US2946671A - Gas generating composition containing - Google Patents

Gas generating composition containing Download PDF

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US2946671A
US2946671A US2946671DA US2946671A US 2946671 A US2946671 A US 2946671A US 2946671D A US2946671D A US 2946671DA US 2946671 A US2946671 A US 2946671A
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    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S149/00—Explosive and thermic compositions or charges
    • Y10S149/11—Particle size of a component
    • Y10S149/112—Inorganic nitrogen-oxygen salt

Definitions

  • thermoplastic.compositionsand morev particularly to thermoplastic compositions comprising a major proportiomof ammonium nitrate and a minor proportion of thermoplastic binder material consisting, of a. polymeric cellulose; acetate-containing ester plasticized with an oxygenecontaining organic, plasticizer;
  • the, invention concerns an improved been required tom-old or extrude the compositions. More- 7 over, the mixing of the ammonium nitrate with the binder has necessitated greater power requirement in the mixing operation due to the relatively high consistency of" the ammonium nitrate-binder mixture at temperatures consistent with safe mixing of the ammonium nitrate.
  • ammonium nitrate-binder compositions In addition to these undesirable processing features for the production of ammonium nitrate-binder compositions the absence of a surfactant has resulted in the production of propellant grains of non-uniform texture, which grains; do not always exhibit ballistic dependability when fi'redi Among the objects of this invention is the production of new and useful plasticized ammonium nitrate composi: tions. Another object of the invention is the production of ammonium nitrate-containing thermoplastic compositions of uniform texture. Still another object of the invention is to reduce the power requirement for the mixing of ammonium nitrate with plasticized cellulose acetate synthetic polymer. A further: object of the invention is to produce an ammonium nitrate-binder propellant composition which is improved with respect to moldability and extrudability. Other objects of the invention will be apparent firom the description thereof set outhereinbelow.
  • the present invention is predicated upon the discovery that a mixture of a major proportion of ammonium nitrate and a minor proportion of a plasticized cellulose acetate binder can be improved with respect to lowered consistency by thepresence of small amount of certain non-ionic surfactants in said mixture.
  • This lowered con sistency results in reduced power requirement in the mixing operation and in the molding and extrusion of the finished composition tofoim propellant grains.
  • Ammonium nitrate is widely used as a component of high explosives particularly the so called safe explosives.
  • ammonium nitrate alone doesnot bum uniformly and has a tendency to go out.
  • oxidizable materials such as carbon, cellulosic materials, hydrocarbons and so forth, have been'admixed with the ammonium nitrate.
  • Rockets comprise essentially a hi walledicasing which. contained a. combustion chamon: containing,- a. quantity. of solid propellant, a nozzle 7 hrough. which the. decomposition gases passed and created the, forward, thrust, stabilizing fins andawarhead which, contained. the; explosive; Alsotherewas. developed the. usepirochet to,-v assistin. the take-0E in either heavily .ladenairplanes or to overcome; a short runway; These? units arezcommqnly known; as; J-ATO (jetassisted take-0th) or ATQt-assistedtake-ofli); units.
  • the ga e era ing thermoplastic; composition of, thi invention comprises, at least. about 70% by weight of ammonium, nitrate; and;at;least-; about, L8%. and not more. t n. bout 30%- n eightoi. pl s ize binder mate ial h b n r ma er ateo s sts. of: romabqut 0%; qabo t by weight of a cellulose acetate-containing; ester p a t iz with. bout 6.0% to ab ut 831%; buvste b e -on.
  • surfactant material selected; from; the. classconsisting of; polymers of alky ene oxides; which oxides; contain from. about 2 to3.
  • fatty alcohol monoethers of said. polymers, fatty acid monoesters; of polymers, fatty acidesters of polyoxyethylene soubitql and fatty acid; esters: oi-inner ethersofi sorbitol.
  • ammonium nitrate nitrate such as conventionally grained ammonium. nitrate. containing a small amountor impuiritiesand which may becoated with a small amount of moisture resistingmaterial such as petrolatum or: parafii'n ormiiltaw grade" ammonium nitrate or-a mixture of minor amounts oi other inorganicnitrates' with theammoniummitrate.
  • Solid ammonium nitrate can exist in five different forms, which are stable in certain. different temperature ranges in: which formsthe nitrate occupies difierent volume.
  • thermoplastic binder of the propellant composition contain combined oxygen. This is necessary in order to maintain stoichiometric balance with respect to oxygen requirement in the combustion of the composition to form Water, carbon monoxide and/ or carbon dioxide. Binders which have high oxygen demand throw the finished grain composition out of 'oxygenbal ance, thus producing a smoky combustion andloss of energy: in the burning of the material. Cellulose esters are relatively high in oxygen content.
  • the binder I material of this. invention consists essentially of" (1) a arisen cellulose acetate-containing synthetic polymeric material plasticized with (2) one or more organic oxygen-containing plasticizers.
  • Illustrative examples of the cellulose acetate-containing material are cellulose acetate, cellulose acetate-propionate and cellulose acetate-butyrate.
  • Partially esterified cellulose acetate having an acetic acid content between about 51 and 57% by weight may be used.
  • percent by weight acetic acid denotes the amount of acetic acid obtained upon saponification of the cellulose acetate and is expressed as percent of initial material. Lacquer grade cellulose acetate is preferred.
  • Cellulose acetate is further described by the viscosity of a 20% solution in acetone. The viscosity of the preferred cellulose acetate is within the range of 2 to 10 centipoises at 25 C.
  • viscosities of cellulose acetate may range from 2 to 80 centipoises at 25 C.
  • the cellulose acetate-butyrate has an acetic acid content between about 5 and 55% by weight and a butyric acid content between about 16% and 61% by weight, and it has a viscosity between about and 40 centipoises at 25 C. when dissolved in acetone at 20% by weight concentration.
  • the plasticizer of the cellulose acetate-containing base material of the binder consists of at least one organic, oxygen-containing plasticizer component although two or more of such components may be used.
  • the plasticizers are selected from the class consisting of nitrodiphenyl ethers, having not more than two nitro groups on any phenyl nucleus and not more than three nitro groups per molecule, mixtures of nitrodiphenyl ethers, polymeric esters, aliphatic ethers of nitrophenols, nitromonocyclic aromatics, esters of polyhydric alcohols and esters of polycarboxylic acids.
  • nitropropanediol diacetate an ester of a polyhydric alcohol
  • plasticizer components which contain nitro groups are dinitrodiphenyl ether, particularly 2,4-dinitrodiphenyl ether, dinitrophenyl propyl ether, 2,4-dinitrophenyl allyl ether, dinitrobenzene and dinitrotoluene, particularly 2,4-dinitrotoluene.
  • Examples of simple esters of polycarboxylic acids, that is, the esterification products of polycarboxylic acids with monoalcohols, which are suitable as plasticizer components, particularly when used in conjunction with nitro group-containing plasticizer components are dimethyl phthalate and dioctyl phthalate.
  • Examples of polymeric esters are ethylene glycol diglycolate and diethylene glycol diglycolate.
  • Ethylene glycol diglycolate prepared according to the procedure described in the application of Norman J. Bowman and Wayne A. Proell entitled Polyester Plasticizer, Ser. No. 471,992, filed November 30, 1954, now abandoned, is a particularly desirable plasticizer when used in conjunction with nitro group-containing plasticizers.
  • the molecular weight of the ethylene glycol diglycolate polymeric ester should preferably be in the range of from about 250 to about 600. Low molecular weight of polymeric esters within this range is attained by using a ratio of about 1.02 mols to about 1.3 mols of glycol to one mol of acid in carrying out the esterification.
  • the inorganic combustion catalyst of this invention is selected from the class consisting of ammonium dichromate and Prussian blue catalyst.
  • Certain iron compounds, broadly designated as Prussian blue are effective for the combustion of ammonium nitrate grains containing the oxidizable organic binder materials.
  • the so called insoluble Prussian blue catalysts are preferred. Mixtures of insoluble Prussian blue catalyst with ammonium dichromate catalyst may be used.
  • the surfactant polymers of alkylene oxides may be the 4, polymers of ethylene oxide, copolymers of ethylene oxide and propylene oxide or block polymers of propylene oxide and ethylene oxide wherein ethylene oxide is added to polymers of propylene oxide.
  • These polyalkylene oxide condensation products are otherwise known as polyoxyalkylene glycols and have from two to three carbon atoms in the oxyalkylene unit.
  • Pluronics which are polyoxypropylene-polyoxyethylene glycols or specifically, block copolymers.
  • Pluronic L-62 which is preferred, has a molecular weight of about 2,000 of which 2,000 molecular weight from about 1500 to about 1800 is furnished by the propylene oxide units, the other alkylone oxide units in the polymer molecule being ethylene oxide units.
  • the general formula for the Pluronics is HO(C H O),,(C I-I O) (C H O) H.
  • Pluronic L-62 has a value of about 26 to about 31.
  • Pluronic L-62 is a liquid having a viscosity at 25 C. of 300 to 500 centipoises.
  • certain derivatives'of the polyoxyalkylene glycols are effective to reduce the'consistency of the ammonium nitrate-binder mixtures.
  • Tergitol XC is a monoether derivative of a copolymer of ethylene oxide and propylene oxide and has the approximate formula wherein R is an acyclic hydrocarbon radical containing from 12 to 20 carbon atoms.
  • R is an acyclic hydrocarbon radical containing from 12 to 20 carbon atoms.
  • the alkylene oxide constituents of the molecule each contribute about 1500 to give about 3000 to the total molecular weight, i.e., not more than about 3300, of the monoether derivative.
  • the number of ethylene oxide units may vary from about 22 to 35 and the number of propylene oxide units may vary from about 18 to about 27.
  • the total molecular weight of these ethers will usually lie within the range of from about 2000 to about 3300.
  • An example of a monoester derivative of a polyoxyalkylene glycol which is effective in reducing the consistency of the ammonium nitrate-base binder composition is the commercial product Nonisol-250.
  • This product is a mono-oleyl ester of polyoxyethylene having a molecular weight of about 1000.
  • the fatty acid esters of polyoxyethylene sorbitol condensation products are effective surfactants for purpose of this invention. These may be produced by condensing ethylene oxide or polyoxyethylone with sorbitol followed by esterification of the condensation product with a 12 to 20 carbon atom fatty acid. In general, suitable products of this type have molecular weights within the range of from about 1000 to about 3300.
  • polyoxyalkylene glycol, ether and fatty acid ester derivatives thereof as used in this specification and claims is defined to include (1) the polyethylene oxide homopolymers, copolymers of ethylene oxide and propylene oxide, block copolymers of propylene oxide and ethylene oxide, said polymers having a molecular weight within the range of from about 1000 to about 3000, (2) the monoethers of the polymers of (1) produced by reacting fatty alcohols having 12 to 20 carbon atoms with polymers of (1) said ethers having a molecularweight of about 2000 to about 3300, and (3) monoesters of the polymers of (1) produced by esterification of said polymers with fatty acids having from 12 to 20 carbon atoms per molecule, said monoesters having molecular weights within the range of about 1000 to about 3300.
  • the fatty acids used to esterify the condensation product of ethylene oxide with sorbitol have from 12 to 20 car: bon atoms, and the fatty acid esters produced have momas er sorbitol. These may be classified as esters of' monoan-' hydro sorbitol and fatty acids having from 12 to 20 car bon atoms.
  • the fatty acid derivatives of monoanhydrized sorbitol, which are defined as sorbitans, aredescribed in U.S. 2,398,193; These arel'cnown commercially as Span and Arlacel products.
  • Span materials for use inffhe composition are essentially partial esters of oleic acid and' the-sorbitol monoanhydrides derived from sorbitol, the sorbitan-oleates containing from 1 to 3 oleateradicals. 'l-ri producing these products, sorbitol is dehydrated by the elimination of one mol of water per mol of sorbitol to give condensed ring structures of the sorbitan which product when esterified with oleic acid produces the Spans or Arlacels.
  • Arlacel C is decolori-zed sorbitan 'sesquioleate having an average of 1% oleyl radicals per mol of sorbitol dehydrated in produc ng the sorbitan intermediate.
  • This material is an oilyfliiquid at 25 C. having a specific gravity of 0.95- 1500 and has a viscosity at 25 C. of 9001100 centipoi'ses.
  • Another closely related very eifective non-ionic surfactant is Span 85, which is a sorbitan trioleate.
  • these fatty acid esters of inner ethers of sorbitol are not definite single compounds but are mixtures of 2 or more esterified, dehydrated, cycliz'ed products of sorbitol as described in the above patent,
  • the amount of surfactant material added to the composition is relatively small, that is, usually within the range of about 0.05 to about 1. preferably from about 0.1% to about 0.3% by weight of thecomposition.
  • thermoplastic propellant composition of this invention is prepared according to the following procedure.
  • the cellulose acetate-containing synthetic polymer is added incrementally to the oxygen-containing plasticizer which is heated to a temperature below about 150 C., preferably below about 140 C.
  • a homogeneousmelt is produced.
  • the plasticized molten mixture which constitutes the binder material is brought to a temperature below about 120 (3., preferably below about 110 C. and usually above about 100 C., and thefinely ground ammonium nitrate is added and mixed therewith to produce the homogeneous plasticized propellant material.
  • the surfactant may be added incrementally during the mixing operation of the ammonium nitrate with the bindermaterial.
  • the inorganic catalyst may be added during this mixing operation or it may be premixed with the finely ground ammonium nitrate and added along with the ammonium nitrate in this final m xing step.
  • This final mixing step usually requires a period of from about 15 minutes to about 90 minutes to obtain intimate contact of the ammonium nitrate with the binder material.
  • the hot mixture is then molded into molds for the shaping of the material into propellant grains. These molds are provided with insets of various shapes such as starform, triform, cylinders, or cruciform to produce uniform internal burning surface of the propellant grains. of the mold is usually about 2%".
  • the mold is subjected to pressures within the range of from about 4,000 to about 10,000 psi.
  • the material may be extruded. Extrusion operations usually require higher pressures.
  • the inclusion of the surfactants of this invention results in the production of propellant grains having improved texture and more uniform distribution of components therein and the presence of the The diameter surfactant res ults in a reduction in the pressure-requirement for the extrusionoperation.
  • the consistency of the finished propellant material may be measured by means of a suitable plastograph.
  • the plastograph used for'measuring the consistency of the materials described herein is the Brabender Farinographplastograph described by E. O. Rhodes, Machine for Testin'g Highway Subgrade Soils, Proc. Amer. Soc. Testing 'Ma't.,-' 38 ⁇ Part 11) 551-72 (1938).
  • This machine is a small driven by a; synchronous motor so mounted that it is free to rotate with the, resistance which the mixing blades encounter in the material under test.
  • the determination of consistency of the propellant mixture is determined by melting in the smallmixing bowl of the'plastograph about 20 grams of the binder material using a thermostat setting of 110 C.
  • the bowl has a practical working volume of about 150 ccs., that is, about gram mix capacity.
  • the bowl temperature that is,
  • the actual mixture temperature is usually within 12 C.
  • a propellant material consisting essentially of finely ground ammonium nitrate as described above in an amount of about 75% of the total composition and a plasticized binder material which made up about 25 %of the total propellant material, was prepared.
  • the binder material consisted of about 25% lacquer grade cellulose acetate .(LL1 grade) and had an acetic acid content of 54-56% by weight, plasticized with a plasticizer consisting of equal amounts by weight of ethylene glycol diglycolate and 2,4-dinitrodiphenyl ether, that is, 37.5% by weight of each of these plasticizer components based on the total weight of the binder.
  • This composition indicated, at 110 C., a plateau on the recorder of the Brabender plastograph corresponding to meter-grams of torque. j Thetaddition.
  • thermoplastic composition consisting at least 70% by weight of ammonium nitrate; from 18% to about 30% by weight of a plasticizable binder consisting essentially of about 20% to about 40% by weight of a cellulose acetate-containing ester plasticized with about 60% to about 80% by Weight of an oxygen-containing organic plasticizer consisting essentially of a mixture of 2,4-dinitrodiphenyl ether and ethylene glycol diglycolate, from about 1% to about by weight of an inorganic combustion catalyst selected from the class consisting of Prussian blue and ammonium dichromate, and from about 0.05% to about 1.0% by weight of a non-ionic surfactant material selected from the class consisting of polyethylene oxide homopolymers, copolymers of ethylene oxide and propylene oxide, and block polymers of propylene oxide and ethylene oxide, said homopolymers, copolymers and block polymers having molecular weights of about 1000 ot 3000; monoethers of 12 to 20 carbon atom fatty alcohols
  • thermoplastic composition comprising at least 70% by weight of ammonium nitrate; from 18% to about 30% by Weight of a plasticizable binder consisting essentially of about 20% to about 40% by weight of a cellulose acetate-containing ester plasticized with about 60% to about 80% by weight of at least one plasticizer selected from the class consisting of nitropropanediol diacetate, dinitrodiphenyl ether, dinitrophenyl propyl ether, 2,4-dinitrophenyl allyl ether, dinitrobenzene, dinitrotoluene, dimethyl phthalate, dioctyl phthalate, ethylene glycol diglycolate, and diethylene glycol diglycolate, from about 1% to about 5% by weight of an inorganic combustion catalyst selected from the class consisting of Prussian blue and ammonium dichromate, and from about 0.05% to about 1.0% by weight of a non-ionic surfactant material selected from the class consisting of polyethylene oxide homo
  • composition as described in claim 2 wherein the cellulose acetate-containing ester is cellulose acetate which analyzes between about 51 and 57% acetic acid.
  • non-ionic surfactant material is a polyoxyethylenepolyoxypropylene glycol block polymer having a molecular weight of about 2000 of which 2000 molecular weight about 1500 to about 1800 is furnished by propylene oxide uints and in which non-ionic surfactant the ethylene oxide units provide the remainder of the total alkylene oxide units.
  • composition as described in claim 2 wherein the nonionic surfactant corresponds to the approximate acyclic hydrocarbon radical containing from 12 to 20 carbon atoms.
  • composition as described in claim 2 wherein the non-ionic surfactant material is the sesquioleate of the inner ether of sorbitol.
  • a process for improving the mixing properties and contact properties of the components of a mixture comprising at least by Weight of ammonium nitrate, about 1% to about 5% by weight of ,an inorganic catalyst selected from the class consisting of Prussian blue and ammonium dichromate and about 18% to about 30% by weight of a binder material consisting of about 20% to about 40% by weight of cellulose acetate-containing ester plasticized with about 60% to about by weight of at least one plasticizer selected from the class consisting of nitropropanediol diacetate, dinitrodiphenyl ether, dinitrophenyl propyl ether, 2,4-dinitrophenyl allyl ether, dinitrobenzene, dinitrotoluene, dimethyl phthalate, dioctyl phthalate, ethylene glycol diglycolate, and diethylene glycol diglycolate, which process consists of mixing said components at a temperature within the range of from about C.
  • a non-ionic surfactant material selected from the class consisting of polyethylene oxide homopolymers, copolymers of ethylene oxide and propylene oxide, and block polymers of propylene oxide and ethylene oxide, said homopolymers, copolymers and block polymers having molecular weights of about 1000 to 3000; monoethers of 12 to 20 carbon atom fatty alcohols and said homopolymers, copolymers and, block polymers said ethers having molecular weights of about 2000 to about 3000; monoesters of 12 to 20 carbon atom fatty acids and said homopolymers, copolymers and block polymers said monoesters having molecular weights within the range of about 1000 to about 3300; esters of 12 to 20 carbon atom fatty acids and the condensation product of ethylene oxide with sorbitol said esters having molecular weights of about 1000 to about 3300; and sorbitan o

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Description

I l l United States GAS. COMPOSITION. GONTAJNING SUREACTANTJ Paul Marti; In, Hammond; Indi, assignor to Standard Oil. Gompany (thicago, 111;, a corporationof' Indiana NoDrawing, EiledApr. 26,1955,- Ser.. No. 504,116 & Claims: (Cl. 52 --.5)
This nventionrelates tothermoplastic.compositionsand morev particularly to thermoplastic compositions comprising a major proportiomof ammonium nitrate and a minor proportion of thermoplastic binder material consisting, of a. polymeric cellulose; acetate-containing ester plasticized with an oxygenecontaining organic, plasticizer; Ina more p particular sense, the, invention: concerns an improved been required tom-old or extrude the compositions. More- 7 over, the mixing of the ammonium nitrate with the binder has necessitated greater power requirement in the mixing operation due to the relatively high consistency of" the ammonium nitrate-binder mixture at temperatures consistent with safe mixing of the ammonium nitrate. In addition to these undesirable processing features for the production of ammonium nitrate-binder compositions the absence of a surfactant has resulted in the production of propellant grains of non-uniform texture, which grains; do not always exhibit ballistic dependability when fi'redi Among the objects of this invention is the production of new and useful plasticized ammonium nitrate composi: tions. Another object of the invention is the production of ammonium nitrate-containing thermoplastic compositions of uniform texture. Still another object of the invention is to reduce the power requirement for the mixing of ammonium nitrate with plasticized cellulose acetate synthetic polymer. A further: object of the invention is to produce an ammonium nitrate-binder propellant composition which is improved with respect to moldability and extrudability. Other objects of the invention will be apparent firom the description thereof set outhereinbelow.
The present invention is predicated upon the discovery that a mixture of a major proportion of ammonium nitrate and a minor proportion of a plasticized cellulose acetate binder can be improved with respect to lowered consistency by thepresence of small amount of certain non-ionic surfactants in said mixture. This lowered con sistency results in reduced power requirement in the mixing operation and in the molding and extrusion of the finished composition tofoim propellant grains.
Ammonium nitrate is widely used as a component of high explosives particularly the so called safe explosives. However, when ignited, ammonium nitrate alone. doesnot bum uniformly and has a tendency to go out. In order to improve the burning quality, to increase the sensitivity and to utilize the excessfiree oxygen available from the decomposition of the ammonium nitrate, oxidizable materials such as carbon, cellulosic materials, hydrocarbons and so forth, have been'admixed with the ammonium nitrate.
tent i Patented. July. 26,1960.
World. War. II. utilized rockets. for. gtound-to-ground e h m Q hor-e missiles. airtmgrouudnul sile n air-tq air missiles. "Dhese. rockets comprise essentially a hi walledicasing which. contained a. combustion chamon: containing,- a. quantity. of solid propellant, a nozzle 7 hrough. which the. decomposition gases passed and created the, forward, thrust, stabilizing fins andawarhead which, contained. the; explosive; Alsotherewas. developed the. usepirochet to,-v assistin. the take-0E in either heavily .ladenairplanes or to overcome; a short runway; These? units arezcommqnly known; as; J-ATO (jetassisted take-0th) or ATQt-assistedtake-ofli); units.
The ga e era ing thermoplastic; composition of, thi invention comprises, at least. about 70% by weight of ammonium, nitrate; and;at;least-; about, L8%. and not more. t n. bout 30%- n eightoi. pl s ize binder mate ial h b n r ma er ateo s sts. of: romabqut 0%; qabo t by weight of a cellulose acetate-containing; ester p a t iz with. bout 6.0% to ab ut 831%; buvste b e -on. the e g t f; he binder, Qfia l ast one oxygenon n us organi plasti iz rz. 'The thermoplastic com- P sition. also contains from about. 1%. toabeut 5%.= .15.811 ino g ni combustion cat lyst:v and; from about: 1.05% to. about 15.0% v'weightof anourionic. surfactant material selected; from; the. classconsisting of; polymers of alky ene oxides; which oxides; contain from. about 2 to3.
u ltbonatomsper 'alliylene oxide. molecule, said; polymers having a. molecular weight: of; from about 100mm about 3.300,. fatty alcohol: monoethers of said. polymers, fatty acid monoesters; of polymers, fatty acidesters of polyoxyethylene soubitql and fatty acid; esters: oi-inner ethersofi sorbitol.
The term ammonium nitrate?" as used in this specifiandin the claims is. intended to mean eitherordinary' commercial. grade. ammonium: nitrate such as conventionally grained ammonium. nitrate. containing a small amountor impuiritiesand which may becoated with a small amount of moisture resistingmaterial such as petrolatum or: parafii'n ormiiltaw grade" ammonium nitrate or-a mixture of minor amounts oi other inorganicnitrates' with theammoniummitrate. Solid ammonium nitrate can exist in five different forms, which are stable in certain. different temperature ranges in: which formsthe nitrate occupies difierent volume. Hence, at transition temperatures where phasechanges occur, internal stresses in shaped plasticized ammonium nitrate compositions are produced. Volume changes occur at about F. and at about 0-' F. Efii'cient binder material to resist fissure formation must be provided for filling the interstices, that is, the voids between the ammonium nitrate granules; Finely ground ammonium nitrate eontains' about 20% or more ofvoids. Finely ground ammonium nitrate is de fined herein as ammonium nitrate, at least 70% of which has been ground at 1'4,000 r.p.m. ina micropulyerizer to give a product, the major part of which will pass through a U.S. Standardsieve. Any voidsoriissuresproduced by phase changes of the ammonium nitrate actas burning surfaces to changeburning rates, thus. making on, predictable the ballistic performance of the propellant grain material.
The components of the thermoplastic binder of the propellant composition contain combined oxygen. This is necessary in order to maintain stoichiometric balance with respect to oxygen requirement in the combustion of the composition to form Water, carbon monoxide and/ or carbon dioxide. Binders which have high oxygen demand throw the finished grain composition out of 'oxygenbal ance, thus producing a smoky combustion andloss of energy: in the burning of the material. Cellulose esters are relatively high in oxygen content. Hence, the binder I material of this. invention consists essentially of" (1) a arisen cellulose acetate-containing synthetic polymeric material plasticized with (2) one or more organic oxygen-containing plasticizers. Illustrative examples of the cellulose acetate-containing material are cellulose acetate, cellulose acetate-propionate and cellulose acetate-butyrate. Partially esterified cellulose acetate having an acetic acid content between about 51 and 57% by weight may be used. The term percent by weight acetic acid denotes the amount of acetic acid obtained upon saponification of the cellulose acetate and is expressed as percent of initial material. Lacquer grade cellulose acetate is preferred. Cellulose acetate is further described by the viscosity of a 20% solution in acetone. The viscosity of the preferred cellulose acetate is within the range of 2 to 10 centipoises at 25 C. although viscosities of cellulose acetate may range from 2 to 80 centipoises at 25 C. The cellulose acetate-butyrate has an acetic acid content between about 5 and 55% by weight and a butyric acid content between about 16% and 61% by weight, and it has a viscosity between about and 40 centipoises at 25 C. when dissolved in acetone at 20% by weight concentration.
The plasticizer of the cellulose acetate-containing base material of the binder consists of at least one organic, oxygen-containing plasticizer component although two or more of such components may be used. In general, the plasticizers are selected from the class consisting of nitrodiphenyl ethers, having not more than two nitro groups on any phenyl nucleus and not more than three nitro groups per molecule, mixtures of nitrodiphenyl ethers, polymeric esters, aliphatic ethers of nitrophenols, nitromonocyclic aromatics, esters of polyhydric alcohols and esters of polycarboxylic acids. I prefer to have present in the binder at least one plasticizer component which contains at least one nitro group, since the nitro compounds increase the combustion rate of the propellant grains. Thus nitropropanediol diacetate, an ester of a polyhydric alcohol, is a good plasticizer for the cellulose acetate-containing synthetic polymer particularly when used in conjunction with other oxygen-containing organic plasticizers. Other examples of plasticizer components which contain nitro groups are dinitrodiphenyl ether, particularly 2,4-dinitrodiphenyl ether, dinitrophenyl propyl ether, 2,4-dinitrophenyl allyl ether, dinitrobenzene and dinitrotoluene, particularly 2,4-dinitrotoluene. Examples of simple esters of polycarboxylic acids, that is, the esterification products of polycarboxylic acids with monoalcohols, which are suitable as plasticizer components, particularly when used in conjunction with nitro group-containing plasticizer components are dimethyl phthalate and dioctyl phthalate. Examples of polymeric esters are ethylene glycol diglycolate and diethylene glycol diglycolate. Ethylene glycol diglycolate prepared according to the procedure described in the application of Norman J. Bowman and Wayne A. Proell entitled Polyester Plasticizer, Ser. No. 471,992, filed November 30, 1954, now abandoned, is a particularly desirable plasticizer when used in conjunction with nitro group-containing plasticizers. The molecular weight of the ethylene glycol diglycolate polymeric ester should preferably be in the range of from about 250 to about 600. Low molecular weight of polymeric esters within this range is attained by using a ratio of about 1.02 mols to about 1.3 mols of glycol to one mol of acid in carrying out the esterification.
The inorganic combustion catalyst of this invention is selected from the class consisting of ammonium dichromate and Prussian blue catalyst. Certain iron compounds, broadly designated as Prussian blue are effective for the combustion of ammonium nitrate grains containing the oxidizable organic binder materials. The so called insoluble Prussian blue catalysts are preferred. Mixtures of insoluble Prussian blue catalyst with ammonium dichromate catalyst may be used.
The surfactant polymers of alkylene oxides may be the 4, polymers of ethylene oxide, copolymers of ethylene oxide and propylene oxide or block polymers of propylene oxide and ethylene oxide wherein ethylene oxide is added to polymers of propylene oxide. These polyalkylene oxide condensation products are otherwise known as polyoxyalkylene glycols and have from two to three carbon atoms in the oxyalkylene unit.
One class of the polyoxyalkylene glycols which are effective in reducing the consistency of ammonium nitrate-binder mixtures are the commercial Pluronics which are polyoxypropylene-polyoxyethylene glycols or specifically, block copolymers. Pluronic L-62 which is preferred, has a molecular weight of about 2,000 of which 2,000 molecular weight from about 1500 to about 1800 is furnished by the propylene oxide units, the other alkylone oxide units in the polymer molecule being ethylene oxide units. The general formula for the Pluronics is HO(C H O),,(C I-I O) (C H O) H. Thus b in this formula, for Pluronic L-62 has a value of about 26 to about 31. Pluronic L-62 is a liquid having a viscosity at 25 C. of 300 to 500 centipoises.
As indicated hereinabove, certain derivatives'of the polyoxyalkylene glycols are effective to reduce the'consistency of the ammonium nitrate-binder mixtures. These.
derivatives are the fatty alcohol monoethers and the fatty acid monoesters. An example of the monoether derivative is Tergitol XC. Tergitol XC is a monoether derivative of a copolymer of ethylene oxide and propylene oxide and has the approximate formula wherein R is an acyclic hydrocarbon radical containing from 12 to 20 carbon atoms. The alkylene oxide constituents of the molecule each contribute about 1500 to give about 3000 to the total molecular weight, i.e., not more than about 3300, of the monoether derivative. In these ether derivative-type surfactants the number of ethylene oxide units may vary from about 22 to 35 and the number of propylene oxide units may vary from about 18 to about 27. The total molecular weight of these ethers will usually lie within the range of from about 2000 to about 3300.
An example of a monoester derivative of a polyoxyalkylene glycol which is effective in reducing the consistency of the ammonium nitrate-base binder composition is the commercial product Nonisol-250. This product is a mono-oleyl ester of polyoxyethylene having a molecular weight of about 1000. The fatty acid esters of polyoxyethylene sorbitol condensation products are effective surfactants for purpose of this invention. These may be produced by condensing ethylene oxide or polyoxyethylone with sorbitol followed by esterification of the condensation product with a 12 to 20 carbon atom fatty acid. In general, suitable products of this type have molecular weights within the range of from about 1000 to about 3300.
The term polyoxyalkylene glycol, ether and fatty acid ester derivatives thereof, as used in this specification and claims is defined to include (1) the polyethylene oxide homopolymers, copolymers of ethylene oxide and propylene oxide, block copolymers of propylene oxide and ethylene oxide, said polymers having a molecular weight within the range of from about 1000 to about 3000, (2) the monoethers of the polymers of (1) produced by reacting fatty alcohols having 12 to 20 carbon atoms with polymers of (1) said ethers having a molecularweight of about 2000 to about 3300, and (3) monoesters of the polymers of (1) produced by esterification of said polymers with fatty acids having from 12 to 20 carbon atoms per molecule, said monoesters having molecular weights within the range of about 1000 to about 3300. The fatty acids used to esterify the condensation product of ethylene oxide with sorbitol have from 12 to 20 car: bon atoms, and the fatty acid esters produced have momas er sorbitol. These may be classified as esters of' monoan-' hydro sorbitol and fatty acids having from 12 to 20 car bon atoms. The fatty acid derivatives of monoanhydrized sorbitol, which are defined as sorbitans, aredescribed in U.S. 2,398,193; These arel'cnown commercially as Span and Arlacel products. -The preferred Span materials for use inffhe composition are essentially partial esters of oleic acid and' the-sorbitol monoanhydrides derived from sorbitol, the sorbitan-oleates containing from 1 to 3 oleateradicals. 'l-ri producing these products, sorbitol is dehydrated by the elimination of one mol of water per mol of sorbitol to give condensed ring structures of the sorbitan which product when esterified with oleic acid produces the Spans or Arlacels. Arlacel C is decolori-zed sorbitan 'sesquioleate having an average of 1% oleyl radicals per mol of sorbitol dehydrated in produc ng the sorbitan intermediate. This material is an oilyfliiquid at 25 C. having a specific gravity of 0.95- 1500 and has a viscosity at 25 C. of 9001100 centipoi'ses. Another closely related very eifective non-ionic surfactant is Span 85, which is a sorbitan trioleate. It is to be understood that these fatty acid esters of inner ethers of sorbitol are not definite single compounds but are mixtures of 2 or more esterified, dehydrated, cycliz'ed products of sorbitol as described in the above patent,
US. 2,398,193. They may be prepared according-to the procedure described in the patent of Kenneth R. Brown, U.S. 2,322,821. I
The amount of surfactant material added to the composition is relatively small, that is, usually within the range of about 0.05 to about 1. preferably from about 0.1% to about 0.3% by weight of thecomposition.
The thermoplastic propellant composition of this invention is prepared according to the following procedure. The cellulose acetate-containing synthetic polymer is added incrementally to the oxygen-containing plasticizer which is heated to a temperature below about 150 C., preferably below about 140 C. A homogeneousmelt is produced. The plasticized molten mixture which constitutes the binder material is brought to a temperature below about 120 (3., preferably below about 110 C. and usually above about 100 C., and thefinely ground ammonium nitrate is added and mixed therewith to produce the homogeneous plasticized propellant material. The surfactant may be added incrementally during the mixing operation of the ammonium nitrate with the bindermaterial. The inorganic catalyst may be added during this mixing operation or it may be premixed with the finely ground ammonium nitrate and added along with the ammonium nitrate in this final m xing step. This final mixing step usually requires a period of from about 15 minutes to about 90 minutes to obtain intimate contact of the ammonium nitrate with the binder material. The hot mixture is then molded into molds for the shaping of the material into propellant grains. These molds are provided with insets of various shapes such as starform, triform, cylinders, or cruciform to produce uniform internal burning surface of the propellant grains. of the mold is usually about 2%". The mold is subjected to pressures within the range of from about 4,000 to about 10,000 psi. ram pressure for a period of about 5 to minutes after which the pressure may be reduced and the reduced pressure may be maintained for an ad; ditional 15 minutes to about 30 minutes. Alternately, the material may be extruded. Extrusion operations usually require higher pressures. The inclusion of the surfactants of this invention results in the production of propellant grains having improved texture and more uniform distribution of components therein and the presence of the The diameter surfactant res ults in a reduction in the pressure-requirement for the extrusionoperation.
' "The consistency of the finished propellant material may be measured by means of a suitable plastograph. The plastograph used for'measuring the consistency of the materials described herein is the Brabender Farinographplastograph described by E. O. Rhodes, Machine for Testin'g Highway Subgrade Soils, Proc. Amer. Soc. Testing 'Ma't.,-' 38 {Part 11) 551-72 (1938). This machine is a small driven by a; synchronous motor so mounted that it is free to rotate with the, resistance which the mixing blades encounter in the material under test. The
resistance asserts itself as a reaction force in the motor casing, whichtends to rotate the motor casing in the opposite direction. This turning movement I in the motor casing is transmitted to a weighing systemYand a'recorder by means of a lever system, the oscillations of which are restricted by a dash pot. Units of measurement of torque are in meter-grams. The plastograph maybe calibrated at a suitable temperature using a polymer having a known high viscosity. Thus the meter-grams of torque as measured in the plastograph may be equated to absolute viscosity.
The determination of consistency of the propellant mixture is determined by melting in the smallmixing bowl of the'plastograph about 20 grams of the binder material usinga thermostat setting of 110 C. The bowl has a practical working volume of about 150 ccs., that is, about gram mix capacity. The bowl temperature, that is,
the actual mixture temperature is usually within 12 C.
with a practical variance of about i5 C. With a tem- 'perature of the binder at about C., the pulverized ammonium nitrate is, added gradually to a molten binder and the plastograph is put in operation. During and after the addition of the solid material the consistency rises sharply. Afterabout one half hour following the addition of ammonium nitrate the equilibrium value or base consistency is attained. This is indicated by a level plateau on the recorder chart which is usually a reading of from to 300 meter-grams of torque for the control composition depending on the specific compositions of the control sample. After the 'base consistency is reached, a surfactant is added and mixing is continued until a new equilibrium plateau is obtained. This usual ly requires 15 to. 30 minutes. The addition of about 1.0% of the. surfactants described above usually causes a decrease inconsistency of at least 25% below the con-v sistency of the control composition containing no surfactant material.
The following illustrations indicate the approximate efiect of adding a surfactant of this invention to an ammonium nitrate-oxygen containing binder material. A propellant material consisting essentially of finely ground ammonium nitrate as described above in an amount of about 75% of the total composition and a plasticized binder material which made up about 25 %of the total propellant material, was prepared. The binder material consisted of about 25% lacquer grade cellulose acetate .(LL1 grade) and had an acetic acid content of 54-56% by weight, plasticized with a plasticizer consisting of equal amounts by weight of ethylene glycol diglycolate and 2,4-dinitrodiphenyl ether, that is, 37.5% by weight of each of these plasticizer components based on the total weight of the binder. This composition indicated, at 110 C., a plateau on the recorder of the Brabender plastograph corresponding to meter-grams of torque. j Thetaddition. to theabov e composition of about 1.0% of a monoether derivative of polypropylene-polyethylene glycol such as Tergitol XC will lower the meter-grams of torque by about 30%. The addition of 1.0% of a sorbitan sesquioleate such as Arlacel C will lower the meter-grams of torque of the mixture at 110 C. by about 40%. The addition of about 1.0% of polyoxyethylene sorbitol hexaoleate, will reduce the consistency of this base formulation by about 50%. If about 1.0% of the ester derivative of polyoxyethylene glycol, Nonisol-ZSO or the polyoxypropylene-polyoxyethylene glycol product Pluronic L-62, is added to this base propellant mixture the consistency in the first instance will be reduced by about 25% and the consistency will be reduced about 25% by the addition of the Pluronic L-62.
Not all non-ionic surfactants are efiective in reducing the consistency of the propellant compositions. Thus it was found that the Tweens which are non-ionic polyalkylene oxide derivatives of the Spans tend to increase the consistency of the mixtures. Ionic surfactants are undesirable and in most cases fail to decrease the consistency of the mixtures.
Having thus described my invention, I claim:
1. A thermoplastic composition consisting at least 70% by weight of ammonium nitrate; from 18% to about 30% by weight of a plasticizable binder consisting essentially of about 20% to about 40% by weight of a cellulose acetate-containing ester plasticized with about 60% to about 80% by Weight of an oxygen-containing organic plasticizer consisting essentially of a mixture of 2,4-dinitrodiphenyl ether and ethylene glycol diglycolate, from about 1% to about by weight of an inorganic combustion catalyst selected from the class consisting of Prussian blue and ammonium dichromate, and from about 0.05% to about 1.0% by weight of a non-ionic surfactant material selected from the class consisting of polyethylene oxide homopolymers, copolymers of ethylene oxide and propylene oxide, and block polymers of propylene oxide and ethylene oxide, said homopolymers, copolymers and block polymers having molecular weights of about 1000 ot 3000; monoethers of 12 to 20 carbon atom fatty alcohols and said homopolymers, copolymers and block polymers said ethers having molecular weights of about 2000 to about 3000; monoesters of 12 to 20 carbon atom fatty acids and said homopolymers, copolymers and block polymers said monoesters having molecular weights within the range of about 1000 to about 3300; esters of 12 to 20 carbon atom fatty acids and the condensation product of ethylene oxide with sorbitol said esters having molecular weights of about 1000 to about 3300; and sorbitan oleates containing from 1 to 3 oleyl radicals.
2. A thermoplastic composition comprising at least 70% by weight of ammonium nitrate; from 18% to about 30% by Weight of a plasticizable binder consisting essentially of about 20% to about 40% by weight of a cellulose acetate-containing ester plasticized with about 60% to about 80% by weight of at least one plasticizer selected from the class consisting of nitropropanediol diacetate, dinitrodiphenyl ether, dinitrophenyl propyl ether, 2,4-dinitrophenyl allyl ether, dinitrobenzene, dinitrotoluene, dimethyl phthalate, dioctyl phthalate, ethylene glycol diglycolate, and diethylene glycol diglycolate, from about 1% to about 5% by weight of an inorganic combustion catalyst selected from the class consisting of Prussian blue and ammonium dichromate, and from about 0.05% to about 1.0% by weight of a non-ionic surfactant material selected from the class consisting of polyethylene oxide homopolymers, copolymers of ethylene oxide and propylene oxide, and block polymers of propylene oxide and ethylene oxide, said homopolymers, copolymers and block polymers having molecular weights of about 1000 to 3000; monoethers of 12 to 20 carbon atom fatty alcohols and said homopolymers, copolymers and block polymers said ethers having molecular Weights of about 2000 to about 3000; monoesters of 12 to 20 carbon atom fatty acids and said homopolymers, copolymers and block polymers said monoester having molecular weights within the range of about 1000 to about 3300; esters of 12 to 20 carbon atom fatty acids and the condensation product of ethylene oxide with sorbitol said esters having molecular weights of about 1000 to about 33-00; and sorbitan oleates containing from 1 to 3 oleyl radicals.
.3. The composition as described in claim 2 wherein the cellulose acetate-containing ester is cellulose acetate which analyzes between about 51 and 57% acetic acid.
4. The composition as described in claim 2 wherein the inorganic combustion catalyst consists essentially of insoluble Prussian blue.
5. The composition as described in claim 2 wherein the non-ionic surfactant material is a polyoxyethylenepolyoxypropylene glycol block polymer having a molecular weight of about 2000 of which 2000 molecular weight about 1500 to about 1800 is furnished by propylene oxide uints and in which non-ionic surfactant the ethylene oxide units provide the remainder of the total alkylene oxide units.
6. The composition as described in claim 2 wherein the nonionic surfactant corresponds to the approximate acyclic hydrocarbon radical containing from 12 to 20 carbon atoms.
7. The composition as described in claim 2 wherein the non-ionic surfactant material is the sesquioleate of the inner ether of sorbitol.
8. A process for improving the mixing properties and contact properties of the components of a mixture comprising at least by Weight of ammonium nitrate, about 1% to about 5% by weight of ,an inorganic catalyst selected from the class consisting of Prussian blue and ammonium dichromate and about 18% to about 30% by weight of a binder material consisting of about 20% to about 40% by weight of cellulose acetate-containing ester plasticized with about 60% to about by weight of at least one plasticizer selected from the class consisting of nitropropanediol diacetate, dinitrodiphenyl ether, dinitrophenyl propyl ether, 2,4-dinitrophenyl allyl ether, dinitrobenzene, dinitrotoluene, dimethyl phthalate, dioctyl phthalate, ethylene glycol diglycolate, and diethylene glycol diglycolate, which process consists of mixing said components at a temperature within the range of from about C. to about C. in the presence of about 0.05 to 1.00% by weight, based on the Weight of said mixture, of a non-ionic surfactant material selected from the class consisting of polyethylene oxide homopolymers, copolymers of ethylene oxide and propylene oxide, and block polymers of propylene oxide and ethylene oxide, said homopolymers, copolymers and block polymers having molecular weights of about 1000 to 3000; monoethers of 12 to 20 carbon atom fatty alcohols and said homopolymers, copolymers and, block polymers said ethers having molecular weights of about 2000 to about 3000; monoesters of 12 to 20 carbon atom fatty acids and said homopolymers, copolymers and block polymers said monoesters having molecular weights within the range of about 1000 to about 3300; esters of 12 to 20 carbon atom fatty acids and the condensation product of ethylene oxide with sorbitol said esters having molecular weights of about 1000 to about 3300; and sorbitan oleates containing from 1 to 3 oleyl radicals.
No references cited.

Claims (1)

1. A THEMOPLASTIC COMPOSITION CONSISTING AT LEAST 70% BY WEIGHT OF AMMONIUM NITRATE? FROM 18% TO ABOUT 30% BY WEIGHT OF A PLASTICIZABLE BINDER CONSISTING ESSENTIALLY OF ABOUT 20% TO ABOUT 40%* BY WEIGHT OF A CELLULOSE ACETATE-CONTAINING ESTER PLASTICIZED WITH ABOUT 60% TO ABOUT 80% BY WEIGHT OF AN OXYGEN-CONTAINING ORGANIC PLASTICIZER CONSISTING ESSENTIALLY OF A MIXTURE OF 4,4-DINITRODIPHENYL ETHER AND ETHYLENE GLYCOL DIGLYCOLATE, FROM ABOUT 1% TO ABOUT 5% BY WEIGHT OF AN INORGANIC COMBUSTION CATALYST SELECTED FROM THE CLASS CONSISTING OF PRUSSIAN BLUE AND AMMONIUM DICHROMATE, AND FROM ABOUT 0.05% TO ABOUT 1.0% BY WEIGHT OF A NON-IONIC SURFACTANT MATERIAL SELECTED FROM THE CLASS CONSISTING OF POLYETHYLENE OXIDE HOMOPOLYMERS, COPOLYMERS OF ETHYLENE OXIDE AND PROPYLENE OXIDE, AND BLOCK POLYMERS OF PROPYLENE OXIDE AND ETHYLENE OXIDE, SAID HOMOPOLYERS, COPOLYMERS AND BLOCK POLYMERS HAVING MOLECULAR WEIGHTED OF ABOUT 10000 OT 3000, MONOETHERS OF 12 TO 20 CARBON ATOM FATTY ALCOHOLS AND SAID HOMOPOLYMERS, COPOLYMERS AND BLOCK POLYMERS SAID ESTERS HAVING MOLECULAR WEIGHTS OF ABOUT 2000 TO ABOUT 3000, MONOESTERS OF 12 TO 20 CARBON ATOM FATTY ACIDS AND SAID HOMOPOLYMERS, COPOLYMERS AND BLOCK POLYMERS SAID MONOESTERS HAVING MOLECULAR WEIGHTS WITHIN THE RANGE OF ABOUT 1000 TO ABOUT 3300, ESTERS OF 12 TO 20 CARBON ATOM FATTY ACIDS AND THE CONDENSATION PRODUCT OF ETHYLENE OXIDE WITH SORBITOL SAID ESTERS HAVING MOLECULAR WEIGHTS OF ABOUT 1000 TO ABOUT 3300, AND SORBITAN OLEATES CONTAINING FROM 1 TO 3 OLEYL RADICALS.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3153604A (en) * 1962-02-23 1964-10-20 Standard Oil Co Ammonium nitrate propellant composition containing nitrilotriacetate
US3508981A (en) * 1968-04-24 1970-04-28 Sumitomo Chemical Co Thickened aqueous slurry explosive composition containing ammonium nitrate trinitrotoluene surface active agent
US3535174A (en) * 1967-12-06 1970-10-20 Us Army Solid bipropellant composition containing a wetting mixture of polyoxyethylated sorbitan monolaurate and lecithin
US3964256A (en) * 1972-10-17 1976-06-22 Societe Nationale Des Poudres Et Explosifs Production of non-toxic gas by combustion of solid propellant
US4221617A (en) * 1966-09-30 1980-09-09 United Technologies Corporation Surfactant additives for solid propellants

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3153604A (en) * 1962-02-23 1964-10-20 Standard Oil Co Ammonium nitrate propellant composition containing nitrilotriacetate
US4221617A (en) * 1966-09-30 1980-09-09 United Technologies Corporation Surfactant additives for solid propellants
US3535174A (en) * 1967-12-06 1970-10-20 Us Army Solid bipropellant composition containing a wetting mixture of polyoxyethylated sorbitan monolaurate and lecithin
US3508981A (en) * 1968-04-24 1970-04-28 Sumitomo Chemical Co Thickened aqueous slurry explosive composition containing ammonium nitrate trinitrotoluene surface active agent
US3964256A (en) * 1972-10-17 1976-06-22 Societe Nationale Des Poudres Et Explosifs Production of non-toxic gas by combustion of solid propellant

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