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EP2784053A1 - Phthalatfreie Treibmittel - Google Patents

Phthalatfreie Treibmittel Download PDF

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Publication number
EP2784053A1
EP2784053A1 EP13275081.1A EP13275081A EP2784053A1 EP 2784053 A1 EP2784053 A1 EP 2784053A1 EP 13275081 A EP13275081 A EP 13275081A EP 2784053 A1 EP2784053 A1 EP 2784053A1
Authority
EP
European Patent Office
Prior art keywords
component
weight
energetic
plasticiser
composition according
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.)
Ceased
Application number
EP13275081.1A
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English (en)
French (fr)
Inventor
designation of the inventor has not yet been filed The
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.)
BAE Systems PLC
Original Assignee
BAE Systems PLC
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BAE Systems PLC filed Critical BAE Systems PLC
Priority to EP13275081.1A priority Critical patent/EP2784053A1/de
Priority to PL14712720T priority patent/PL2978731T3/pl
Priority to ES14712720T priority patent/ES2815524T3/es
Priority to EP14712720.3A priority patent/EP2978731B1/de
Priority to PCT/GB2014/050849 priority patent/WO2014155061A1/en
Priority to US14/780,899 priority patent/US10526256B2/en
Priority to AU2014242707A priority patent/AU2014242707B2/en
Publication of EP2784053A1 publication Critical patent/EP2784053A1/de
Priority to IL241898A priority patent/IL241898B/en
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
    • 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
    • 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

Definitions

  • the invention relates to Insensitive Munition (IM) energetic materials particularly non- phthalate IM propellant compositions.
  • IM Insensitive Munition
  • Low and high energy gun propellants and their energetic compositions are based on colloidal mixtures of nitroglycerine, nitrocellulose and nitroguanidine (also called picrite) in varying proportions, such as those discussed in GB2371297 .
  • the technology used to manufacture these has changed little in 100 years.
  • Colloidal compositions are, generally, classed as single, double, or, triple base compositions depending on the proportions of the major constituents present (i.e. one, two or three major components, respectively). Other components, e.g. nitramines, have been incorporated to increase the force constant, or, energy level, of these compositions and colloidal compositions comprising three, or, more major components, may be referred to as multibase compositions.
  • Colloidal propellants particularly for high energy applications, suffer from the disadvantage that they are highly vulnerable to unwanted ignition when in a hostile environment and subjected to attack by an energetic projectile, e.g. a projectile comprising a shaped warhead charge.
  • an energetic projectile e.g. a projectile comprising a shaped warhead charge.
  • an energetic composition suitable for use as a propellant comprises the following components in the following relative proportions:
  • dialkyl esters such as those defined by Formula (A) may be used to replace phthalates.
  • plasticiser The role of a plasticiser has a two-fold effect. It is used as a processing aid to increase pliability of the dough like material, reducing its viscosity and hence enables ease of pressing into a suitable propellant shape. It also improves the physical properties of the propellant by increasing its flexibility, making it easier to work with.. In contrast, plasticisers used in HE compositions are employed to ensure flow of material into a fixed cavity and are used in very small quantities, less than 2%wt.
  • component A provides the high energy capability of the composition. It may be desirable to replace a portion of the highly energetic filler with an IM energetic filler, in the range of from 10-40%wt.
  • Components B and C provides processability enabling mixtures to be formed together with component A which may be worked into a suitable dough-like material which may be pressed, rolled or extruded to form suitable propellant products.
  • component A which may be worked into a suitable dough-like material which may be pressed, rolled or extruded to form suitable propellant products.
  • the mutual combination of these components is specially selected in compositions according to the present invention because of the unexpected advantages such a combination provides as follows.
  • compositions according to the present invention can be suitably processed to provide propellant materials, eg for use as gun or rocket propellants, especially gun propellants, which unexpectedly and beneficially can show an improved, ie. reduced vulnerability over colloidal propellants, but without a corresponding decrease in energy normally associated with such an improvement.
  • propellant materials eg for use as gun or rocket propellants, especially gun propellants, which unexpectedly and beneficially can show an improved, ie. reduced vulnerability over colloidal propellants, but without a corresponding decrease in energy normally associated with such an improvement.
  • the propellant compositions embodying the invention are suitable for forming propellant products having unexpectedly all of aforementioned desirable properties.
  • the component A may be selected from high energy energetic filler, present in the range of 60% to 90% wt.
  • high energy energetic filler present in the range of 60% to 90% wt.
  • examples are heteroalicyclic nitramines, such as for example RDX(cyclo-1,3,5-trimethylene, 2,4,6-trinitramine, cyclonite or Hexagen), HMX (cyclo-1,3,5,7-tetramethylene-2,4,6,8-tetranitramine, Octogen) or TATND (tetranitro-tetraminodecalin) and mixtures thereof.
  • high energetic fillers may be TAGN, aromatic nitramines such as tetryl, ethylene dinitramine, and nitrate esters such as nitroglycerine (glycerol trinitrate), butane triol trinitrate or pentaerythrital tetranitrate, and inorganic perchlorates and nitrates such as ammonium perchlorate optionally together with metallic fuel such as aluminium particles.
  • aromatic nitramines such as tetryl, ethylene dinitramine
  • nitrate esters such as nitroglycerine (glycerol trinitrate), butane triol trinitrate or pentaerythrital tetranitrate
  • inorganic perchlorates and nitrates such as ammonium perchlorate optionally together with metallic fuel such as aluminium particles.
  • the IM energetic filler may be selected from such as, for example, Nitrotriazolone (NTO), Hexanitrostilbene (HNS), Nitroguanidine (Picrite), Triaminotrinitrobenzene (TATB), Guarnylureadinitramide (FOX-12), 1,1-diamino 2,2-dinitro ethylene (FOX-7).
  • NTO Nitrotriazolone
  • HNS Hexanitrostilbene
  • Nitroguanidine Pieridine
  • TATB Triaminotrinitrobenzene
  • FOX-12 Guarnylureadinitramide
  • the IM energetic filler is one which, without modification, has an FOI greater than 100.
  • Many energetic fillers, including RDX and HMX may be modified, either via stabilisers or coatings such that they have a degree of IM compliance, and an FOI of greater than 100.
  • the component A is selected from a material which is inherently IM, such as will have an FOI>100, without any processing or modification. It has been advantageously found that the inclusion of an IM energetic fill in the amount of from 5% to 25% by weight, provides a final composition which has a high level of IM compliance.
  • the binder may be selected from a non-energetic binder and/or an energetic binder, present in the range of from 8% to 16%wt.
  • the binder is a mixture of an energetic and non-energetic binder; more preferably the energetic binder is present in the range of from 5%- 10% by weight, non-energetic binder is present in the range of from 5%-15% by weight, with a binder %wt in the range of from 8%- 16%wt.
  • suitable non-energetic binder materials which may be blended with EVA are cellulosic materials such as esters, ego cellulose acetate, cellulose acetate butyrate, polyurethanes, polyesters, polybutadienes, polyethylenes, polyvinyl acetate and blends and/or copolymers thereof.
  • Suitable energetic binder materials which may be used along side a non energetic binder, such as EVA are nitrocellulose, polyvinyl nitrate, nitroethylene, nitroallyl acetate, nitroethyl acrylate, nitroethy methacrylate, trinitroethyl acrylate, dinitropropyl acrylate, C-nitropolystyrene and its derivatives, polyurethanes with aliphatic C- and N- nitro groups, polyesters made from dinitrocarboxylic acids and dinitrodiol and homopolymers of 3-nitrato-3 methyl oxetane (PolyNIMMO).
  • the composition comprises component C a plasticiser, wherein the plasticiser comprises a compound formula (A) of from 5% to 10% by weight.
  • plasticisers which may be selected from a non-energetic plasticiser and/or an energetic plasticiser.
  • the plasticiser is a mixture of energetic and non-energetic plasticisers; yet more preferably when both are present the; energetic plasticiser is present in the range of from 0%- 8% by weight, and non-energetic plasticiser, which includes formula (A), is present in the range of from 2%-10% by weight; such that the total plasticiser is preferably 5%-10%wt.
  • energetic plasticisers may be Butyl NENA, GAP (glycidyl azide polymer), BDNPA/F (bis-2,2-dinitropropylacetol/formal), dimethylmethylene dinitroamine, bis(2,2,2-trinitropropyl)formal, bis(2,2,2-trinitroethyl)formal, bis (2-fluoro-2,2-dinitroethyl)formal, diethylene gylcol dinitrate, glycerol trinitrate, glycol trinitrate, triethylene glycol dinitrate, tetrethylene glycol dinitrate, trimethylolethane trinitrate, butanetriol trinitrate, or 1,2,4-butanetriol trinitrate.
  • Examples of Formula (A) may be, Di Octyl adipate(DOA), Di Octyl Sebacate (DOS), dialkyl esters comprising sebacic adipic or maleic homologues, Further non-energtic non-phthalates binders may alos be present such as tricresyl phosphate, polyalkylene glycols and their alkyl ether derivatives, eg polyethylene glycol, polypropylene gycol, and diethylene glycol butyl ether.
  • DOA Di Octyl adipate
  • DOS Di Octyl Sebacate
  • binders may alos be present such as tricresyl phosphate, polyalkylene glycols and their alkyl ether derivatives, eg polyethylene glycol, polypropylene gycol, and diethylene glycol butyl ether.
  • the plasticiser contains only a compound of formula (A), and is present in the range of from 5%-10%wt.
  • minor additives may for example comprise one or more stabilisers, e.g. carbamite (N,N1-diphenyl, NN1-diethylurea) or PNMA (paranitromethylmethoxyaniline); and/or one or more ballistic modifiers, e.g. carbon black or lead salts: and/or one or more flash suppressants, e.g. one or more sodium or potassium salts, e.g. sodium or potassium sulphate or bicarbonate and one or more binder-to-energetic filler coupling agents and one or more antioxidants.
  • stabilisers e.g. carbamite (N,N1-diphenyl, NN1-diethylurea) or PNMA (paranitromethylmethoxyaniline)
  • ballistic modifiers e.g. carbon black or lead salts
  • flash suppressants e.g. one or more sodium or potassium salts, e.g. sodium or potassium sulphate or bicarbonate and one or more binder
  • a gun propellant comprising sticks or granules comprising a composition according to any one of the preceding claims.
  • compositions according to the present invention may be processed into propellants by techniques which are known to those skilled in the art.
  • the ingredients are incorporated in a suitable kneader to form a homogeneous composition.
  • the composition produced is pressed, rolled or extruded in the form of a dough-like material through suitably shaped extrusion dies. Extrusion may be carried out using a co-rotating twin screw extrusion machine.
  • Sticks are usually formed by cutting to suitable length rods or strands extruded through suitable dies giving a shape including a longitudinal slot.
  • Granules are usually similarly formed by cutting to much shorter lengths rods or sticks obtained by extrusion. Normally, such granules have small holes, ego seven holes running lengthwise therethrough to provide suitable burning surfaces.
  • compositions are outlined in Table 1, below.
  • Table 1 IM propellant compositions Component Ingredient Comp 424 % wt Comp 463 % wt Comp 469 % wt Component A HMX 74.5 74.5 74.5 Component B EVA 7 7 7 Component B Nitrocellulose 8.5 8.5 8.5 Plasticiser DBP 9 Formula (A) DOA 9 Formula (A) DOS 9 stabiliser Carbamite 1 1 1 SCJ attack response Type III/IV III/IV III/IV
  • compositions in Table 1 were subjected to a test set-up in accordance with STANAG 4526, namely response to a shaped charge attack.
  • the response was measured by taking into account the combined evidence from blast overpressure results, witness plate damage observed and from propellant debris observations.
  • Comp 424 is a known propellant composition which is prepared using a dibutyl phthalate plasticiser (DBP).
  • DBP dibutyl phthalate plasticiser
  • Compounds 463 and 469 are phthalate free, and use DOA and DOS plasticisers, with no deleterious effect on the IM properties of the propellant composition. It has been unexpectedly found that phthalate plasticisers may be replaced by dialkyl diester plasticisers without compromising the IM properties of the propellant.
  • Figure 1 shows a three-dimensional representation of a bundle of propellant sticks
  • FIG 1 there is provided an end portion of a bundle 1 of a plurality of propellant sticks 2.
  • a resilient ligature 3 has been wound around the plurality of sticks 2 three times using a tying machine (not shown). The securing of the ligature 3 may be afforded by using a knot and subsequently cutting the ligature 3. Further ligatures may be applied to other distinct circumferences and in fact it may be preferred to have at least two ligatures applied at distinct circumferences in order to prevent the propellant sticks 2 from splaying.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Molecular Biology (AREA)
  • Medicinal Preparation (AREA)
EP13275081.1A 2013-03-27 2013-03-27 Phthalatfreie Treibmittel Ceased EP2784053A1 (de)

Priority Applications (8)

Application Number Priority Date Filing Date Title
EP13275081.1A EP2784053A1 (de) 2013-03-27 2013-03-27 Phthalatfreie Treibmittel
PL14712720T PL2978731T3 (pl) 2013-03-27 2014-03-18 Nieftalanowe materiały miotające
ES14712720T ES2815524T3 (es) 2013-03-27 2014-03-18 Propulsores sin ftalatos
EP14712720.3A EP2978731B1 (de) 2013-03-27 2014-03-18 Phthalatfreie treibmittel
PCT/GB2014/050849 WO2014155061A1 (en) 2013-03-27 2014-03-18 Non-phthalate propellants
US14/780,899 US10526256B2 (en) 2013-03-27 2014-03-18 Non-phthalate propellants
AU2014242707A AU2014242707B2 (en) 2013-03-27 2014-03-18 Non-phthalate propellants
IL241898A IL241898B (en) 2013-03-27 2015-10-06 Non-phthalate propellants

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP13275081.1A EP2784053A1 (de) 2013-03-27 2013-03-27 Phthalatfreie Treibmittel

Publications (1)

Publication Number Publication Date
EP2784053A1 true EP2784053A1 (de) 2014-10-01

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Application Number Title Priority Date Filing Date
EP13275081.1A Ceased EP2784053A1 (de) 2013-03-27 2013-03-27 Phthalatfreie Treibmittel

Country Status (1)

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EP (1) EP2784053A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105130720A (zh) * 2014-05-30 2015-12-09 湖北航天化学技术研究所 一种高能低燃速温度敏感系数推进剂

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB964001A (en) * 1960-09-28 1964-07-15 Ici Ltd Improvements in and relating to the production of unsaturated esters
GB1554636A (en) * 1975-07-02 1979-10-24 Dynamit Nobel Ag Explosive mouldings
US5034073A (en) * 1990-10-09 1991-07-23 Aerojet General Corporation Insensitive high explosive
GB2264942A (en) * 1992-03-11 1993-09-15 Poudres & Explosifs Ste Nale Ignition-sensitive low vulnerability propellant producers
GB2371297A (en) 1989-04-18 2002-07-24 Royal Ordnance Plc Propellant compositions and propellants produced therefrom
US6833037B1 (en) * 1989-01-25 2004-12-21 Bae Systems Plc Polymer bonded energetic materials
US7211140B1 (en) * 2001-12-14 2007-05-01 Cognis Corporation Low temperature plasticizers for flexible polyvinyl chloride resin applications
WO2009131563A1 (en) * 2008-04-22 2009-10-29 The Government Of The U.S.A, As Represented By The Secretary Of The Navy Office Of Counsel Insensitive gun propellant, ammunition round assembly, armament system, and related methods

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB964001A (en) * 1960-09-28 1964-07-15 Ici Ltd Improvements in and relating to the production of unsaturated esters
GB1554636A (en) * 1975-07-02 1979-10-24 Dynamit Nobel Ag Explosive mouldings
US6833037B1 (en) * 1989-01-25 2004-12-21 Bae Systems Plc Polymer bonded energetic materials
GB2371297A (en) 1989-04-18 2002-07-24 Royal Ordnance Plc Propellant compositions and propellants produced therefrom
US5034073A (en) * 1990-10-09 1991-07-23 Aerojet General Corporation Insensitive high explosive
GB2264942A (en) * 1992-03-11 1993-09-15 Poudres & Explosifs Ste Nale Ignition-sensitive low vulnerability propellant producers
US7211140B1 (en) * 2001-12-14 2007-05-01 Cognis Corporation Low temperature plasticizers for flexible polyvinyl chloride resin applications
WO2009131563A1 (en) * 2008-04-22 2009-10-29 The Government Of The U.S.A, As Represented By The Secretary Of The Navy Office Of Counsel Insensitive gun propellant, ammunition round assembly, armament system, and related methods

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ERYTHROPEL H C ET AL: "Designing green plasticizers: Influence of molecular geometry on biodegradation and plasticization properties", CHEMOSPHERE FEBRUARY 2012 ELSEVIER LTD GBR, vol. 86, no. 8, February 2012 (2012-02-01), pages 759 - 766, XP002711922, DOI: 10.1016/J.CHEMOSPHERE.2011.10.054 *
RAHMAN M ET AL: "The plasticizer market: An assessment of traditional plasticizers and research trends to meet new challenges", PROGRESS IN POLYMER SCIENCE (OXFORD) DECEMBER 2004 ELSEVIER LTD GB, vol. 29, no. 12, December 2004 (2004-12-01), pages 1223 - 1248, XP002711921, DOI: 10.1016/J.PROGPOLYMSCI.2004.10.001 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105130720A (zh) * 2014-05-30 2015-12-09 湖北航天化学技术研究所 一种高能低燃速温度敏感系数推进剂

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