US3894894A - Modified double base propellants with diisocyanate crosslinker - Google Patents

Modified double base propellants with diisocyanate crosslinker Download PDF

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US3894894A
US3894894A US202355A US20235562A US3894894A US 3894894 A US3894894 A US 3894894A US 202355 A US202355 A US 202355A US 20235562 A US20235562 A US 20235562A US 3894894 A US3894894 A US 3894894A
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nitrocellulose
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diisocyanate
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nitroglycerin
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Donald E Elrick
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US Department of Navy
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    • CCHEMISTRY; METALLURGY
    • C06EXPLOSIVES; MATCHES
    • C06BEXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/001Fillers, gelling and thickening agents (e.g. fibres), absorbents for nitroglycerine
    • CCHEMISTRY; METALLURGY
    • C06EXPLOSIVES; MATCHES
    • C06BEXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0033Shaping the mixture
    • C06B21/0058Shaping the mixture by casting a curable composition, e.g. of the plastisol type
    • CCHEMISTRY; METALLURGY
    • C06EXPLOSIVES; MATCHES
    • C06BEXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00Compositions containing a nitrated organic compound
    • C06B25/18Compositions containing a nitrated organic compound the compound being nitrocellulose present as 10% or more by weight of the total composition
    • C06B25/24Compositions containing a nitrated organic compound the compound being nitrocellulose present as 10% or more by weight of the total composition with nitroglycerine
    • C06B25/26Compositions containing a nitrated organic compound the compound being nitrocellulose present as 10% or more by weight of the total composition with nitroglycerine with an organic non-explosive or an organic non-thermic component
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/64Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6484Polysaccharides and derivatives thereof

Definitions

  • a propellant composition consisting of at least one of a member of nitrocelluloses selected from a group consisting of densified nitrocellulose, fluid ball powder nitrocellulose and plastisol nitrocellulose, at least one of a member of solid oxidizers selected from a group consisting of ammonium perchlorate, cyclotetramethylene tetranitramine, cyclotrimethylene trinitramine and nitroguanide, at least one of a member of explosive plasticizers selected from a group consisting of nitroglycerin, diethylene glycol dinitrate, triethylene glycol dinitrate and metriol trinitrate, at least one of a member of non-explosive plasticizers selected from a group consisting of triacetin, diallyl phthalate, di-n-propyl adipate, dimethyl sebacate, adiponitrile, isophorone (3,5,5-trimethyl-2-cyclohexen-l-one), ochloronitrobenzene
  • the present invention relates to the crosslinking of modified double base propellants by reacting the nitrocellulose binder with a suitable polyfunctional crosslinking agent such as a diisocyanate. Reaction occurs during cure and results in improved physical properties over hon-crosslinked versions provided that the amount of nitrocellulose in the binder phase is sufficiently small.
  • Modified doubled base propellants contain a solid oxidizer such as ammonium perchlorate. a metal fuel such as aluminum. and a liquid organic nitrate plasticizcr such as nitroglycerin in addition to the nitrocellulose binder and can be prepared in a number of ways. Most modified double base propellants are prepared using a casting process, wherein casting powder granules containing nitrocellulose. solid oxidizer, metal fuel and a plasticizer (usually nitroglycerin) are immersed in additional plasticizer and allowed to cure. during cure the granules expand and coalesce to form the cast propellant. These propellants have satisfactory physical properties if the nitrocellulose content in the binder phase is sufficiently high, about 23 volume percent.
  • modified double base propellants are prepared using a slurry-cast process, wherein nitrocellulose in the form of very small. hard particles is mixed with the ingredients previously mentioned and the resulting slurry is poured into a container in which it is cured. During cure. the liquids plasticize the nitrocellulose and there is some swelling of the latter. The swelling, however. does not occur to the same extent as it does in cast propellants for the physical properties of cast propellants are better than those of slurry-cast propellants tvhich are of similar composition.
  • Crosslinked slurry-cast propellants do show increased tensile strength and elongation when compared to noncrosslinked versions and most of the experimental data ll'l this invention is used to support this observation.
  • This invention also concerns solution cast propellants which comprise a third method of preparing modified double base propellants.
  • a slurry of the previously mentioned ingredients is prepared and poured into a container and cured.
  • the method is thus similar to slurry-cast propellants and differs from that type of propellant in that the nitrocellulose of the solution cast propellant is completely in solution prior to pouring.
  • Solutions of normally used (military grade it) I 8 sec.) nitrocellulose are quite viscous and a very low viscosity nitrocellulose (18-25 cp.) is crosslinked during the curing phase to convert the slurry to a solid mass. ln this method the solid ingredients (nitrocellulose. solid oxidizer, and metal fuel) are added to a solution of casting solvent.
  • Nitrocellulose is essentially insoluble in this solution and thus may be well dispersed by stirring so that dissolution does occur readily as methylene chloride is gradually removed. When about 10% methylene chloride remains in this slurry, nitrocellulose is in solution. The crosslinker is added and dispersed at this time. The slurry is now transferred to a curing container under reduced pressure and heat is applied to facilitate removal of the remaining methylene chloride.
  • the purpose of the diluent, methylene chloride is thus twofold: a means of ensuring rapid dissolution of nitrocellulose and a means of increasing fluidity so that transfer can be more readily effected.
  • the primary purpose of the present invention is to improve the physical properties of slurry-cast propellants by crosslinking the nitrocellulose binder.
  • Other purposes include the improvement by cross-linking of physical properties of cast propellants containing small amounts, less than about 23 volume percent, of nitrocellulose in the binder phase and a new method of preparing modified double base propellants, wherein a slurry containing nitrocellulose in solution is made more or less rigid by crosslinking that binder.
  • Another object is the improvement of specific impulse.
  • Still another object is to provide a process for the production of propellant grains which has the economic advantages of reduced time, equipment and labor.
  • a further object of the present invention is the provision of a method for casting propellant grains which has the potential advantage of even greater simplicity and versatility than the standard casting procedure.
  • a still further object is the preparation of a propellant composition that can be poured into a motor and by suitable means polymerized to a solid bonded to the motor.
  • the mechanism of the crosslinking involves the reaction of the hydroxyl groups of the nitrocellulose with a polyfunctional crosslinker such as a diisocyanate.
  • a polyfunctional crosslinker such as a diisocyanate.
  • Commercial nitrocellulose has roughly 2.2 to 2.5 nitrate groups and 0.8 to 0.5 hydroxyl groups per monomer length.
  • These hydroxyl groups can react more or less readily with difunctional molecules to form crosslinks which, in effect, increase the size of the molecule, change the structure from linear to branched, and alter the physical characteristics of the polymer.
  • Crosslinking tends to increase the rigidity of the propellant matrix and the tendency for flow to occur at normal temperatures is decreased. Because of this change the tensile strength and modulus are increased and the elongation decreased at normal temperatures.
  • Crosslinking then improves the physical properties of solution cast propellants, which would flow if not crosslinked and should improve the physical properties of cast propellants containing small amounts of nitrocellulose by making the propellant matrices more rigid.
  • Crosslinking apparently improves physical properties of slurry cast propellants by strengthening the nitrocellulose which has expanded into the areas immediately surrounding the metal fuel and solid oxidizer.
  • 2.4-tolylene di isocyanate was the principal diisocyanate used because it was readily available. Hexamethylene diisocyanate and bitolylene diisocyanate have been used in other work and were shown to react at a similar rate and with similar effects. Polyaryl polyisocyanate was used as a substitute for 2,4-tolylene diisocyanate in a solution cast propellant with good results. Other diisocyanates such as 2.6-tolylene diisocyanate or 3.3'-dimethyl diphenylmethane 4,4-diisocyanate could also be used.
  • the crosslinking catalyst for the diisocyanatehydroxyl reaction was either ferric acetylacetonate or lead 2- ethylhexoate.
  • Other catalysts as di-n-butyl tin diacetate should also give satisfactory results.
  • Other crosslinking systems that could be used include titanates. and anhydrides.
  • Nitroguanidine, cyclotetramethylene tetranitramine (HMX) and cyclotrirnethylene trinitramine were also successfully incorporated as oxidizers into the crosslinked solution or slurry cast propellants.
  • 2- Nitrodiphenylamine and resorcinol are usually used as stabilizers in modified double base propellants. That amine or ethyl Centralite (symmetrical diethyldiphenylurea) can be used in crosslinked versions but resorcinol does react with the diisocyanate. Resorcinol diacetate does not react with a diisocyanate and has been used as the second stabilizer.
  • plasticizer which is composed of explosive (an organic nitrate) and non-explosive (an ester, ketone, nitrile or nitro compound) components, is likewise only limited by consideration of reactivity and compatibility and the additional consideration of volatibility.
  • organic nitrates such as diethylene glycol dinitrate. triethylene glycol dinitrate and metriol trinitrate have been successfully used in crosslinked propellants.
  • Esters such as triacetin (glycerol triacetate).
  • diallyl phthalate, di-npropyl adipate and dimethyl sebacate and a nitrile such as adiponitrile have been used and a ketone such as isophorone (3.5.5-trimethyl-2cyclohexen-l-one) or a nitro compound such as o-chloronitrobenzene or dinitrotoluene can be used.
  • a curing time of 16 hours at 50 C. was ade quate. Casting time of l to 3 hours and gel time of 6 to lo hours were used. The gel time is the time required for the slurry to change to a nonfluid mass. Physical properties of a representative sample of this propellant at 77 F. showed tensile strength of 19 psi, a modulus of 130 psiv and an elongation value of 21%.
  • EXAMPLE ll EXAMPLE lll Composition (71 by filghll Nitrocellulose (denslfied. sub 40 mesh) l0 Ammonium perchlorate 20 Aluminum 20 Nitroglycerin 36.2 Di-n-propyl adipate I I5 2Nitrodiphenylaminc It) Resorcinol diacetate It) 2.4-Tolylene diisocyanate .25 Fern'c acetylacetonate .05
  • the mixing procedure of this composition involves mixing of the above ingredients (200 g) in a Morton stirring flask at a reduced pressure (2 mm.). The slurry was transferred under pressure into a glass container and subjected to reduced pressure to remove entrained and dissolved air. The propcllane was not cured for 4 days at l40 F. This sample showed a low tensile strength of 24 psi. a modulus of psi., and an elongation value of 81% at 77 F.
  • the stirring of the ingredients may also be accom plished in a modified Aseptic Dispersal] Unit which is driven by a Waring Blendor.
  • the batch size was 300 grams. Ingredients were mixed in a modified Aseptic Dispersall Unit which was driven by a Waring Blendor. To a solution of all ingredients (tolylene diisocyanate, resorcinol diacetate, and ferric acetylacetonate) which are soluble in the casting solvent (liquid organic nitrate and non-explosive plasticizer) was added the solid ingredients. These were added singly to minimize the amount of material that must be folded in at any one time. The order of addition was nitrocellulose, oxidizer, and then aluminum. Reduced pressure was applied after solids wetting was completed to remove most of the entrained air. The slurry was transferred into a glass container in which removal of entrained air was completed. The propellant was cured for 4 days at 120 F. Tests of this sample at 77 F. showed the modulus value at 450 psi.; tensile strength at 81 psi. and elongation at 57%.
  • Ferric ucetylacetonate EXAMPLE VII Composition by weight) Nitrocellulose (densified sub 40 mesh) Ammonium perchlorate 7 Cyclotetramethylene tetranitramine 14 Aluminum 16 Nitroglycerin 32.28 Di-n-propyl adipate 10.33 Z-Nitrodiphenylamine 1.0 Resorcinol diacetate 1.0 2.4-Tolylene diisocyanate 0.38 Ferric acetylacetonate Ferric oxide The above ingredients were rotationally mixed in an Aseptic Dispersall Unit as described in Example V. The product was then cured 4 days at F. Tests were made which show the following physical characteristics at 77 F.: tensile strength, 46 psi.; modulus, 350 psi.; and elongation value 44%.
  • Example 2 The above ingredients were rotationally mixed in the same manner as described in Example "I.
  • the product was cured for 6 days at 140 F. and tests show the following physical properties at 77 F tensile strength, 47 psi.; modulus, 590 psi.; and elongation 25%.
  • EXAMPLE lX Composition by weight Nitrocellulose (densified, sub 40 mesh) 15 Ammonium perchlorate 20 Aluminum 20 Nitroglycerin 32. 19 Triacetin 10.30 Z-Nitrodiphenylamine 1.0 Resorcinol diacetate 1.0 2.4-Tolylene diisocyanate 0.50 Ferric acetylacetonate 0.01
  • Example V The above ingredients were mixed as described in Example V.
  • the propellant was cured for 6 days at 140 F. and tests show the following physical properties at 77 F.: tensile strength, 38 psi.; modulus, 380 psi.; and elongation 28%.
  • the above ingredients were rotationally mixed in an Aseptic Dispersall Unit, the dry ingredients being added singly; first the nitrocellulose, then the oxidizer and aluminum as described in Example V. After the solids were wetted by the remainder of the ingredients, the slurry was poured into a container and cured for a week at F.
  • the test results show the following physical characteristics at 77 F.; tensile strength, 66 psi.; modulus, 500 psi.; and elongation value 37%.
  • Example 1V The above ingredients were mixed as described in Example 1V and cured for 7 days at 120 F.
  • the nitrocellulose was fluid ball powder with average particle size of 70 .1,.
  • a test of the cured product shows the following physical characteristics at 77 F.: tensile strength, 95 psi; modulus. 760 psi.', and elongation value 40%.
  • EXAMPLE XII Composition 1% by weight) Nitrocellulose Ammonium perchlorate 10 Aluminum 10 Nitroglycerin 32.15 Triacetin 10.29 2Nitrodiphenylamine 1.54 Ethyl Centralite (symmetrical 0.46
  • Example V The ingredients were mixed in the manner described in Example V and cured for one day at 1 14 F. and 3 days at F.
  • a sample of this composition showed the following physical characteristics at 77 F.: tensile strength. 1 13 psi.; modulus. psi.; and elongation of 91%.
  • EXAMPLE XlV Composition (7: by weight) Nitrocellulose (densified, sub 40 mesh) 15 Ammonium perchlorate 20 Aluminum 20 Triethylene glycol dinitrate 42.86 Z-Nitrodiphenylamine 1.0 Resorcinol diacetate 1.03
  • Example 111 A test of this propellant composition gives the following physical characteristics at 77 F.: tensile strength. 46 psi.; modulus, 320 psi.; and elongation 30%.
  • EXAMPLE XV The above ingredients were mixed in the manner described in Example V and cured for 7 days at 120 F. A sample of this composition was tested giving the following physical characteristics at 77 F.: tensile strength. 102 psi; modulus, 740 psi; and elongation value 34%.
  • Fluid ball powder and plastisol nitrocellulose are small. essentially spherical nitrocelluloses whose average particle sizes vary by a factor of seven. Again the material with the smaller particle size gave the better physical properties as is illustrated by the following Table lll wherein the samples are the same as those compared in Table I.
  • compositions containing other organic nitrates such as diethylene glycol dinitrate (see Table l. Samples 27 and 28) and triethylene glycol dinitrate (Table l, Sample were incorporated into crosslinked propellants in this invention and it was found necessary to decrease the crosslinker concentration from that used in the nitroglycerin based propellant from about 13 stoichiometric percent to about 4 5 stoichiometric percent to obtain satisfactory physical properties. A decrease in the catalyst level from 0.01 to 0.002% was also necessary for the propellant containing diethylene glycol dinitrate (Table I, Sample 28).
  • Solid oxidizers such as cyclotetramethylene tetranitramine and nitroguanidine were satisfactorily incorporated into the crosslinked propellants of this invention as shown in Samples No. 9 and 10 of Table l. respec' tively.
  • the casting of the propellants of this invention was accomplished by allowing the slurry with its crosslink' ing agent to flow into a suitable container while applying reduced pressure to that container to remove entrained air.
  • Solution cast propellants contained methylene chloride and that diluent had to be removed while pouring.
  • the sample size of solution cast propellants (Example I) was 200 to 300 g. These were cast in containers to a depth of from 3.5 to 6.5 inches.
  • the propellant mixture was cast in a one-inch inside diameter glass test tube. which had been coated with a protective material that would permit the cured propellant mass to be removed intact. and type E tensile dumbbells were machined from the cured mass.
  • the sample size of slurry cast propellants (those de scribed in Table ll was 200 600 g. Most of the specimens for physical property testing were obtained by casting and curing the slurry in a cellulose acetate beaker and then machining type 2 tensile dumbbells from the cured mass.
  • a propellant composition consisting of at least one of a member of nitrocelluloses selected from a group consisting of densified nitrocellulose. fluid ball powder nitrocellulose and plastisol nitrocellulose. at least one of a member of solid oxidizers selected from a group consisting of ammonium perchlorate, cyclotetramethylene tetranitramine. cyclotrimethylene trinitramine and nitroguanide. at least one of a member of explosive plasticizers selected from a group consisting of nitroglycerin, diethylene glycol dinitrate, triethylene glycol dinitrate and metriol trinitrate.
  • a member of non-explosive plasticizers selected from a group consisting of triacetin. diallyl phthalate. di-n-propyl adipate. dimethyl sebacate. adiponitrile. isophorone (3.5- .5-trimethyl-2-cyclohcxen-l-one).
  • ochloronitrobenzene and dinitrotoluene a stabilizer selected from a group consisting of Z-nitrodiphenylamine resorcinol diaeetate and symmetrical diethyldiphenylurea.
  • a crosslinking agent selected from a group consisting of 2.4-tolylene diisocyanate. hexamethylene diisocyanate.
  • bitolylene diisocyanate polyaryl polyisocyanate. 2 6'diisocyanatc and 3.3'-dimethyl diphenylmethane 4.4'-diisocyanate, and a crosslinking catalyst selected from a group consisting of ferric acelylacetonate. lead Z-ethylhexoate, and di-n-butyl tin diacetate.
  • a method for the preparation of a modified double base propellant grain comprising the steps of l adding while stirring at about 2 mm pressure nitrocellulose. ammonium perchlorate and aluminum to a solution composed of nitroglycerin, di-n-propyl adipate, 2- nitrophenylamine. resorcinol diacetate, 2,4-tolylene diisocyanate and ferric acetylaeetonate, (2) transferring the resulting mixture under lower pressure to a container, and (3 curing for about seven days at a tem perature ranging between to l20 C.
  • a method for the preparation of modified double base propellants comprising the steps of (l) stirring 100 parts of the following mixture consisting of (a) l 1 parts by weight nitrocellulose. (b) 22 parts by weight ammonium perchlorate. (c) 20 parts by weight aluminum, (d) 34.79 parts by weight nitroglycerin. (e) 11.13 parts by weight triacetin. (f) 1.03 parts by weight 2- nitrodiphenylamine and (g) 0.07 parts by weight lead Z-ethylhexoate. with 58 parts methylene chloride until the solids are well dispersed, (2) removing all but about l0% of the methylene chloride by heating to a temperature of about 40 45 C. (3) adding 0.3 parts by weight 2.4-tolylene diisocyanatc. (4) transferring the mixture under pressure of about 15 psi. to a curing container and curing for about 16 hours at about 50 C.
  • a propellant composition consisting of a binder composed of nitrocellulose, an oxidizer selected from the group consisting of ammonium perchlorate, nitroguanidine. cyclotetramethylene tetranitramine, and cyclotrimethylene tetranitramine, a solvent composed of a mixture selected from the group consisting of nitroglycerin. triacetin, nitrodiphenylamine, triethylene glycol dinitrate and diethylene glycol dinitrate.
  • aluminum metal powder a catalyst selected from the group consisting of lead-2-ethylhexoate and ferric acetylacetonate, and a crosslinking agent selected from the class of diisocyanates consisting of 2,4-tolylene diisocyanate. 3.3'-diisocyanate, hexamethylene diisocyanate and bitolylene diisocyanate.
  • a propellant composition consisting essentially of nitrocellulose, ammonium perchlorate, aluminum, nitroglycerin. di-n-propyl adipate, 2-nitrodiphenylamine, resorcinol diacetate, 2,4-tolylene diisocyanate and ferll'lC acetylacetonate.
  • a propellant composition consisting essentially of from 10 to 20% nitrocellulose, about 20% ammonium perchlorate, about 20% aluminum, 28.4 to 36.2% nitroglycerin, 9 to 11.5% di-n-propyl adipate, 1% resorcinol diacetate, 1% 2-nitrodiphenylamine, 0.15 to 0.50% 2,4-tolylene diisocyanate and 0.007 to 0.05% ferric acetylacetonate; all percentages being by weight.
  • a propellant composition consisting essentially of 15 to 21.6% nitrocellulose of p. particle size, 20 to 20.2% ammonium perchlorate, 20 to 20.9% aluminum, 26.3 to 32.4% nitroglycerin, 8.4 to 10.15% triacetin, 1.0% Z-nitrodiphenylamine, 1.0% resorcinol, 0.10% calcium phosphate, 0.38 to 0.40% 2.4-toly1ene diisocyanate, 0.01% ferric acetylacetonate and 0.03 to 0.04% dioctyl phthalate; all percentages being by weight.
  • a propellant composition consisting essentially of 15% plastisol nitrocellulose, 20% ammonium perchlorate, 20% aluminum, 32.1 to 32.25% nitroglycerin, 10.2 to 10.3% triacetin, 1.2 to 1.55% 2- nitrodiphenylamine, 0.4 to 0.8% symmetrical diethyldiphenylurea, 0.1% calcium phosphate, 0.30 to 0.45% 2,4-tolylene diisocyanate and 0.01% ferric acetylacetonate; all percentages being be weight.

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Abstract

1. A propellant composition consisting of at least one of a member of nitrocelluloses selected from a group consisting of densified nitrocellulose, fluid ball powder nitrocellulose and plastisol nitrocellulose, at least one of a member of solid oxidizers selected from a group consisting of ammonium perchlorate, cyclotetramethylene tetranitramine, cyclotrimethylene trinitramine and nitroguanide, at least one of a member of explosive plasticizers selected from a group consisting of nitroglycerin, diethylene glycol dinitrate, triethylene glycol dinitrate and metriol trinitrate, at least one of a member of non-explosive plasticizers selected from a group consisting of triacetin, diallyl phthalate, di-n-propyl adipate, dimethyl sebacate, adiponitrile, isophorone (3,5,5-trimethyl-2cyclohexen-1-one), o-chloronitrobenzene and dinitrotoluene, a stabilizer selected from a group consisting of 2nitrodiphenylamine resorcinol diacetate and symmetrical diethyldiphenylurea, a crosslinking agent selected from a group consisting of 2,4-tolylene diisocyanate, hexamethylene diisocyanate, bitolylene diisocyanate, polyaryl polyisocyanate, 2,6-diisocyanate and 3,3''-dimethyl diphenylmethane 4,4''diisocyanate, and a crosslinking catalyst selected from a group consisting of ferric acelylacetonate, lead 2-ethylhexoate, and di-n-butyl tin diacetate.

Description

United tates Patent 1 Elrick [45] July 15, 1975 MODIFIED DOUBLE BASE PROPELLANTS WITH DIISOCYANATE CROSSLINKER Donald E. Elrick, Cumberland, Md.
1173] Assignee: The United States of America as represented by the Secretary of the Navy, Washington, DC.
[22] Filed: June 8,1962
21 Appl.No.:202,355
[75] inventor:
[52] US. Cl. l49/l9.4; l49/l9.8; 149/l9.92; 149/20; 149/38; 149/98; 149/92 [51] Int. Cl C06d 5/06 [58] Field of Search Primary Examiner-Benjamin R. Padgett Assistant E.\'aminer-E. A. Miller Almrney. Agent. or Firm-R. S. Sciascia; Roy Miller EXEMPLARY CLAIM l. A propellant composition consisting of at least one of a member of nitrocelluloses selected from a group consisting of densified nitrocellulose, fluid ball powder nitrocellulose and plastisol nitrocellulose, at least one of a member of solid oxidizers selected from a group consisting of ammonium perchlorate, cyclotetramethylene tetranitramine, cyclotrimethylene trinitramine and nitroguanide, at least one of a member of explosive plasticizers selected from a group consisting of nitroglycerin, diethylene glycol dinitrate, triethylene glycol dinitrate and metriol trinitrate, at least one of a member of non-explosive plasticizers selected from a group consisting of triacetin, diallyl phthalate, di-n-propyl adipate, dimethyl sebacate, adiponitrile, isophorone (3,5,5-trimethyl-2-cyclohexen-l-one), ochloronitrobenzene and dinitrotoluene, a stabilizer selected from a group consisting of 2- nitrodiphenylamine resorcinol diacetate and symmetrical diethyldiphenylurea, a crosslinking agent selected from a group consisting of 2,4-tolylene diisocyanate, hexamethylene diisocyanate, bitolylene diisocyanate, polyaryl polyisocyanate, 2,6-diisocyanate and 3,3- dimethyl diphenylmethane 4,4'-diisocyanate, and a crosslinking catalyst selected from a group consisting of ferric acelylacetonate, lead 2-ethylhexoate, and din-butyl tin diacetate.
8 Claims, N0 Drawings MODIFIED DOUBLE BASE PROPELLANTS WITH DTISOCYANATE CROSSLINKER The present invention relates to the crosslinking of modified double base propellants by reacting the nitrocellulose binder with a suitable polyfunctional crosslinking agent such as a diisocyanate. Reaction occurs during cure and results in improved physical properties over hon-crosslinked versions provided that the amount of nitrocellulose in the binder phase is sufficiently small.
Modified doubled base propellants contain a solid oxidizer such as ammonium perchlorate. a metal fuel such as aluminum. and a liquid organic nitrate plasticizcr such as nitroglycerin in addition to the nitrocellulose binder and can be prepared in a number of ways. Most modified double base propellants are prepared using a casting process, wherein casting powder granules containing nitrocellulose. solid oxidizer, metal fuel and a plasticizer (usually nitroglycerin) are immersed in additional plasticizer and allowed to cure. during cure the granules expand and coalesce to form the cast propellant. These propellants have satisfactory physical properties if the nitrocellulose content in the binder phase is sufficiently high, about 23 volume percent. Specific impulse of the propellant would be improved if additional solid oxidizer could be substituted for a portion of the nitrocellulose. There are two reasons that the nitrocellulose content in propellants is kept above this level. First, high density casting powder containing small amounts of nitrocellulose is very difficult to prepare. and second, physical properties particularly modulus and tensile strength, would be quite low. The econd disadvantage could be overcome by the use of crosslinking but there is no experimental evidence of this.
Other modified double base propellants are prepared using a slurry-cast process, wherein nitrocellulose in the form of very small. hard particles is mixed with the ingredients previously mentioned and the resulting slurry is poured into a container in which it is cured. During cure. the liquids plasticize the nitrocellulose and there is some swelling of the latter. The swelling, however. does not occur to the same extent as it does in cast propellants for the physical properties of cast propellants are better than those of slurry-cast propellants tvhich are of similar composition. Crosslinked slurry-cast propellants do show increased tensile strength and elongation when compared to noncrosslinked versions and most of the experimental data ll'l this invention is used to support this observation.
This invention also concerns solution cast propellants which comprise a third method of preparing modified double base propellants. In this method, a slurry of the previously mentioned ingredients is prepared and poured into a container and cured. The method is thus similar to slurry-cast propellants and differs from that type of propellant in that the nitrocellulose of the solution cast propellant is completely in solution prior to pouring. Solutions of normally used (military grade it) I 8 sec.) nitrocellulose are quite viscous and a very low viscosity nitrocellulose (18-25 cp.) is crosslinked during the curing phase to convert the slurry to a solid mass. ln this method the solid ingredients (nitrocellulose. solid oxidizer, and metal fuel) are added to a solution of casting solvent. stabilizer and crosslinking catalyst in methylene chloride. Nitrocellulose is essentially insoluble in this solution and thus may be well dispersed by stirring so that dissolution does occur readily as methylene chloride is gradually removed. When about 10% methylene chloride remains in this slurry, nitrocellulose is in solution. The crosslinker is added and dispersed at this time. The slurry is now transferred to a curing container under reduced pressure and heat is applied to facilitate removal of the remaining methylene chloride. The purpose of the diluent, methylene chloride, is thus twofold: a means of ensuring rapid dissolution of nitrocellulose and a means of increasing fluidity so that transfer can be more readily effected.
The primary purpose of the present invention is to improve the physical properties of slurry-cast propellants by crosslinking the nitrocellulose binder. Other purposes include the improvement by cross-linking of physical properties of cast propellants containing small amounts, less than about 23 volume percent, of nitrocellulose in the binder phase and a new method of preparing modified double base propellants, wherein a slurry containing nitrocellulose in solution is made more or less rigid by crosslinking that binder.
It is, therefore, an object of the present invention to improve physical properties of modified double base propellants.
Another object is the improvement of specific impulse.
Still another object is to provide a process for the production of propellant grains which has the economic advantages of reduced time, equipment and labor.
A further object of the present invention is the provision ofa method for casting propellant grains which has the potential advantage of even greater simplicity and versatility than the standard casting procedure.
A still further object is the preparation of a propellant composition that can be poured into a motor and by suitable means polymerized to a solid bonded to the motor.
Other objects and many of the attendant advantages of this invention will be readily appreciated as the same become better understood in the following detailed description.
The mechanism of the crosslinking involves the reaction of the hydroxyl groups of the nitrocellulose with a polyfunctional crosslinker such as a diisocyanate. Commercial nitrocellulose has roughly 2.2 to 2.5 nitrate groups and 0.8 to 0.5 hydroxyl groups per monomer length. These hydroxyl groups can react more or less readily with difunctional molecules to form crosslinks which, in effect, increase the size of the molecule, change the structure from linear to branched, and alter the physical characteristics of the polymer. Crosslinking tends to increase the rigidity of the propellant matrix and the tendency for flow to occur at normal temperatures is decreased. Because of this change the tensile strength and modulus are increased and the elongation decreased at normal temperatures.
Crosslinking then improves the physical properties of solution cast propellants, which would flow if not crosslinked and should improve the physical properties of cast propellants containing small amounts of nitrocellulose by making the propellant matrices more rigid. Crosslinking apparently improves physical properties of slurry cast propellants by strengthening the nitrocellulose which has expanded into the areas immediately surrounding the metal fuel and solid oxidizer.
In addition to nitrocellulose. the ingredients involved in the crosslinking reaction are the crosslinker and crosslinking catalyst. ln this invention 2.4-tolylene di isocyanate was the principal diisocyanate used because it was readily available. Hexamethylene diisocyanate and bitolylene diisocyanate have been used in other work and were shown to react at a similar rate and with similar effects. Polyaryl polyisocyanate was used as a substitute for 2,4-tolylene diisocyanate in a solution cast propellant with good results. Other diisocyanates such as 2.6-tolylene diisocyanate or 3.3'-dimethyl diphenylmethane 4,4-diisocyanate could also be used. The crosslinking catalyst for the diisocyanatehydroxyl reaction was either ferric acetylacetonate or lead 2- ethylhexoate. Other catalysts as di-n-butyl tin diacetate should also give satisfactory results. Other crosslinking systems that could be used include titanates. and anhydrides.
Any ingredient, which does not interfere with the crosslinking action or does not adversely affect propel lant stability, may be used in crosslinked modified double base propellants. A metal powder. such as aluminum, is used as a fuel to obtain a high theoretical specific impulse. A liquid fuel. such as carboranylmethyl acrylate, has also been incorporated. A solid oxidizer such as ammonium perchlorate should also be present in the propellant to obtain acceptable delivered impulses. Nitroguanidine, cyclotetramethylene tetranitramine (HMX) and cyclotrirnethylene trinitramine were also successfully incorporated as oxidizers into the crosslinked solution or slurry cast propellants. 2- Nitrodiphenylamine and resorcinol are usually used as stabilizers in modified double base propellants. That amine or ethyl Centralite (symmetrical diethyldiphenylurea) can be used in crosslinked versions but resorcinol does react with the diisocyanate. Resorcinol diacetate does not react with a diisocyanate and has been used as the second stabilizer.
The choice of a plasticizer, which is composed of explosive (an organic nitrate) and non-explosive (an ester, ketone, nitrile or nitro compound) components, is likewise only limited by consideration of reactivity and compatibility and the additional consideration of volatibility. In addition to nitroglycerin. other organic nitrates such as diethylene glycol dinitrate. triethylene glycol dinitrate and metriol trinitrate have been successfully used in crosslinked propellants. Esters such as triacetin (glycerol triacetate). diallyl phthalate, di-npropyl adipate and dimethyl sebacate and a nitrile such as adiponitrile have been used and a ketone such as isophorone (3.5.5-trimethyl-2cyclohexen-l-one) or a nitro compound such as o-chloronitrobenzene or dinitrotoluene can be used.
A more comprehensive understanding of this invention is obtained by reference to the following examples:
EXAMPLE 1 Composition l Parts by weight) Nitrocellulose (l2.2%N, 18-25 cp.) l
Nitroglycerin Triacetin Z-Nitrodiphenylamine Lead Z-ethylhexoate 2.4-Tolylene diisocyanate l I ll H13 0.07 l) 30 The mixing procedure involves mixing all the ingredients above listed parts) except for the crosslinker (2.4-tolylene diisocyanate) and 58 parts methylene chloride in a rotating container until the solids are well dispersed. Methylene chloride was gradually removed by heating and reduced pressure application as rotational stirring was continued. When only about l0% methylene chloride remained, the crosslinking agent. 2,4-toluene diisocyanate was added and mixed. The mixture was now transferred to a curing container under reduced pressure lmm. and heated to 40 45 C. to facilitate removal of the remaining methylene chloride. A curing time of 16 hours at 50 C. was ade quate. Casting time of l to 3 hours and gel time of 6 to lo hours were used. The gel time is the time required for the slurry to change to a nonfluid mass. Physical properties of a representative sample of this propellant at 77 F. showed tensile strength of 19 psi, a modulus of 130 psiv and an elongation value of 21%.
EXAMPLE ll EXAMPLE lll Composition (71 by filghll Nitrocellulose (denslfied. sub 40 mesh) l0 Ammonium perchlorate 20 Aluminum 20 Nitroglycerin 36.2 Di-n-propyl adipate I I5 2Nitrodiphenylaminc It) Resorcinol diacetate It) 2.4-Tolylene diisocyanate .25 Fern'c acetylacetonate .05
The mixing procedure of this composition involves mixing of the above ingredients (200 g) in a Morton stirring flask at a reduced pressure (2 mm.). The slurry was transferred under pressure into a glass container and subjected to reduced pressure to remove entrained and dissolved air. The propcllane was not cured for 4 days at l40 F. This sample showed a low tensile strength of 24 psi. a modulus of psi., and an elongation value of 81% at 77 F.
The stirring of the ingredients may also be accom plished in a modified Aseptic Dispersal] Unit which is driven by a Waring Blendor.
The above ingredients (550 g) were all mixed in a stirring flask at reduced pressure as described in Exam-- ple lll. Physical properties at 77 F. were as follows:
tensile strength 42 psi., modulus 220 psi. and elongation 42%.
The batch size was 300 grams. Ingredients were mixed in a modified Aseptic Dispersall Unit which was driven by a Waring Blendor. To a solution of all ingredients (tolylene diisocyanate, resorcinol diacetate, and ferric acetylacetonate) which are soluble in the casting solvent (liquid organic nitrate and non-explosive plasticizer) was added the solid ingredients. These were added singly to minimize the amount of material that must be folded in at any one time. The order of addition was nitrocellulose, oxidizer, and then aluminum. Reduced pressure was applied after solids wetting was completed to remove most of the entrained air. The slurry was transferred into a glass container in which removal of entrained air was completed. The propellant was cured for 4 days at 120 F. Tests of this sample at 77 F. showed the modulus value at 450 psi.; tensile strength at 81 psi. and elongation at 57%.
EXAMPLE Vl Composition by weight) Nitrocellulose (densified, washed) 20 Ammonium perchlorate 20 Aluminum 20 Nitroglycerin 28.64 lDi-npropyl adipate 9.17 I-Nitrodipheny amine 1.0 Resorcinol diacetate 1.0 I.4-Tolylene diisocyanate 0.18
Ferric ucetylacetonate EXAMPLE VII Composition by weight) Nitrocellulose (densified sub 40 mesh) Ammonium perchlorate 7 Cyclotetramethylene tetranitramine 14 Aluminum 16 Nitroglycerin 32.28 Di-n-propyl adipate 10.33 Z-Nitrodiphenylamine 1.0 Resorcinol diacetate 1.0 2.4-Tolylene diisocyanate 0.38 Ferric acetylacetonate Ferric oxide The above ingredients were rotationally mixed in an Aseptic Dispersall Unit as described in Example V. The product was then cured 4 days at F. Tests were made which show the following physical characteristics at 77 F.: tensile strength, 46 psi.; modulus, 350 psi.; and elongation value 44%.
EXAMPLE VllI Composition by weight) Nitrocellulose (densified, sub 40 mesh) 15 Ammonium perchlorate l0 Nitroguanidine 10 Aluminum 20 Nitroglycerin 32.28 Di-n-propyl adipate 10.33 2Nitrodiphenylamine l .0 Resorcinol diacetate 1.0 2,4-Tolylene diisocyanate 0.38 Ferric acetylacetonate 0.01
The above ingredients were rotationally mixed in the same manner as described in Example "I. The product was cured for 6 days at 140 F. and tests show the following physical properties at 77 F tensile strength, 47 psi.; modulus, 590 psi.; and elongation 25%.
EXAMPLE lX Composition by weight) Nitrocellulose (densified, sub 40 mesh) 15 Ammonium perchlorate 20 Aluminum 20 Nitroglycerin 32. 19 Triacetin 10.30 Z-Nitrodiphenylamine 1.0 Resorcinol diacetate 1.0 2.4-Tolylene diisocyanate 0.50 Ferric acetylacetonate 0.01
The above ingredients were mixed as described in Example V. The propellant was cured for 6 days at 140 F. and tests show the following physical properties at 77 F.: tensile strength, 38 psi.; modulus, 380 psi.; and elongation 28%.
The above ingredients were rotationally mixed in an Aseptic Dispersall Unit, the dry ingredients being added singly; first the nitrocellulose, then the oxidizer and aluminum as described in Example V. After the solids were wetted by the remainder of the ingredients, the slurry was poured into a container and cured for a week at F. The test results show the following physical characteristics at 77 F.; tensile strength, 66 psi.; modulus, 500 psi.; and elongation value 37%.
The above ingredients were mixed as described in Example 1V and cured for 7 days at 120 F. The nitrocellulose was fluid ball powder with average particle size of 70 .1,. A test of the cured product shows the following physical characteristics at 77 F.: tensile strength, 95 psi; modulus. 760 psi.', and elongation value 40%.
EXAMPLE XII Composition 1% by weight) Nitrocellulose Ammonium perchlorate 10 Aluminum 10 Nitroglycerin 32.15 Triacetin 10.29 2Nitrodiphenylamine 1.54 Ethyl Centralite (symmetrical 0.46
diethyldiphenylurea) Calcium phosphate 0.10 2.4Tolylene diisocyanate 0.45
Ferric acetylacetonate 0.01
EXAMPLE XllI Composition 1% by weight] Nitrocellulose (plastisol. 10p! Ammonium perchlorate Aluminum 20 Nitroglycerin 32.20 Diallyl phthalate 10.31 Z-Nitrodiphenylamine 1.0 Resorcinol diacetate 1.0
2.4-Tolylene diisocyanate Ferric acetylacetonate 0.01
The ingredients were mixed in the manner described in Example V and cured for one day at 1 14 F. and 3 days at F. A sample of this composition showed the following physical characteristics at 77 F.: tensile strength. 1 13 psi.; modulus. psi.; and elongation of 91%.
EXAMPLE XlV Composition (7: by weight) Nitrocellulose (densified, sub 40 mesh) 15 Ammonium perchlorate 20 Aluminum 20 Triethylene glycol dinitrate 42.86 Z-Nitrodiphenylamine 1.0 Resorcinol diacetate 1.03
Z,4-Tolylene diisocyanate Ferric acetylacetonate 0.01
These ingredients were mixed and cured in the manner described in Example 111. A test of this propellant composition gives the following physical characteristics at 77 F.: tensile strength. 46 psi.; modulus, 320 psi.; and elongation 30%.
EXAMPLE XV The above ingredients were mixed in the manner described in Example V and cured for 7 days at 120 F. A sample of this composition was tested giving the following physical characteristics at 77 F.: tensile strength. 102 psi; modulus, 740 psi; and elongation value 34%.
The following table (page 15) shows the composition and physical properties of nineteen crosslinked slurrycast propellants of this invention and nine noncrosslinked slurry-cast propellants to show by comparison the improvements in physical properties that were obtained by crosslinking. In this study tolylene diisocyanate (TDl) was the only crosslinker investigated because it was readily available. However, others such as polyaryl polyisocyanate and hexamethylene diisocyanate are as satisfactory.
The improvement in physical properties by crosslinking may be readily noted by comparing the physical properties of the following pairs of samples as set out in the above Table: 2 to 3. 4 to 5, 6 to 8, 11 to l2, 15 to l6. 17 to 18. 21 to 22, 24 to 25 and 26 to 28. In these pairs, a portion of the plasticizer in the non-crosslinked propellant was replaced in Table 1 (page 15) the abbreviations used refer to the following:
TABLE] Comparison of Physical Properties of Crosslinked and Non-crosslinked Propellants COMPOSITION Samp NC AP HMXNGD Al Nitrate Non Ex Pl NDPA EC Res RDA CP TD1 FAA DOP FO No. l%)( 1 Name Name 1 10 20 20 NO 36.2 DnPA 11.5 1 1 0.25 0.05 '2 15 20 20 NC 32.6 DnPA 10.4 1 I 3 15 20 20 NO 32.25 DnPA 10.32 1 l 0.38 0.05 *4 I5 20 20 NC] 32.6 DnPA 10.4 1 1 5 15 20 20 NO 32.28 DnPA 10.33 1 1 0.38 0.01 *6 20 20 20 NC 28.8 DnPA 9.2 1 l 7 20 20 20 NO 28.40 DnPA 9.09 1 1 0.50 0.01 l"; 20 20 20 NO 28.64 DnPA 9.17 1 l 0.18 0.007 n I5 7 14 16 NO 32.28 DnPA 10.33 1 l 0.38 0.01 3.0 10 l5 10 10 20 NO 32.28 DnPA 10.33 1 l 0.38 0.01 ll 20 NO 32.6 TA 10.4 1 1 12 15 20 20 NO 32.19 TA 10.30 1 1 0.50 0.01 113 15 20 20 NO 32.34 TA 10.14 1 1 0.10 0.38 0.01 0.03 114 15 20 20 NO 32.29 TA 10.12 1 1 0.10 0.45 0.01 0.03 15 I0 20 20 NO 28.81 TA 9.15 1 1 0.04 16 20 20 20 NO 2842 TA 9.03 1 1 0.10 0.40 0.01 0.04 17 21620.2 209 NO 26.64 TA 8.52 1 l 0.10 0.04 18 216202 20.9 NO 26.34 TA 8.41 1 l 0.10 0.40 0.01 0.04 l9 15 20 20 NO 32.21 TA 10.30 1.21 0.79 0.10 0.38 0.01 10 15 20 20 NO 32.15 TA 10.29 1.54 0.46 0.10 0.45 0.01 21 15 20 20 NO 32.6 DAP 10.4 1 1 .22 15 20 20 NC 32.28 DAP 10.33 1 1 0.38 0.01 .13 [5 20 20 NO 32.20 DAP 10.31 1 l 0.38 0.01 24 15 20 20 TGDN 43 1 1 25 15 20 20 TGDN 42.86 1 l 0.13 0.01 26 20 20 20 DGDN 37.50 1.36 1 .10 0.04 1720 20 20 DGDN 37.26 NG 0.08 1.36 1 0.10 0.15 0.01 0.04 .18 20 20 20 DGDN 37.27 NG 0.08 1.36 1 0.10 0.15 0.002 0.04
PHYSICAL PROPERTIES Rate Mod Ten St Elong (in/min/in) (psi) (psi) 0.1 24 81 1.0 500 33 21 0.74 220 42 42 1.0 390 37 26 1.0 450 81 57 0.1 860 48 14 0.1 860 60 19 0.1 800 72 29 0.74 350 46 44 0.1 590 47 25 0.1 7 24 0.1 380 37 28 1.0 200 37 44 1.0 500 66 37 1.0 550 52 32 1.0 850 103 55 0.74 620 83 29 0.74 760 95 40 0.74 190 117 134 0.74 240 148 118 0.1 190 15 13 0.74 250 54 43 0.1 113 91 0.1 230 16 20 0.1 320 46 30 0.74 670 68 19 0.74 510 59 16 0.74 740 102 34 Res Resorcinol RDA Resorcinol diacetate CP Calcium phosphate (coating for ammonium perchlorate) TDI 2,4-Tolylene diisocyanate (a crosslinker) FAA Ferric acetylacetonate (a crosslinking'catalyst) DOP Dioctyl phthalate (present in fluid ball powder to harden surface) FO Ferric oxide Mod Modulus Ten St Tensile strength Elong Elongation value by crosslinker and catalyst in the crosslinked propellant and increases were obtained in both tensile strength and in elongation. a non-crosslinked version of Sample No. 1 shown in Table 1 would not have sufficient strength to maintain its shape.
There was also an improvement in physical properties when the nitrocellulose particle size was reduced. This can be shown by grouping Samples 2 through 5 as While there was some improvement in physical properties by reducing particle size in non-crosslinkcd versions (2 and 4). the improvement was more pronounced in the crosslinked versions (3 and 5).
Fluid ball powder and plastisol nitrocellulose are small. essentially spherical nitrocelluloses whose average particle sizes vary by a factor of seven. Again the material with the smaller particle size gave the better physical properties as is illustrated by the following Table lll wherein the samples are the same as those compared in Table I.
TABLE III Average Cross Tensile Sample Nitro- Particle linker Strength Elongation No. cellulose Size (u) (71) (psi) ('71 l 1] 71 ball 70 0.38 37 44 14 I571 hall 70 0.45 no 37 I9 I57: PNC 10 038 [I7 I34 [5'71 PNC IO 0.45 I48 H8 Ball fluid ball powder with average particle size of 70p" PNC plastisol nitrocellulose with 10p average particle size.
These samples l3, l4. l9 and 20. the composition of which is found in Table I. show the effect of crosslinker concentration on physical properties. An increase in crosslinker concentration gave an increase in tensile strength and a decrease in elongation.
Compositions containing other organic nitrates such as diethylene glycol dinitrate (see Table l. Samples 27 and 28) and triethylene glycol dinitrate (Table l, Sample were incorporated into crosslinked propellants in this invention and it was found necessary to decrease the crosslinker concentration from that used in the nitroglycerin based propellant from about 13 stoichiometric percent to about 4 5 stoichiometric percent to obtain satisfactory physical properties. A decrease in the catalyst level from 0.01 to 0.002% was also necessary for the propellant containing diethylene glycol dinitrate (Table I, Sample 28).
Solid oxidizers such as cyclotetramethylene tetranitramine and nitroguanidine were satisfactorily incorporated into the crosslinked propellants of this invention as shown in Samples No. 9 and 10 of Table l. respec' tively.
The casting of the propellants of this invention was accomplished by allowing the slurry with its crosslink' ing agent to flow into a suitable container while applying reduced pressure to that container to remove entrained air. Solution cast propellants contained methylene chloride and that diluent had to be removed while pouring. The sample size of solution cast propellants (Example I) was 200 to 300 g. These were cast in containers to a depth of from 3.5 to 6.5 inches. To obtain specimens for physical property testing. the propellant mixture was cast in a one-inch inside diameter glass test tube. which had been coated with a protective material that would permit the cured propellant mass to be removed intact. and type E tensile dumbbells were machined from the cured mass.
The sample size of slurry cast propellants (those de scribed in Table ll was 200 600 g. Most of the specimens for physical property testing were obtained by casting and curing the slurry in a cellulose acetate beaker and then machining type 2 tensile dumbbells from the cured mass.
Although the invention has been described in detail in the foregoing specification it is to be understood that many variations can be made by those skilled in the art without departing from the scope thereof except as limited by the appended claims.
What is claimed is:
l. A propellant composition consisting of at least one of a member of nitrocelluloses selected from a group consisting of densified nitrocellulose. fluid ball powder nitrocellulose and plastisol nitrocellulose. at least one of a member of solid oxidizers selected from a group consisting of ammonium perchlorate, cyclotetramethylene tetranitramine. cyclotrimethylene trinitramine and nitroguanide. at least one of a member of explosive plasticizers selected from a group consisting of nitroglycerin, diethylene glycol dinitrate, triethylene glycol dinitrate and metriol trinitrate. at least one of a member of non-explosive plasticizers selected from a group consisting of triacetin. diallyl phthalate. di-n-propyl adipate. dimethyl sebacate. adiponitrile. isophorone (3.5- .5-trimethyl-2-cyclohcxen-l-one). ochloronitrobenzene and dinitrotoluene a stabilizer selected from a group consisting of Z-nitrodiphenylamine resorcinol diaeetate and symmetrical diethyldiphenylurea. a crosslinking agent selected from a group consisting of 2.4-tolylene diisocyanate. hexamethylene diisocyanate. bitolylene diisocyanate, polyaryl polyisocyanate. 2 6'diisocyanatc and 3.3'-dimethyl diphenylmethane 4.4'-diisocyanate, and a crosslinking catalyst selected from a group consisting of ferric acelylacetonate. lead Z-ethylhexoate, and di-n-butyl tin diacetate.
2. A method for the preparation of a modified double base propellant grain comprising the steps of l adding while stirring at about 2 mm pressure nitrocellulose. ammonium perchlorate and aluminum to a solution composed of nitroglycerin, di-n-propyl adipate, 2- nitrophenylamine. resorcinol diacetate, 2,4-tolylene diisocyanate and ferric acetylaeetonate, (2) transferring the resulting mixture under lower pressure to a container, and (3 curing for about seven days at a tem perature ranging between to l20 C.
3. A method for the preparation of modified double base propellants comprising the steps of (l) stirring 100 parts of the following mixture consisting of (a) l 1 parts by weight nitrocellulose. (b) 22 parts by weight ammonium perchlorate. (c) 20 parts by weight aluminum, (d) 34.79 parts by weight nitroglycerin. (e) 11.13 parts by weight triacetin. (f) 1.03 parts by weight 2- nitrodiphenylamine and (g) 0.07 parts by weight lead Z-ethylhexoate. with 58 parts methylene chloride until the solids are well dispersed, (2) removing all but about l0% of the methylene chloride by heating to a temperature of about 40 45 C. (3) adding 0.3 parts by weight 2.4-tolylene diisocyanatc. (4) transferring the mixture under pressure of about 15 psi. to a curing container and curing for about 16 hours at about 50 C.
4. A propellant composition consisting of a binder composed of nitrocellulose, an oxidizer selected from the group consisting of ammonium perchlorate, nitroguanidine. cyclotetramethylene tetranitramine, and cyclotrimethylene tetranitramine, a solvent composed of a mixture selected from the group consisting of nitroglycerin. triacetin, nitrodiphenylamine, triethylene glycol dinitrate and diethylene glycol dinitrate. aluminum metal powder, a catalyst selected from the group consisting of lead-2-ethylhexoate and ferric acetylacetonate, and a crosslinking agent selected from the class of diisocyanates consisting of 2,4-tolylene diisocyanate. 3.3'-diisocyanate, hexamethylene diisocyanate and bitolylene diisocyanate.
5. A propellant composition consisting essentially of nitrocellulose, ammonium perchlorate, aluminum, nitroglycerin. di-n-propyl adipate, 2-nitrodiphenylamine, resorcinol diacetate, 2,4-tolylene diisocyanate and ferll'lC acetylacetonate.
b. A propellant composition consisting essentially of from 10 to 20% nitrocellulose, about 20% ammonium perchlorate, about 20% aluminum, 28.4 to 36.2% nitroglycerin, 9 to 11.5% di-n-propyl adipate, 1% resorcinol diacetate, 1% 2-nitrodiphenylamine, 0.15 to 0.50% 2,4-tolylene diisocyanate and 0.007 to 0.05% ferric acetylacetonate; all percentages being by weight.
7. A propellant composition consisting essentially of 15 to 21.6% nitrocellulose of p. particle size, 20 to 20.2% ammonium perchlorate, 20 to 20.9% aluminum, 26.3 to 32.4% nitroglycerin, 8.4 to 10.15% triacetin, 1.0% Z-nitrodiphenylamine, 1.0% resorcinol, 0.10% calcium phosphate, 0.38 to 0.40% 2.4-toly1ene diisocyanate, 0.01% ferric acetylacetonate and 0.03 to 0.04% dioctyl phthalate; all percentages being by weight.
8. A propellant composition consisting essentially of 15% plastisol nitrocellulose, 20% ammonium perchlorate, 20% aluminum, 32.1 to 32.25% nitroglycerin, 10.2 to 10.3% triacetin, 1.2 to 1.55% 2- nitrodiphenylamine, 0.4 to 0.8% symmetrical diethyldiphenylurea, 0.1% calcium phosphate, 0.30 to 0.45% 2,4-tolylene diisocyanate and 0.01% ferric acetylacetonate; all percentages being be weight.

Claims (8)

1. A PROPELLANT COMPOSITION CONSISTING OF AT LEAST ONE OF A MEMBER OF NITROCELLULOSES SELECTED FROM A GROUP CONSISTING OF DENSIFIED NITROCELLULOSE, FLUID BALL POWDER NITROCELLULOSE AND PLASTISOL NITROCELLULOSE, AT LEAST ONE OF A MEMBER OF SOLID OXIDIZERS SELECTED FROM A GROUP CONSISTING OF AMMONIUM PERCHLORATE, CYCLOTETRAMETHYLENE TETRANITRAMINE, CYCLOTRIMETHYLENE TRINITRAMINE AND NITROGUANIDE, AT LEAST ONE OF A MEMBER OF EXPLOSIVE PLASTICIZERS SELECTED FROM A GROUP CONSISTING OF NITROGLYCERIN, DIETHYLENE GLYCOL DINITRATE, TRIETHYLENE GLYCOL DINITRATE AND METRIOL TRINITRATE, AT LEAST ONE OF A MEMBER OF NON-EXPLOSIVE PLASTICIZERS SELECTED FROM A GROUP CONSISTING OF TRIACETIN, DIALLYL PHTHALATE, DI-N-PROPYL ADIPATE, DIMETHYL SEBACATE, ADIPONITRILE, ISOPHORONE (3,5,5-TRIMETHYL-2-CYCLOHEXEN1-ONE), O-CHLORONITROBENZENE AND DINITROTOLUENE A STABILIZER SELECTED FROM A GROUP CONSISTING OF 2-NITRODIPHENYLAMINE RESORCINOL DIACETATE AND SYMMETRICAL DIETHYLDIPHENYLUREA, A CROSSLINKING AGENT SELECTED FROM A GROUP CONSISTING OF 2,4TOLYLENE DIISOCYANATE, HEXAMETHYLENE DIISOCYANATE, BITOLYLENE DIISOCYANATE, POLYARYL POLYISOCYANATE, 2,6-DIISOCYANATE AND 3,3''-DIMETHYL DIPHENYLMETHANE 4,4''-DIISOCYANATE, AND A CROSSLINKING CATALYST SELECTED FROM A GROUP CONSISTING OF FERRIC ACELYLACETONATE, LEAD 2-ETHYLHEXOATE, AND DI-N-BUTYL TIN DIACETATE.
2. A method for the preparation of a modified double base propellant grain comprising the steps of (1) adding while stirring at about 2 mm pressure nitrocellulose, ammonium perchlorate and aluminum to a solution composed of nitroglycerin, di-n-propyl adipate, 2-nitrophenylamine, resorcinol diacetate, 2, 4-tolylene diisocyanate and ferric acetylacetonate, (2) transferring the resulting mixture under lower pressure to a container, and (3) curing for about seven days at a temperature ranging between 100* to 120* C.
3. A method for the preparation of modified double base propellants comprising the steps of (1) stirring 100 parts of the following mixture consisting of (a) 11 parts by weight nitrocellulose, (b) 22 parts by weight ammonium perchlorate, (c) 20 parts by weight aluminum, (d) 34.79 parts by weight nitroglycerin, (e) 11.13 parts by weight triacetin, (f) 1.03 parts by weight 2-nitrodiphenylamine and (g) 0.07 parts by weight lead 2-ethylhexoate, with 58 parts methylene chloride until the solids are well dispersed, (2) removing all but about 10% of the methylene chloride by heating to a temperature of about 40* -45* C., (3) adding 0.3 parts by weight 2,4-tolylene diisocyanate, (4) transferring the mixture under pressure of about 15 psi. to a curing container and (5) curing for about 16 hours at about 50* C.
4. A propellant composition consisting of a binder composed of nitrocellulose, an oxidizer selected from the group consisting of ammonium perchlorate, nitroguanidine, cyclotetramethylene tetranitramine, and cyclotrimethylene tetranitramine, a solvent composed of a mixture selected from the group consisting of nitroglycerin, triacetin, nitrodiphenylamine, triethylene glycol dinitrate and diethylene glycol dinitrate, aluminum metal powder, a catalyst selected from the group consisting of lead-2-ethylhexoate and ferric acetylacetonate, and a crosslinking agent selected from the class of diisocyanates consisting of 2,4-tolylene diisocyanate, 3,3''-diisocyanate, hexamethylene diisocyanate and bitolylene diisocyanate.
5. A propellant composition consisting essentially of nitrocellulose, ammonium perchlorate, aluminum, nitroglycerin, di-n-propyl adipate, 2-nitrodiphenylamine, resorcinol diacetate, 2,4-tolylene diisocyanate and ferric acetylacetonate.
6. A propellant composition consisting essentially of from 10 to 20% nitrocellulose, about 20% ammonium perchlorate, about 20% aluminum, 28.4 to 36.2% nitroglycerin, 9 to 11.5% di-n-propyl adipate, 1% resorcinol diacetate, 1% 2-nitrodiphenylamine, 0.15 to 0.50% 2,4-tolylene diisocyanate and 0.007 to 0.05% ferric acetylacetonate; all percentages being by weight.
7. A propellant composition consisting essentially of 15 to 21.6% nitrocellulose of 70 Mu particle size, 20 to 20.2% ammonium perchlorate, 20 to 20.9% aluminum, 26.3 to 32.4% nitroglycerin, 8.4 to 10.15% triacetin, 1.0% 2-nitrodiphenylamine, 1.0% resorcinol, 0.10% calcium phosphate, 0.38 to 0.40% 2,4-tolylene diisocyanate, 0.01% ferric acetylacetonate and 0.03 to 0.04% dioctyl phthalate; all percentages being by weight.
8. A propellant composition consisting essentially of 15% plastisol nitrocellulose, 20% ammonium perchlorate, 20% aluminum, 32.1 to 32.25% nitroglycerin, 10.2 to 10.3% triacetin, 1.2 to 1.55% 2-nitrodiphenylamine, 0.4 to 0.8% symmetrical diethyldiphenylurea, 0.1% calcium phosphate, 0.30 to 0.45% 2,4-tolylene diIsocyanate and 0.01% ferric acetylacetonate; all percentages being be weight.
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Cited By (26)

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Publication number Priority date Publication date Assignee Title
US3979236A (en) * 1975-05-21 1976-09-07 The United States Of America As Represented By The Secretary Of The Army Anti-erosive, solid rocket double-base propellant compositions
US4043850A (en) * 1976-08-06 1977-08-23 The United States Of America As Represented By The Secretary Of The Navy Polymeric-coated HMX crystals for use with propellant materials
US4045261A (en) * 1976-08-02 1977-08-30 The United States Of America As Represented By The Secretary Of The Navy Molecular sieve containing stabilization system for urethane - crosslinked double base propellant
US4142927A (en) * 1975-09-04 1979-03-06 Walker Franklin E Free radical explosive composition
US4214927A (en) * 1977-11-30 1980-07-29 Nippon Oil And Fats Co., Ltd. Granular propellant
US4234364A (en) * 1978-05-30 1980-11-18 Hercules Incorporated Crosslinked double base propellant binders
US4299636A (en) * 1974-04-05 1981-11-10 Hercules Incorporated Alkoxy substituted aromatic stabilizers for crosslinked CMDB propellant
US4462848A (en) * 1979-12-28 1984-07-31 Hercules Incorporated Slurry casting method for double base propellants
US4490196A (en) * 1984-04-05 1984-12-25 Hercules Incorporated Low detonation velocity explosive composition
EP0159843A1 (en) * 1984-04-05 1985-10-30 Ireco Incorporated Low detonation velocity explosive composition
US4597924A (en) * 1985-10-21 1986-07-01 The United States Of America As Represented By The Secretary Of The Army Tetra-alkyl titanates as bonding agents for thermoplastic propellants
US4713127A (en) * 1985-09-12 1987-12-15 Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Triplebasic propellant powder and process for the production thereof
US5387295A (en) * 1977-01-05 1995-02-07 Hercules Incorporated Stabilizers for cross-linked composite modified double base propellants
EP0649897A1 (en) * 1993-10-26 1995-04-26 Chiminove S.A. Combustible solid material, firelighters, and method of manufacturing
US5520756A (en) * 1990-12-11 1996-05-28 Hercules Incorporated Stable plasticizers for nitrocellulose nitroguanidine-type compositions
US5798481A (en) * 1995-11-13 1998-08-25 The United States Of America As Represented By The Secretary Of The Army High energy TNAZ, nitrocellulose gun propellant
US6066213A (en) * 1998-09-18 2000-05-23 Atlantic Research Corporation Minimum smoke propellant composition
US6126763A (en) * 1998-12-01 2000-10-03 Atlantic Research Corporation Minimum smoke propellant composition
WO2000063139A2 (en) * 1999-04-20 2000-10-26 Atlantic Research Corporation Family of propellant compositions and method
US6241833B1 (en) 1998-07-16 2001-06-05 Alliant Techsystems, Inc. High energy gun propellants
US6599379B2 (en) * 2001-04-12 2003-07-29 Dmd Systems, Llc Low-smoke nitroguanidine and nitrocellulose based pyrotechnic compositions
WO2007090278A1 (en) * 2006-02-09 2007-08-16 General Dynamics Ordnance And Tactical Systems - Canada Valleyfield Inc. Black powder substitutes for small caliber firearms
WO2009010723A1 (en) * 2007-07-13 2009-01-22 Akcros Chemicals Ltd. Bonding compositions
CN101205159B (en) * 2006-12-22 2011-11-16 比亚迪股份有限公司 Safety gas-bag aerogenesis medicine and preparation method thereof
US20130308233A1 (en) * 2011-02-02 2013-11-21 Showa Denko K.K. Discharge gap-filling composition and electrostatic discharge protector
JP2016003176A (en) * 2014-06-19 2016-01-12 日油株式会社 Triple-base propellant composition

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Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4299636A (en) * 1974-04-05 1981-11-10 Hercules Incorporated Alkoxy substituted aromatic stabilizers for crosslinked CMDB propellant
US3979236A (en) * 1975-05-21 1976-09-07 The United States Of America As Represented By The Secretary Of The Army Anti-erosive, solid rocket double-base propellant compositions
US4142927A (en) * 1975-09-04 1979-03-06 Walker Franklin E Free radical explosive composition
US4045261A (en) * 1976-08-02 1977-08-30 The United States Of America As Represented By The Secretary Of The Navy Molecular sieve containing stabilization system for urethane - crosslinked double base propellant
US4043850A (en) * 1976-08-06 1977-08-23 The United States Of America As Represented By The Secretary Of The Navy Polymeric-coated HMX crystals for use with propellant materials
US5387295A (en) * 1977-01-05 1995-02-07 Hercules Incorporated Stabilizers for cross-linked composite modified double base propellants
US4214927A (en) * 1977-11-30 1980-07-29 Nippon Oil And Fats Co., Ltd. Granular propellant
US4234364A (en) * 1978-05-30 1980-11-18 Hercules Incorporated Crosslinked double base propellant binders
US4462848A (en) * 1979-12-28 1984-07-31 Hercules Incorporated Slurry casting method for double base propellants
US4490196A (en) * 1984-04-05 1984-12-25 Hercules Incorporated Low detonation velocity explosive composition
EP0159843A1 (en) * 1984-04-05 1985-10-30 Ireco Incorporated Low detonation velocity explosive composition
US4555279A (en) * 1984-04-05 1985-11-26 Hercules Incorporated Low detonation velocity explosive composition
US4713127A (en) * 1985-09-12 1987-12-15 Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Triplebasic propellant powder and process for the production thereof
US4597924A (en) * 1985-10-21 1986-07-01 The United States Of America As Represented By The Secretary Of The Army Tetra-alkyl titanates as bonding agents for thermoplastic propellants
US5520756A (en) * 1990-12-11 1996-05-28 Hercules Incorporated Stable plasticizers for nitrocellulose nitroguanidine-type compositions
EP0649897A1 (en) * 1993-10-26 1995-04-26 Chiminove S.A. Combustible solid material, firelighters, and method of manufacturing
FR2711668A1 (en) * 1993-10-26 1995-05-05 Poudres & Explosifs Ste Nale Solid fuel material. Firelighters. Manufacturing process.
US5798481A (en) * 1995-11-13 1998-08-25 The United States Of America As Represented By The Secretary Of The Army High energy TNAZ, nitrocellulose gun propellant
US6241833B1 (en) 1998-07-16 2001-06-05 Alliant Techsystems, Inc. High energy gun propellants
US6066213A (en) * 1998-09-18 2000-05-23 Atlantic Research Corporation Minimum smoke propellant composition
US6126763A (en) * 1998-12-01 2000-10-03 Atlantic Research Corporation Minimum smoke propellant composition
WO2000063139A3 (en) * 1999-04-20 2001-05-10 Atlantic Res Corp Family of propellant compositions and method
WO2000063139A2 (en) * 1999-04-20 2000-10-26 Atlantic Research Corporation Family of propellant compositions and method
US6599379B2 (en) * 2001-04-12 2003-07-29 Dmd Systems, Llc Low-smoke nitroguanidine and nitrocellulose based pyrotechnic compositions
WO2007090278A1 (en) * 2006-02-09 2007-08-16 General Dynamics Ordnance And Tactical Systems - Canada Valleyfield Inc. Black powder substitutes for small caliber firearms
US20090223611A1 (en) * 2006-02-09 2009-09-10 General Dynamics Ordnance And Tactical Systems- Canada Valleyfield Inc. Black Powder Substitutes for Small Caliber Firearms
US8133335B2 (en) 2006-02-09 2012-03-13 Mathieu Racette Black powder substitutes for small caliber firearms
CN101205159B (en) * 2006-12-22 2011-11-16 比亚迪股份有限公司 Safety gas-bag aerogenesis medicine and preparation method thereof
WO2009010723A1 (en) * 2007-07-13 2009-01-22 Akcros Chemicals Ltd. Bonding compositions
US20130308233A1 (en) * 2011-02-02 2013-11-21 Showa Denko K.K. Discharge gap-filling composition and electrostatic discharge protector
JP2016003176A (en) * 2014-06-19 2016-01-12 日油株式会社 Triple-base propellant composition

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