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WO1999021794A1 - Method of producing adn prills suitable for use in a polymer system - Google Patents

Method of producing adn prills suitable for use in a polymer system Download PDF

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Publication number
WO1999021794A1
WO1999021794A1 PCT/SE1998/001937 SE9801937W WO9921794A1 WO 1999021794 A1 WO1999021794 A1 WO 1999021794A1 SE 9801937 W SE9801937 W SE 9801937W WO 9921794 A1 WO9921794 A1 WO 9921794A1
Authority
WO
WIPO (PCT)
Prior art keywords
medium
prills
adn
nonpolar
polymer system
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
PCT/SE1998/001937
Other languages
French (fr)
Swedish (sv)
Inventor
Abraham Langlet
Martin Johansson
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.)
Forsvarets Forskningsanstalt
Forsvarets Forskningsanstalt (FOA)
Original Assignee
Forsvarets Forskningsanstalt
Forsvarets Forskningsanstalt (FOA)
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 Forsvarets Forskningsanstalt, Forsvarets Forskningsanstalt (FOA) filed Critical Forsvarets Forskningsanstalt
Priority to AU97716/98A priority Critical patent/AU9771698A/en
Publication of WO1999021794A1 publication Critical patent/WO1999021794A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/087—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0033—Shaping the mixture
    • C06B21/005—By a process involving melting at least part of the ingredients
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0033—Shaping the mixture
    • C06B21/0066—Shaping the mixture by granulation, e.g. flaking
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/32—Compounds containing nitrogen bound to oxygen

Definitions

  • the invention relates to a method of producing particles, prills, of ammonium dinitramide (ADN). More specifically, the invention concerns a method of producing in liquid phase ADN prills intended to be mixed with a polymer system.
  • ADN ammonium dinitramide
  • Ammonium dinitramide is an energetic oxidiser which can be used in many applications.
  • One application is that as oxidiser in rocket propellents, which is disclosed in e.g. US 5,498,303.
  • Advantages of using ADN in composite propellants instead of ammonium nitrate are described in, for instance, US 5,498,303 and WO 97/06099.
  • the product When producing ADN, the product is obtained in the form of crystal aggregates which are not very suited to be directly mixed with a polymer system for producing a composite propellant. It is therefore desirable to produce prills of ADN. Prills allow a simpler handling system and result in a better rheology in mixing with polymer systems.
  • prills in liquid phase are previously known.
  • the substance is molten and dispersed to droplets in a liquid phase which is inert in relation to the sub- stance.
  • the liquid phase is cooled to solidify the droplets into prills, and these are separated from the liquid phase.
  • Such a method for prilling of ADN is mentioned in Challenges in Propellants and Combustion - 100 Years after Nobel (Conference Proceedings, 1996, pp 627-635); May Lee Chan et al: ADN Propellant Technology.
  • a problem is that the particles must be washed clean with an organic solvent before they can be used in the production of propellants.
  • An object of the present invention is to produce ADN prills which can be directly mixed with a polymer system without any preceding washing of the particles. This is achieved by a method as defined in the appended claims.
  • the invention comprises melting and dispersion of ADN in a nonpolar medium to obtain droplets of ADN in the medium; cooling of the medium to solidify the droplets into prills and separation of said prills from the medium.
  • Characteristic of the invention is that the nonpolar medium essentially consists of a plasticiser which is com- patible with said polymer system.
  • the nonpolar medium may contain a polymer for adjusting the viscosity of the medium.
  • the polymer can be, for instance, HTPB or some other polymer which is used in composite propellants and plastic-bonded explosives.
  • a suitable viscosity of the nonpolar medium is 10-250 mPas.
  • a small amount of surfactant can advantageously be added to the nonpolar medium.
  • the surfactant makes the prills have a smooth and nice surface.
  • the added amount is normally smaller than 5% by weight based on the nonpolar medium.
  • Suitable surfactants are, for instance, laurylium sulphate, stearyl alcohol, sodium stearate, octylamine and dodecylamine.
  • Suitable plasticisers are DOS, DOA, vacuum oil, transformer oil, K-10, BTTN, M/E- NENA, TMETN, Me-NENA, Et-NENA, WM3, FEFO, BDNPF/A, DANPE, DINA, and GAPA. K-10 up to and including GAPA are all energetic plasticisers.
  • the prills can be directly mixed with a polymer system when producing composite propellants and plastic-bonded explosives without the particles first needing to be washed.
  • the plasticiser and, where appropriate, the viscosity-controlling polymer are selected in consideration of the polymer system with which the prills are to be mixed.
  • the plasticiser also protects the particles from the humidity of the air.
  • Prilling was carried out in a 1 -litre stainless steel batch reactor consisting of a cylindrical container with a tight cover.
  • the container was provided with a propeller agitator and baffles.
  • the container was enclosed by a jacket to be passed by a heating medium and a cooling medium, respectively.
  • Through the cover there was arranged a connection for a vacuum pump to evacuate gases from the medium.
  • the reactor was supplied with 5 g of ADN, 700 ml of plasticiser (DOS, dioctyl sebacate) as a nonpolar medium and 200 mg of surfactant (laurylium sulphate).
  • the reactor was closed and gases were evacuated by means of the vacuum pump.
  • the mixture was heated to 96°C and kept at this temperature for 5 min during stirring by means of the propeller agitator at a rate of 60 rpm.
  • the mixture was then quickly cooled to 20°C.
  • the resulting prills were filtered off by suction filtration on a paper filter.
  • the prills had a particle size of about 200 ⁇ m.
  • the stirring intensity was increased, whereby prills having a particle size of about 120 ⁇ m were produced.
  • prills were mixed with a polymer system (HTPB) without any preceding washing, and propellant elements were prepared.
  • HTPB polymer system
  • Propellant elements of high strength were obtained after hardening, without any problems.
  • Example 1 The reactor according to Example 1 was provided with an anchor agitator instead of the propeller agitator and new prillings were earned out in the same way as in Example 1 , but with the following changes:
  • a nonpolar medium use was made of a mixture of DOS and HTPB (Krasol® supplied by Kaucuk A.S.). 24.5 g of HTPB were mixed with DOS to a total volume of 300 ml. 20 g of ADN were added. The stirring rate was 400 rpm.
  • Example 3a was repeated with a nonpolar medium consisting of a mixture of 31.5 g of HTPB and DOS to a total volume of 300 ml. The stirring rate was 600 rpm. The product was filtered off and mixed with a polymer system (HTPB) without any preceding washing, and propellant elements were prepared. Propellant elements of high strength were obtained after hardening, without any problems.
  • a nonpolar medium consisting of a mixture of 31.5 g of HTPB and DOS to a total volume of 300 ml.
  • the stirring rate was 600 rpm.
  • the product was filtered off and mixed with a polymer system (HTPB) without any preceding washing, and propellant elements were prepared. Propellant elements of high strength were obtained after hardening, without any problems.
  • HTPB polymer system
  • Example 3 b was repeated with a stirring rate of 800 rpm. Prills of good quality with a size distributed around 60 ⁇ m were produced.
  • Example 3c was repeated with 30 g of ADN in the nonpolar medium. In this case, the prills became smaller than in -Example 3c and were of good quality.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Peptides Or Proteins (AREA)
  • Apparatus Associated With Microorganisms And Enzymes (AREA)

Abstract

The invention relates to a method of producing prills of ADN intended to be mixed with a polymer system. The method comprises melting and dispersion of ADN in a nonpolar medium to obtain droplets of ADN in the medium; cooling of the medium to solidify the droplets into prills, and separation of said prills from the medium. The invention is characterised in that the nonpolar medium essentially consists of a plasticiser which is compatible with said polymer system. The nonpolar system may also contain a polymer, such as HTPB, for adjusting the viscosity of the medium.

Description

Method of Producing ADN Prills suitable for Use in a Polymer System
The invention relates to a method of producing particles, prills, of ammonium dinitramide (ADN). More specifically, the invention concerns a method of producing in liquid phase ADN prills intended to be mixed with a polymer system.
Ammonium dinitramide is an energetic oxidiser which can be used in many applications. One application is that as oxidiser in rocket propellents, which is disclosed in e.g. US 5,498,303. Advantages of using ADN in composite propellants instead of ammonium nitrate are described in, for instance, US 5,498,303 and WO 97/06099.
When producing ADN, the product is obtained in the form of crystal aggregates which are not very suited to be directly mixed with a polymer system for producing a composite propellant. It is therefore desirable to produce prills of ADN. Prills allow a simpler handling system and result in a better rheology in mixing with polymer systems.
The production of prills in liquid phase is previously known. The substance is molten and dispersed to droplets in a liquid phase which is inert in relation to the sub- stance. The liquid phase is cooled to solidify the droplets into prills, and these are separated from the liquid phase. Such a method for prilling of ADN is mentioned in Challenges in Propellants and Combustion - 100 Years after Nobel (Conference Proceedings, 1996, pp 627-635); May Lee Chan et al: ADN Propellant Technology. A problem, however, is that the particles must be washed clean with an organic solvent before they can be used in the production of propellants.
An object of the present invention is to produce ADN prills which can be directly mixed with a polymer system without any preceding washing of the particles. This is achieved by a method as defined in the appended claims.
The invention comprises melting and dispersion of ADN in a nonpolar medium to obtain droplets of ADN in the medium; cooling of the medium to solidify the droplets into prills and separation of said prills from the medium. Characteristic of the invention is that the nonpolar medium essentially consists of a plasticiser which is com- patible with said polymer system.
In addition to a plasticiser, the nonpolar medium may contain a polymer for adjusting the viscosity of the medium. The polymer can be, for instance, HTPB or some other polymer which is used in composite propellants and plastic-bonded explosives. A suitable viscosity of the nonpolar medium is 10-250 mPas.
A small amount of surfactant can advantageously be added to the nonpolar medium. The surfactant makes the prills have a smooth and nice surface. The added amount is normally smaller than 5% by weight based on the nonpolar medium. Suitable surfactants are, for instance, laurylium sulphate, stearyl alcohol, sodium stearate, octylamine and dodecylamine.
Suitable plasticisers are DOS, DOA, vacuum oil, transformer oil, K-10, BTTN, M/E- NENA, TMETN, Me-NENA, Et-NENA, WM3, FEFO, BDNPF/A, DANPE, DINA, and GAPA. K-10 up to and including GAPA are all energetic plasticisers.
By using a plasticiser as a nonpolar medium, the prills can be directly mixed with a polymer system when producing composite propellants and plastic-bonded explosives without the particles first needing to be washed. The plasticiser and, where appropriate, the viscosity-controlling polymer are selected in consideration of the polymer system with which the prills are to be mixed. The plasticiser also protects the particles from the humidity of the air.
The invention will now be described by means of -Examples.
[Example 1
Prilling was carried out in a 1 -litre stainless steel batch reactor consisting of a cylindrical container with a tight cover. The container was provided with a propeller agitator and baffles. The container was enclosed by a jacket to be passed by a heating medium and a cooling medium, respectively. Through the cover there was arranged a connection for a vacuum pump to evacuate gases from the medium.
The reactor was supplied with 5 g of ADN, 700 ml of plasticiser (DOS, dioctyl sebacate) as a nonpolar medium and 200 mg of surfactant (laurylium sulphate). The reactor was closed and gases were evacuated by means of the vacuum pump. The mixture was heated to 96°C and kept at this temperature for 5 min during stirring by means of the propeller agitator at a rate of 60 rpm. The mixture was then quickly cooled to 20°C. The resulting prills were filtered off by suction filtration on a paper filter. The prills had a particle size of about 200 μm. In repeated experiments, the stirring intensity was increased, whereby prills having a particle size of about 120 μm were produced.
The resulting prills were mixed with a polymer system (HTPB) without any preceding washing, and propellant elements were prepared. Propellant elements of high strength were obtained after hardening, without any problems.
Repeated experiments were made with other plasticisers as a nonpolar medium, DOA, vacuum oil, transformer oil, K-10, BTTN, M/E-NENA, TMETN, Me-NENA, Et- NENA, WM3, FEFO, BDNPF/A, DANPE, DINA and GAPA being tested.
Example 2
The reactor according to Example 1 was provided with an anchor agitator instead of the propeller agitator and new prillings were earned out in the same way as in Example 1 , but with the following changes:
a) As a nonpolar medium use was made of a mixture of DOS and HTPB (Krasol® supplied by Kaucuk A.S.). 24.5 g of HTPB were mixed with DOS to a total volume of 300 ml. 20 g of ADN were added. The stirring rate was 400 rpm.
The produced prills became relatively large.
b) Example 3a was repeated with a nonpolar medium consisting of a mixture of 31.5 g of HTPB and DOS to a total volume of 300 ml. The stirring rate was 600 rpm. The product was filtered off and mixed with a polymer system (HTPB) without any preceding washing, and propellant elements were prepared. Propellant elements of high strength were obtained after hardening, without any problems.
The resulting prills had a particle size distributed around about 200 μm. c) Example 3 b was repeated with a stirring rate of 800 rpm. Prills of good quality with a size distributed around 60 μm were produced.
d) Example 3c was repeated with 30 g of ADN in the nonpolar medium. In this case, the prills became smaller than in -Example 3c and were of good quality.

Claims

Claims.
1. A method of producing prills of ADN intended to be mixed with a polymer system, comprising melting and dispersion of ADN in a nonpolar medium to obtain droplets of ADN in the medium; cooling of the medium to solidify the droplets into prills, and separation of said prills from the medium, characterised in that the non- polar medium essentially consists of a plasticiser which is compatible with said polymer system.
2. A method as claimed in claim 1 , characterised in that the nonpolar medium has a viscosity of 10-250 mPas.
3. A method as claimed in claim 2, characterised in that the nonpolar medium contains a polymer for adjusting the viscosity of the medium.
4. A medium as claimed in claim 1 , characterised in that a surfactant is added to the nonpolar medium.
5. A method as claimed in claim 1 , characterised in that the plasticiser is selected from the group consisting of DOS, DOA, vacuum oil, transformer oil, K-10, BTTN, M/E-NENA, TMETN, Me-NEMA, Et-NENA, WM3, FEFO, BDNPF/A, DANPE, DINA and GAPA.
6. A method as claimed in claim 3, characterised in that the polymer is HTPB.
PCT/SE1998/001937 1997-10-28 1998-10-27 Method of producing adn prills suitable for use in a polymer system Ceased WO1999021794A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU97716/98A AU9771698A (en) 1997-10-28 1998-10-27 Method of producing adn prills suitable for use in a polymer system

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE9703928-3 1997-10-28
SE9703928A SE512396C2 (en) 1997-10-28 1997-10-28 Methods of Preparing Prills of Ammonium Dinitramide (ADN)

Publications (1)

Publication Number Publication Date
WO1999021794A1 true WO1999021794A1 (en) 1999-05-06

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PCT/SE1998/001938 Ceased WO1999021795A1 (en) 1997-10-28 1998-10-27 Method of producing adn prills
PCT/SE1998/001936 Ceased WO1999021793A1 (en) 1997-10-28 1998-10-27 Method of producing prills of ammonium dinitramide (adn)
PCT/SE1998/001937 Ceased WO1999021794A1 (en) 1997-10-28 1998-10-27 Method of producing adn prills suitable for use in a polymer system

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PCT/SE1998/001936 Ceased WO1999021793A1 (en) 1997-10-28 1998-10-27 Method of producing prills of ammonium dinitramide (adn)

Country Status (3)

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AU (3) AU9771798A (en)
SE (1) SE512396C2 (en)
WO (3) WO1999021795A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8491736B2 (en) 2008-09-18 2013-07-23 Herakles Method for obtaining ADN crystals through crystallization in a viscous medium
WO2019229385A1 (en) 2018-05-30 2019-12-05 Arianegroup Sas Method for producing ammonium dinitramide (adn) crystals, adn crystals and energetic composites containing same

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6610157B1 (en) 2000-01-14 2003-08-26 Alliant Techsystems Inc. Prilled energetic particles, and process for making the same
WO2013043099A2 (en) * 2011-09-22 2013-03-28 Ijorari Hb Process for manufacturing particles and particles thereby manufactured

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5587553A (en) * 1994-11-07 1996-12-24 Thiokol Corporation High performance pressable explosive compositions
WO1997047571A1 (en) * 1996-06-11 1997-12-18 United Technologies Corporation Process for preparing spherical particles of energetic compounds
US5759458A (en) * 1996-07-26 1998-06-02 Thiokol Corporation Process for the manufacture of high performance gun propellants

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5415852A (en) * 1992-01-29 1995-05-16 Sri International Process for forming a dinitramide salt or acid by reaction of a salt or free acid of an N(alkoxycarbonyl)N-nitroamide with a nitronium-containing compound followed by reaction of the intermediate product respectively with a base or alcohol
JP3719614B2 (en) * 1995-05-26 2005-11-24 株式会社アイ・エイチ・アイ・エアロスペース Synthesis method of ADN
SE516719C2 (en) * 1995-08-08 2002-02-19 Totalfoersvarets Forskningsins Methods for preparing dinitramic acid and salts thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5587553A (en) * 1994-11-07 1996-12-24 Thiokol Corporation High performance pressable explosive compositions
WO1997047571A1 (en) * 1996-06-11 1997-12-18 United Technologies Corporation Process for preparing spherical particles of energetic compounds
US5759458A (en) * 1996-07-26 1998-06-02 Thiokol Corporation Process for the manufacture of high performance gun propellants

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8491736B2 (en) 2008-09-18 2013-07-23 Herakles Method for obtaining ADN crystals through crystallization in a viscous medium
WO2019229385A1 (en) 2018-05-30 2019-12-05 Arianegroup Sas Method for producing ammonium dinitramide (adn) crystals, adn crystals and energetic composites containing same

Also Published As

Publication number Publication date
WO1999021793A1 (en) 1999-05-06
SE9703928L (en) 1999-04-29
AU9771698A (en) 1999-05-17
SE9703928D0 (en) 1997-10-28
SE512396C2 (en) 2000-03-13
AU9771798A (en) 1999-05-17
AU9771598A (en) 1999-05-17
WO1999021795A1 (en) 1999-05-06

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