOR THE SYNTHESIS OF 4,S-EPOXYCYCLOHEXYLMETHYL 4'5 '-epoxycyclohexylcarboxylate cs c Metallic sodium (3g., 0.13 g-atom) is dissolved by warming for one-half hour in 4,5-epoxycyclohexylmethyl alcohol (82g. 0.65 mole). After the mixture has cooled to room temperature, the solution is added gradually, with thorough mixing, to 4,5-epoxycyclohexaldehyde (529g, 4.3 moles) (which contains less than 1% of 4,5-epoxycyclohexycarboxylic acid). The reaction mixture has a tendency to become warm, but the temperature should be maintained somewhat below 50-60, by cooling, if necessary. A pasty, gelatinous mass results. After about one-half hour, the temperature of the mixture no longer rises; it is then warmed on a water bath for 1-2 hours with occasional shaking.
The cooled reaction product is treated with water (200 ml.); the layer of oil is separated; washed once with a second portion of water, and subjected to distillation under reduced pressure. The first fraction of the distillate contains recovered epoxycyclohexylmethyl alcohol together with unchanged epoxycyclohexaldehyde, as well as a small quantity of water. The temperature then rises rapidly to the boiling point of the epoxycyclohexylmethyl epoxycyclohexylcarboxylate. The product boils at 184-185/5mm or in the range of about 350-360C/760mm. The yield is 410-420g (75-80% of the theoretical amount).
8 The resulting product has a viscosity of 350-450 centipoise at 25C;-a specific gravity of 1.16-1.18; its color on the Gardner Color Comparator is less than 1.
The method of synthesis is by a Cannizzaro-type redox reaction, as summarized by the following chemical equation:
cs0 CH Q'Na O O cs 0 0 o o *The 5" in the hexagon means cyclohexane.
We claim:
1. A solid propellant composition comprising: a mixture of an inorganic oxidizing salt selected from ammonium, alkali metal, and alkaline earth metal salts of nitric, perchloric, and chloric acids and mixtures thereof; an NF binder comprised of the plasticizer 1,2,3- tris(1,2-bis-difluoramino) ethoxy propane in combination with a material selected from a terpolymer of 2,3- bis(difluoramino) propyl acrylate, carboranyl methyl acrylate, and acrylic acid, or a copolymer of ethyl acrylate and acrylic acid with the added plasticizer, l-isopropenylcarboranyl-acetone; and a dicyclo diepoxy carboxylate curing agent.
2. The solid propellant composition of claim 1 and additionally comprising a metal additive selected from the powdered metals consisting .of aluminum, magnesium, titanium, zirconium, boron, and beryllium.
3. The solid propellant composition of claim 1 and wherein said inorganic oxidizing salt is ammonium perchlorate present in amount from about 45 to about 76 weight percent; said NF binder is comprised of the plasticizer 1,2,3-tris(1,2-bis-difluoramino) ethoxy propane from about 4 to about 36 weight percent of said propellant composition in combination with a terpolymer of 2,3-bis(difluoramino)-propyl acrylate up to about 10 weight percent of said solid propellant composition, carboranyl methyl acrylate from about 3 to about 22 weight percent of said solid propellant composition, and acrylic acid from about 0.20 to about 7 weight percent of said solid propellant composition; and said curing agent is present in an amount from about 1 to about 2 parts per parts of the total propellant ingredients; and wherein said composition further comprises a metal additive of aluminum in the amount up to about 20 weight percent.
4. The propellant composition of claim 3 wherein said ammonium perchlorate has particle size in the range from about 8 micron to about 55 micron; and wherein said terpolymer is comprised of about 71 parts 2,3-bis(difluoramino) propyl acrylate, of about 25 parts carboranyl methyl acrylate, and of about 4 parts acrylic acid, said terpolymer being present in an amount of about 1 part to about 2 parts of said 1,2,3- tris( l,2,-bis-difluoramino) ethoxy propane.
5. The propellant composition of claim 1 and wherein said inorganic oxidizing salt is ammonium perchlorate present in an amount from about 45 to about 76 weight percent; said NF binder is comprised of 1,2,3-tris(1,2-bis-difluoramino) ethoxy propane from 6. The propellant composition of claim 5 and wherein said ammonium perchlorate has particle size in the range from about 8 micron to about 55 micron, and said l-isopropenyl-carboranyl-acetone being used in a ratio of from about 1 part to about 6 parts to each part of copolymer used.
7. The propellant composition of claim 6 and wherein said l-isopropenyl-carboranyl-acetone is used in a ratio with said l,2,3-tris(1,2-bis-difluoramino) ethoxy propane from about 1/ l to about 1/6; and wherein said composition further comprises a metal additive of aluminum in the amount of about 5 weight percent.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,914,139
DAT I October 21 1975 lNVENTOR(S). Marvin L. Jones et al It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
The compound: "I ,2,3-tris(l ,2-bis-difluoramino) ethoxy propane" should be printed as fol lows --l ,2,3-tris[l ,2-bis(difl'uoramino)ethoxy]propane--. The compound appears in the fol lowing places in the Specification and Claims:
In the Specification and Claims: Column l lines 25 and 26; Column 6 8, lines 27, 28; 43; 64, 65; and 70; and Column 10, lines 9 and l0.
In the Specification: Column 3, line 3, capitalize "the"; and approximately line 48, HH", should be: --%H--.
Column 4, about line 31 insert heading: --Table I--; and about line 56, insert heading: --Table II--.
Column 5, line 12, insert heading: --Table III--; and line l7, Q Composition H is the composition in Table III headed by the component where EA equals 3.4.
Signed and Scaled this sixteenth Day Of March 1976 [SEAL] Attest:
RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner oj'Patents and Trademarks UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT N0. 3,9l4,l 39
DATED 1 October 2I I975 INVENTOR(S) Marvin L. Jones et al It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
' The compound: "I,2,3-tris(l,2-bis-difluoramino) ethoxy propane" should be printed as follows: -I,2,3-tris[l,Z-bis(difl'uoramino)ethoxy]propane--. The compound appears in the fol lowing places in the Specification and Claims:
In the Specification and Claims: Column 1 lines 25 and 26; Column 8, lines 27, 28; 43; 64, 65; and 70; and Column l0, lines 9 and I0.
- In the Specification: Column 3, line 3, capitalize "the"; and approximately line 48, HH" should be: --%H--.
Column 4, about line 3l, insert heading: --Table I--; and about line 56, insert heading: --Table II-.
Column 5, line 12, insert heading: --Table III--; and line l7,
Composition H is the composition in Table III headed by the component where EA equals 3.4.
Signed and Scaled this sixteenth Day Of March 1976 [SEALl A ttes I.
RUTH C. MASON C. MARSHALL DANN Al csting ()jfivt Commissioner ufParents and Trademarks

Claims (7)

1. A SOLID PROPELLANT COMPOSITION COMPRISING: A MIXTURE OF AN INORGANIC OXIDIZING SALT SELECTED FROM AMMONIUM, ALKALI METAL, AND ALKALINE EARTH METAL SALTS OF NITTRIC, PERCHLORIC, AND CHLORIC ACIDS AND MIXTURES THEREOF, AN NF BINDER COMPRISED OF THE PLASTICIZER 1,2,3-TRIS(1,2-BIS-DIFLUORAMINO) ETHOXY PROPANE IN COMBINATION WITH A MATERIAL SELECTED FROM A TERPOLYMER OF 2,3-BIS(DIFLUORAMINO) PROPYL ACRYLATE, CARBORANYL METHYL ACRYLATE AND ACRYLIC ACID, OR A COPOLYMER OF ETHYL ACRYLATE AND ACRYLIC ACID WITH THE ADDED PLASTICIZER, 1-ISOPROPENYLCARBORANYL-ACETONE, AND A DICYCLO DIEPOXY CARBOXYLATE CURING AGENT.
2. The solid propellant composition of claim 1 and additionally comprising a metal additive selected from the powdered metals consisting of aluminum, magnesium, titanium, zirconium, boron, and beryllium.
3. The solid propellant composition of claim 1 and wherein said inorganiC oxidizing salt is ammonium perchlorate present in amount from about 45 to about 76 weight percent; said NF binder is comprised of the plasticizer 1,2,3-tris(1,2-bis-difluoramino) ethoxy propane from about 4 to about 36 weight percent of said propellant composition in combination with a terpolymer of 2,3-bis(difluoramino)-propyl acrylate up to about 10 weight percent of said solid propellant composition, carboranyl methyl acrylate from about 3 to about 22 weight percent of said solid propellant composition, and acrylic acid from about 0.20 to about 7 weight percent of said solid propellant composition; and said curing agent is present in an amount from about 1 to about 2 parts per 100 parts of the total propellant ingredients; and wherein said composition further comprises a metal additive of aluminum in the amount up to about 20 weight percent.
4. The propellant composition of claim 3 wherein said ammonium perchlorate has particle size in the range from about 8 micron to about 55 micron; and wherein said terpolymer is comprised of about 71 parts 2,3-bis(difluoramino) propyl acrylate, of about 25 parts carboranyl methyl acrylate, and of about 4 parts acrylic acid, said terpolymer being present in an amount of about 1 part to about 2 parts of said 1,2,3-tris(1,2,-bis-difluoramino) ethoxy propane.
5. The propellant composition of claim 1 and wherein said inorganic oxidizing salt is ammonium perchlorate present in an amount from about 45 to about 76 weight percent; said NF binder is comprised of 1,2,3-tris(1,2-bis-difluoramino) ethoxy propane from about 4 to about 36 weight percent of said propellant composition, in combination with a copolymer comprised of ethyl acrylate from about 2 to about 7 weight percent of said propellant composition and of acrylic acid from about 0.20 to about 7 weight percent of said propellant composition with added compound 1-isopropenyl-carboranyl-acetone from about 3 to about 22 weight percent of said propellant composition; and said curing agent is present in an amount from about 1 to about 2 parts per 100 parts of the total propellant ingredients.
6. The propellant composition of claim 5 and wherein said ammonium perchlorate has particle size in the range from about 8 micron to about 55 micron, and said 1-isopropenyl-carboranyl-acetone being used in a ratio of from about 1 part to about 6 parts to each part of copolymer used.
7. The propellant composition of claim 6 and wherein said 1-isopropenyl-carboranyl-acetone is used in a ratio with said 1,2, 3-tris(1,2-bis-difluoramino) ethoxy propane from about 1/1 to about 1/6; and wherein said composition further comprises a metal additive of aluminum in the amount of about 5 weight percent.
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