WO 2015/115962 Al 6 August 2015 (06.08.2015) P O P C T

(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date WO 2015/115962 Al 6 August 2015 (06.08.2015) P O P C T

(51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every C06B 25/34 (2006.01) C01B 21/082 (2006.01) kind of national protection available): AE, AG, AL, AM, AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, (21) International Application Number: BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, PCT/SE20 15/000004 DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, (22) International Filing Date: HN, HR, HU, ID, IL, IN, IR, IS, JP, KE, KG, KN, KP, KR, 29 January 2015 (29.01 .2015) KZ, LA, LC, LK, LR, LS, LU, LY, MA, MD, ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, OM, (25) Filing Language: Swedish PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA, SC, (26) Publication Language: English SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (30) Priority Data: 1400043-4 30 January 2014 (30.01.2014) SE (84) Designated States (unless otherwise indicated, for every kind of regional protection available): ARIPO (BW, GH, (71) Applicant: TOTALFORSVARETS FORSKNINGSIN- GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ, STITUT [SE/SE]; S-164 90 (SE). TZ, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ, TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, (72) Inventors: EK, Stefan; FOI Grindsjons forsknings station, DK, EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, S-147 25 Tumba (SE). SKARSTIND, Martin; FOI Grind LV, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, sjons forskningsstation, S-147 25 Tumba (SE). LATY- SM, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, POV, Nikolaj; Torptjarnsvagen 30 a, S-669 30 Deje (SE). GW, KM, ML, MR, NE, SN, TD, TG). SKIFS, Henrik; Eurenco Ab, S-691 86 Karlsskoga (SE). JOHANSSON, Jonas; Slatbaksvagen 38, S-120 5 1 Arsta Published: (SE). — with international search report (Art. 21(3)) (74) Agent: FORSVARETS MATERIELVERK; Patentene- hten, 115 88 Stockholm (SE).

(54) Title: SYNTHESIS OF AMONNIUM DINITRAMIDE, ADN (57) Abstract: The invention concerns a method for making ADN from GUDN in one single process step. GUDN is reacted with an ammonium source (ammonium- sulfamate, ammonium- sulfate) and an ion-change gives ADN from GUDN in one process stage. The advantages are that the process gives pure ADN without potassium contaminants and that a smaller amount of solvent is necessary. • GUDN and the ammonium source are heated together with water until everything is solved into a solution. Thereafter, an alcohol is added and the precipitate formed is filtered off. The filtrate is concentrated and the residue is suspended in an alcohol. The precipit - ate is filtered off and ADN is obtained by concentrating the filtrate. An alternative is to, after adding the alcohol, partially concen trate the then formed mixture. The filtering off of the particles from this mixture yields a solution of ADN in alcohol. Evaporation of this solution yields clean ADN after only one filtering stage. Ammonia can also be used as a source of ammonium. GUDN is then dissolved in ammonia where after then formed ammonium-dimtramide and guanylurea are separated through separation on a column filled with active carbon. The eluted solution is concentrated until dry which yields ADN. GUDN can also be reacted with ammoni - um-sulfate in alcohol creating a precipitate which is filtered off. The filtrate is concentrated and the remainder is suspended in alco - hoi. The un-soluted particles are filtered off and ADN is obtained through concentrating Synthesis of Amonnium Dinitramide, ADN The present state of technology and problems with the current production of ADN

Currently, ammonium dinitramide (ADN) is produced by reacting guanylureadinitramide in a solution of alcohol and water with potassium-hydroxide which yields potassium-dinitramide (PDN). The process is described in US7981393. In a second process stage KDN is reacted with ammonium- sulfate in a water solution which yields ADN. The second process stage is described in EP0843647. A problem with this production is that the process includes potassium. The potassium will be left in the final product, ADN, which is a problem. It is difficult and expensive to remove the potassium from the ADN. Potassium presents an increased signature when combusting solid rocket fuels and in liquid fuels it creates problems with catalyst poisoning. Another problem with the current production process is that the process involves two process steps. Additional process steps create a more expensive and more time consuming process. A further problem with using the current process is that it demands the use of a large amount of solvent. Solvents have to be taken care of, and possess an environmental burden which preferably should be avoided. The current process is hence expensive, time consuming, environmentally burdening and yields ADN that can be polluted by potassium.

The invention and advantages with the invention The invention comprises a process by which ADN can be produced using GUDN. GUDN is reacted with an ammonium source, for example ammonium- sulfate, ammonium-sulfamate or ammonia, where an ion-change forms ADN from GUDN in a single process stage. The advantages are that the process involves only one process stage and that a smaller amount of solvent is needed. Hence, the process is simpler and more environmentally friendly than previously known processes. Furthermore, the process does not involve potassium and, thus, does not give any potassium residues in produced ADN.

Closer description of the invention The invention is comprises reacting GUDN with an ammonium source whereby ADN is formed through an ion-exchange reaction. In the first of four described methods GUDN is heated together with an ammonium source, for example ammonium-sulfate or ammonium-sulfamate in a water solution until the solution is homogenous. Thereafter the heat source is removed and alcohol, for instance methanol, ethanol, propanols, butanols or similar is added when guanylurea-sulfate (when using ammonium-sulfate) or guanylurea-sulfamate (using ammonium-sulfamate) precipitates from the solution and is filtered off. A filtrate is achieved that, among other things contains ADN and un-reacted GUDN. The filtrate is concentrated and the residue from this stage is suspended in one of the above mentioned alcohols, and ADN is dissolved in it. GUDN remains undissolved and is discarded through filtration. The filtrate is concentrated to dryness which yields pure ADN. In a second described method ammonia is used as a source of ammonium. A solution of ammonia and GUDN is made. Then an ion-exchange takes place at which ADN and guanylurea is formed in the solution. The solution is passed through a column with active carbon which has been pre-treated with diluted ammonia. Guanylurea then remained in the column and ADN leaves the column together with the solvent. Evaporation of this, so called, eluted solution yields pure ADN. In a third described method GUDN and ammonium-sulfate are mixed in an alcohol, for example methanol, ethanol, propanols and butanols or similar. A mixture of alcohol, GUDN and ammonium-sulfate is backflow-boiled to achieve an ion-exchange. Thereafter the mix is left to cool and a precipitate is formed. The precipitate is filtered off and a filtrate is achieved. In the filtrate there is, among other things, ADN and un-reacted GUDN. The filtrate is concentrated to dryness and the remains from this stage is suspended in one of the above mentioned alcohols, at which time ADN is dissolved. GUDN remains un-dissolved and is removed through filtration. The filtrate which is achieved is concentrated to dryness yielding pure ADN. In a fourth described method GUDN is mixed with ammonium-sulfate in a solution of water and alcohol. Alcohols that can be used are, for example, propanols, pentanols or similar so that a two-phase system is achieved. The mixture is heated until a homogenous solution is achieved. Thereafter the heat is removed and the phases separate again. The organic phase is taken aside. The water phase is extracted using one of the above mentioned alcohols. After separation the organic phase from this extraction is mixed with the organic phase from the previous step. This mixture is concentrated to dryness which yields pure ADN.

Example 1 A mixture was made consisting of GUDN (1g, 4,78 mmole), ammonium- sulfate (0,758g, 5,74 mmole) and water (10 g). The mixture was heated to about 00° C while stirring until it was homogenous, in other words about 5 minutes. Thereafter the heat source was removed and 2-propanol (100 ml) was added which produced a precipitate. The precipitate was filtered and washed with 2-propanol (50 ml). The filtrate and the wash fluid were then mixed and concentrated to dryness. The remains from this stage was suspended in 2-propanol (100 ml) and the unsolved particles were filtered off. The filtrate from this stage was concentrated which yielded ADN. The return was 0,470 g (79,2%).

Example 2 A mixture was made consisting of GUDN (1g, 4,78 mmole), ammonium- sulfamate (0,0655g, 5,74 mmole) and water (10 g). The mixture was heated to about 100° C while stirring until it was homogenous, in other words about 5 minutes. Thereafter the heat source was removed and 2-propanol ( 100 ml) was added which produced a precipitate. The precipitate was filtered and washed with 2-propanol (50 ml). The filtrate and the wash fluid were then mixed and concentrated to dryness. The remains from this step was suspended in 2-propanol (100 ml) and the unsolved particles were filtered off. The filtrate from this stage was concentrated which yielded ADN. The return was 0,457 g (76,9%).

Example 3 A mixture was made consisting of GUDN (1g, 4,78 mmole), ammonium- sulfate (0,758g, 5,74 mmole) and water (10 g). The mixture was heated to about 100° C while stirring until it was homogenous, in other words about 5 minutes. Thereafter the heat source was removed and 2-propanol (200 ml) was added. Approximately 150 ml of the solvent was removed from the mixture through rotary evaporation under vacuum. The remainder from this concentrating stage was filtered. The precipitate that was filtered off was washed with 2-propanol (50 ml). This wash fluid was mixed with the filtrate. The mixture was concentrated which yielded ADN. The return was 0,327 g (55,1%).

Example 4 A mixture was made consisting of GUDN (1g, 4,78 mmole), ammonium- sulfate (0,758g, 5,74 mmole), water (5 ml) and 2-butanol (10 ml). The mixture was heated to about 100° C while stirring until it was homogenous, in other words about 5 minutes. Thereafter the heat source was removed. The solution then separated into an organic phase and a water phase. The organic phase and the water phase were parted. The water phase was extracted using 2-butanol (50 ml), when the solution separated into an organic phase and a water phase. The organic phases from the two separations were combined and concentrated which yields ADN . The return was 0,160 g (26,9%).

Example 5 A mixture was made consisting of GUDN (1g, 4,78 mmole), ammonium- sulfate (0,758g, 5,74 mmole) and methanol (50 ml). The mixture was backflow-boiled for 2 hours whereafter the heat source was removed. The unsolved particles were filtered away and washed with 2-propanol (50 ml). The filtered off reaction solution was mixed with the wash fluid. This mixture was then concentrated to dryness. The filtrate and the wash fluid were then mixed and concentrated to dryness. The remains from this step was suspended in 2-propanol (100 ml) and the unsolved particles were filtered away. The filtrate was concentrated which yielded pure ADN. The return was 0,145 g (24,4%).

Example 6 A column was filled with activated carbon (20 g). The carbon was rinsed with diluted ammonia (5% NH3 aq). A solution was made using GUDN ( 1 ,5 g, 7,17 mmole) and NH3 (6 g, 25% aq). The solution was applied on the column, which then was eluated using diluted ammonia (5 % NH3 aq). The obtained eluent was then concentrated to dryness which yielded ADN. The return was 0,667 g (75%) Claims

Method for producing ammonium dinitramide c h a r a c t e r i z e d i n t h a t guanylureadinitramide is reacted with an ammonium source so that an ion-change takes place and ammonium dinitramide is formed.

Method for producing ammonium dinitramide according to claim 1 c h a r a c t e r i z e d i n t h a t guanylurea dinitramide is reacted with an ammonium source in a solution of water and alcohol.

Method for producing ammonium dinitramide according to claim 2 c h a r a c t e r i z e d i n t h a t the alcohol is methanol.

Method for producing ammonium dinitramide according to claim 2 c h a r a c t e r i z e d i n t h a t the alcohol is ethanol.

Method for producing ammonium-dinitramide according to claim 2 c h a r a c t e r i z e d i n t h a t the alcohol is a propanol.

Method for producing ammonium dinitramide according to claim 2 c h a r a c t e r i z e d i n t h a t the alcohol is a butanol.

Method for producing ammonium dinitramide according to claim 2 c h a r a c t e r i z e d i n t h a t the ammonium source is ammonium-sulfamate.

8 . Method for producing ammonium dinitramide according to claim 2 c h a r a c t e r i z e d i n t h a t the ammonium source is ammonium sulfate. 9 . Method for producing ammonium dinitramide according to claim 1 c h a r a c t e r i z e d i n t h a t the reaction of guanylureadinitramide is reacted an ammonium source in a solution of alcohol.

10. Method for producing ammonium dinitramide according to claim 9 c h a r a c t e r i z e d i n t h a t the ammonium source is ammonium sulfate.

11.Method for producing ammonium dinitramide according to claim 9 c h a r a c t e r i z e d i n t h a t the ammonium source is ammonium sulfamate.

12. Method for producing ammonium dinitramide according to demand 9 c h a r a c t e r i z e d i n t h a t the alcohol is methanol.

13. Method for producing ammonium dinitramide according to claim 9 c h a r a c t e r i z e d i n t h a t the alcohol is ethanol.

14. Method for producing ammonium dinitramide according to claim 9 c h a r a c t e r i z e d i n t h a t the alcohol is a propanol.

15. Method for producing ammonium dinitramide according to claim 9 c h a r a c t e r i z e d i n t h a t the alcohol is a butanol.

16. Method for producing ammonium dinitramide according to claim 1 c h a r a c t e r i z e d i n t h a t the ammonium source is ammonia. 17. Method for producing ammonium-dinitramide according to claim 16 c h a r a c t e r i z e d i n t h a t ammonium dinitramide is isolated through separation using a carbon column. INTERNATIONAL SEARCH REPORT International application No. PCT/SE201 5/000004

A. CLASSIFICATION OF SUBJECT MATTER IPC: see extra sheet According to International Patent Classification (IPC) or to both national classification and IPC B. FIELDS SEARCHED Minimum documentation searched (classification system followed by classification symbols) IPC: C01 B, C06B

Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched SE, DK, Fl, NO classes as above

Electronic data base consulted during the international search (name of data base and, where practicable, search terms used) EPO-lntemal, PAJ, WPI data, CHEM ABS Data, COMPENDEX, IBM-TDB

C. DOCUMENTS CONSIDERED TO BE RELEVANT

Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

US 7981 393 B2 (VORDE CARIN ET AL), 18 September 2008 1- 17 (2008-09-1 8); column 2 , line 13 - line 67; column 2 , line 13 - line 67

EP 0843647 B 1 (FOERSVARETS FORSKNINGSANSTALT), 1- 17 27 May 1998 ( 1 998-05-27); paragraphs [0026]-[0027]

TALAWAR M. B.; SIVABALAN R.; MUKUNDAN T.; 1- 17 MUTHURAJAN H.; SIKDER A . K.; GANDHE B. R ; SUBHANANDA RAO A."Environmentally compatible next generation green energetic materials (GEMs) ". Journal of Hazardous Materials. ISSN 0304-3894. pp. 589-607.; page 596, line 27 - line 36

I I Further documents are listed in the continuation of Box C . See patent family annex.

Special categories of cited documents: T " later document published after the international filing date or priority " document defining the general state of the art which is not considered date and not in conflict with the application but cited to understand to be of particular relevance the principle or theory underlying the invention "E" earlier application or patent but published on or after the international 'X" document of particular relevance; the claimed invention cannot be filing date considered novel or cannot be considered to involve an inventive "L" document which may throw doubts on priority claim(s) or which is step when the document is taken alone cited to establish the publication date of another citation or other Ύ document of particular relevance; the claimed invention cannot be special reason (as specified) considered to involve an inventive step when the document is "O" document referring to an oral disclosure, use, exhibition or other combined with one or more other such documents, such combination means being obvious to a person skilled in the art "P" document published prior to the international filing date but later than '&" document member of the same patent family the priority date claimed Date of the actual completion of the international search Date of mailing of the international search report 15-04-201 5 16-04-201 5

Name and mailing address of the ISA/SE Authorized officer Patent- och registreringsverket Box 5055 Bengt Christensson S- 2 42 STOCKHOLM Facsimile No. + 46 8 666 02 86 Telephone No. + 46 8 782 25 oo Form PCT/ISA/210 (second sheet) (July 2009) INTERNATIONAL SEARCH REPORT International application No. PCT/SE201 5/000004

Continuation of: second sheet International Patent Classification (IPC) C06B 25/34 (2006.01 ) C01B 21/082 (2006.01 )

Form PCT/ISA/210 (extra sheet) (July 2009) INTERNATIONAL SEARCH REPORT International application No. Information on patent family members PCT/SE201 5/000004

US 7981 393 B2 A U 2005206466 A 1 04/08/2005 BR PI0506957 A 26/06/2007 CA 2552765 C 27/1 1/201 2 EP 1706354 A 1 04/1 0/2006 IL 176722 A 30/1 1/201 0 P 2007519600 A 19/07/2007 P 4847875 B2 28/1 2/201 1 NO 20063241 A 10/1 0/2006 SE 526402 C2 06/09/2005 SE 04001 17 A 22/07/2005 US 20080226533 A 1 18/09/2008 O 2005070823 A 1 04/08/2005 EP 0843647 B 1 AT 200470 T 15/04/2001 A U 6539696 A 05/03/1997 A U 703767 B2 01/04/1999 BR 9609993 A 06/07/1999 CA 2227625 A 1 20/02/1997 DE 6961 2497 D 1 17/05/2001 ES 2 159039 T3 16/09/2001 IL 122880 A 31/1 0/2000 P 4 1 18947 B2 16/07/2008 P H 1 1514323 A 07/1 2/1999 NO 321 198 B 1 03/04/2006 NO 980534 A 06/02/1998 SE 5 1671 9 C2 19/02/2002 SE 9503326 L 09/02/1997 T R 98001 29 T 1 21/04/1998 US 5976483 A 02/1 1/1999 O 9706099 A 1 20/02/1997

Form PCT/ISA/210 (patent family annex) (July 2009)