EP0116795B1 - Nouveaux inhibiteurs de combustion à base d'élastomère polyuréthanne oxygéné comportant des fibres pour propergols double base - Google Patents

Nouveaux inhibiteurs de combustion à base d'élastomère polyuréthanne oxygéné comportant des fibres pour propergols double base Download PDF

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Publication number
EP0116795B1
EP0116795B1 EP83402373A EP83402373A EP0116795B1 EP 0116795 B1 EP0116795 B1 EP 0116795B1 EP 83402373 A EP83402373 A EP 83402373A EP 83402373 A EP83402373 A EP 83402373A EP 0116795 B1 EP0116795 B1 EP 0116795B1
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EP
European Patent Office
Prior art keywords
inhibitor
combustion
parts
aliphatic
double base
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP83402373A
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German (de)
English (en)
French (fr)
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EP0116795A1 (fr
Inventor
André Lelu
Bruno Gonthier
Jean Grignon
Jean-Michel Tauzia
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Societe Nationale des Poudres et Explosifs
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Societe Nationale des Poudres et Explosifs
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
    • C06B45/12—Compositions or products which are defined by structure or arrangement of component of product having contiguous layers or zones

Definitions

  • the present invention relates to new combustion inhibitors for dual base propellants comprising a polyurethane elastomer comprising in chemically combined form an aliphatic constituent, polyesterpolyol or polyetherpolyol or a mixture of the two containing 2 to 6 hydroxyl groups per molecule, an aliphatic polyisocyanate constituent , optionally a low molecular weight polyol as chain extender, the inhibitor optionally comprising a gasifiable organic filler and / or an aliphatic plasticizer.
  • Combustion inhibitors are materials which cover the surface of a block of propellant, apart from the surface of the combustion zone, and which protects the combustion zone from any unintentional ignition which may occur for example under the action of hot gases from combustion.
  • One of the main functions of combustion inhibitors is therefore to regulate the combustion of a propellant block by making it possible to maintain a regular combustion zone for the duration of the latter.
  • Double base propellants are by nature "discreet”, that is to say that their combustion gases do not hinder the guidance of the vehicle.
  • Inhibitors are the main cause of the phenomena of opacity which occur during combustion since the surface layers in contact with the propellant block emit fumes which interfere with guidance.
  • nitroglycerin present in the double base propellant, tends to migrate into the inhibitor, when the latter has certain affinities with it, which further increases the combustion of the latter and therefore the emission of smoke.
  • the migration of nitroglycerin also has the drawback of peeling off the propellant block inhibitor, which causes detrimental combustion irregularities when fired.
  • a first solution consists in using a material which ablates during combustion by giving off transparent gases.
  • This solution therefore uses "gasifiable" materials under the effect of hot gases.
  • the invention relates to this type of material and this allows it to differentiate itself from the other solution also proposed and which consists in using materials having excellent thermal resistance such as silicones or aromatic polymers and which, unlike precedents do not tarnish and therefore do not give off obscuring gases.
  • French Patent No. 2,275,425 illustrates an embodiment in which the inhibitor material consists of an aliphatic polyurethane based on a polyol and an aliphatic polyisocyanate and a cooling filler.
  • the object of the present invention is to provide a significant improvement over the previous inhibitory materials which have just been discussed as regards the migration of plasticizer (in particular nitroglycerin), discretion.
  • the invention is characterized in that the combustion inhibitor also comprises 0.1 to 10 parts (by weight) of thermostable mineral or organic fibers of length between 0.1 mm and 15 mm per 100 parts of inhibitor.
  • French Patent 2,290,825 cites an inhibitor composition for a double base propellant consisting of an elastomer and a powdery filler material constituting at least 50% of the total composition. It is also indicated that, preferably, the particles of the material present in the material inhibiting combustion have less than one micron. It is clear that this document designed to propose the incorporation of fibers to the skilled person would rather deter it.
  • the fibers do not have the function of preventing the ablation of the inhibitor but on the contrary of allowing the material to gasify on the spot by ensuring better mechanical resistance to the surface matter in the process of gasification.
  • aliphatic polyurethanes polyurethanes which do not substantially contain aromatic units. This obviously does not exclude that a small proportion of the patterns is aromatic, but this proportion should not exceed 10%.
  • polyurethanes must be oxygenated and preferably consist of the addition reaction between aliphatic polyisocyanates and polyol polyol or polyether polyol comprising 2 to 6 hydroxyl groups per molecule or a mixture of these polyesters or polyether polyol.
  • the ratio between the number of carbon and the number of oxygen is less than 5.
  • the polyurethane compositions leading to the polyurethane elastomer must preferably be pourable although shaping according to the methods of rubber manufacturers is not excluded for the compositions which require it.
  • the polyols preferably have a molecular weight of between 400 and 5,000 and advantageously between 500 and 3,000.
  • Suitable polyesters include those derived from dicarboxylic acids such as adipic, succinic or sebacic acids and low molecular weight glycols such as ethylene glycol, propylene glycol, diethylene glycol, 1,4 butanediol and 1,6 hexanediol.
  • lactone polymers are polymers formed from polyfunctional initiators by successive decyclization of lactone monomers.
  • lactones suitable for the invention correspond to the formula: n being less than or equal to 4.
  • polyesters of this type mention may be made of poty-e-caprotactone or poly-y-butyrolactone.
  • the adducts of these polyesters can also be used on low molecular weight polyols.
  • polyethers which are suitable are in particular polyethylene glycol, polypropylene glycol, polypropylene ethylene glycol, polypropylene glycol, polytetramethylene glycol and the adducts of these polyesters on low molecular weight polyols such as trimethylolpropane, glycerol, pentaerythritol, sorbitol.
  • chain extenders such as low molecular weight glycols (1,4-butanediol for example) or diamines.
  • the NCO: OH ratio is preferably equal to 1 or close to 1.
  • Crosslinking takes place in the presence of well known catalysts such as for example those based on tin such as dibutyl tin diacetate.
  • polyether polyols For reasons of mechanical properties, it is preferable to use polyether polyols. However, it is also very advantageous to use these polyether polyols in admixture with a polylactone, in particular e-polycaprolactone.
  • an aliphatic plasticizer to the polyurethane composition such as, for example, glycerol triacetate or acetyl tri-n-butyl citrate.
  • plasticizer Up to 40 parts of plasticizer can be added per 100 parts of polyurethane.
  • Certain gasifiable organic fillers having a melting temperature equal to or higher than that of the polyurethane can be advantageously added.
  • fillers should preferably be non-hygroscopic because the presence of water interferes with crosslinking.
  • oxygenated organic fillers having a ratio of number of carbon atoms: number of oxygen atoms close to 1, so as to favor the oxidation reactions compared to the polymerization reactions and preferably in fine particle size.
  • Oxamide will advantageously be used because of its very high melting point (approximately 400 ° C.).
  • the aliphatic polyisocyanate component is preferably consisting of aliphatic or cycloaliphatic diisocyanate.
  • the combustion inhibitor will advantageously comprise 0.3 to 8 parts (by weight) of fibers between 0.1 and 6 mm in length and preferably 0.5 to 4 parts by weight per 100 parts of inhibitor.
  • the constituents of the polyurethane, possibly the cooling charge, the plasticizer and the fibers, are mixed by means of a mixer.
  • the increase in weight of the inhibitor is measured at regular intervals by immersion of a sample of said inhibitor in nitroglycerin and the increase in weight is followed.
  • the absorption rate is:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
EP83402373A 1982-12-28 1983-12-08 Nouveaux inhibiteurs de combustion à base d'élastomère polyuréthanne oxygéné comportant des fibres pour propergols double base Expired EP0116795B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8221880A FR2538378A1 (fr) 1982-12-28 1982-12-28 Nouveaux inhibiteurs de combustion a base d'elastomere polyurethanne oxygene comportant des fibres pour progergols double base
FR8221880 1982-12-28

Publications (2)

Publication Number Publication Date
EP0116795A1 EP0116795A1 (fr) 1984-08-29
EP0116795B1 true EP0116795B1 (fr) 1986-07-23

Family

ID=9280570

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83402373A Expired EP0116795B1 (fr) 1982-12-28 1983-12-08 Nouveaux inhibiteurs de combustion à base d'élastomère polyuréthanne oxygéné comportant des fibres pour propergols double base

Country Status (4)

Country Link
US (1) US4536235A (enrdf_load_stackoverflow)
EP (1) EP0116795B1 (enrdf_load_stackoverflow)
DE (1) DE3364773D1 (enrdf_load_stackoverflow)
FR (1) FR2538378A1 (enrdf_load_stackoverflow)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6026749A (en) * 1973-05-11 2000-02-22 Imperial Metal Industries (Kynoch) Limited Multiple base propellant with combustion inhibitor
FR2564457B1 (fr) * 1984-05-17 1986-09-26 Poudres & Explosifs Ste Nale Inhibiteur de combustion a base d'elastomere polyurethanne aliphatique pour propergol, et bloc revetu par cet inhibiteur
US5000885A (en) * 1986-09-18 1991-03-19 The United States Of America As Represented By The Secretary Of The Air Force Chemical inhibitor for solid propellants
US4853051A (en) * 1986-11-06 1989-08-01 Morton Thiokol, Inc. Propellant binder prepared from a PCP/HTPB block polymer
US4775432A (en) * 1986-11-06 1988-10-04 Morton Thiokol, Inc. High molecular weight polycaprolactone prepolymers used in high-energy formulations
DE3644239A1 (de) * 1986-12-23 1988-07-07 Bayern Chemie Gmbh Flugchemie Zwischenschicht zwischen dem treibsatz und der isolierschicht eines raketenfeststoff-treibsatzes
US6051087A (en) * 1992-01-29 2000-04-18 Cordant Technologies Inc. Low smoke rocket motor liner compositions
US5503079A (en) * 1992-02-10 1996-04-02 Daicel Chemical Industries, Ltd. Linear gas generant and filter structure for gas generator
EP0645415B1 (en) * 1993-09-17 1998-05-20 AlliedSignal Inc. High strength composite
US5547525A (en) * 1993-09-29 1996-08-20 Thiokol Corporation Electrostatic discharge reduction in energetic compositions
US5470408A (en) * 1993-10-22 1995-11-28 Thiokol Corporation Use of carbon fibrils to enhance burn rate of pyrotechnics and gas generants
US5580922A (en) * 1995-06-06 1996-12-03 Weyerhaeuser Company Cellulose products treated with isocyanate compositions
US6607617B1 (en) * 2000-08-16 2003-08-19 Alliant Techsystems Inc. Double-base rocket propellants, and rocket assemblies comprising the same
US6904749B2 (en) * 2002-10-18 2005-06-14 Physical Sciences, Inc. Polyoxymethylene as structural support member and propellant
FR2853872B1 (fr) * 2003-04-15 2006-01-13 Seva Technologies Dispositif de mise en oeuvre d'un element de securite pour la protection des biens et/ou des personnes

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4072546A (en) * 1971-12-22 1978-02-07 Hercules Incorporated Use of graphite fibers to augment propellant burning rate
US4187215A (en) * 1972-09-25 1980-02-05 Aerojet-General Corporation Polymeric isocyanate-hydroxy terminated polybutadiene compositions
US4328281A (en) * 1972-09-25 1982-05-04 Aerojet-General Corporation Dimer isocyanate liner compositions
US3924405A (en) * 1973-06-07 1975-12-09 Aerojet General Co Solid propellants with stability enhanced additives of particulate refractory carbides or oxides
US4284442A (en) * 1978-03-13 1981-08-18 The United States Of America As Represented By The Secretary Of The Army Castable TNT compositions containing a broad spectrum preformed thermoplastic polyurethane elastomer additive
US4232608A (en) * 1978-12-04 1980-11-11 Aerojet-General Corporation Dimer isocyanate liner compositions
GB2038346B (en) * 1978-12-21 1983-02-16 Secr Defence Inhibition coating for propellant charges

Also Published As

Publication number Publication date
DE3364773D1 (en) 1986-08-28
EP0116795A1 (fr) 1984-08-29
FR2538378A1 (fr) 1984-06-29
US4536235A (en) 1985-08-20
FR2538378B1 (enrdf_load_stackoverflow) 1985-03-08

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