Methods forobtainingoctogen(HMX) Octogen characteristic Introduction tetramine) pentamethylene (dinitro DPT is octogen obtaining at aimed nitration industrial processesrequiresconversion fromthealphatobetaform. The in which form, alpha polymorphic its in octogen of production to lead octogen. – cases most obtained in synthesis of conditions environmental and temperature is compound polinitrosamine segment eight- an conditions milder Under (RDX). hexogen – polynitrosamine cyclic six-segment a mainly of forming to leads conditions severe nitration under The synthesis. of conditions temperature the and feeding of sequence proportion, the on depends effect in difference the while materials, raw same the from produced are hexogen and octogen Both hexamethylenetetramine. octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazine further researchfocusedonsynthesisingthecompound. out carries institute Warsaw.The in Chemistry Organic Industrial of carried out according to the original method developed by is the production Institute The scale. industrial an on countries produced is few octogen where the of one is Poland applications. civil and military both in used widely is explosive this characteristics performance high its to stability.Thanks thermal high featuring and velocity detonation high a having Poland in manufactured explosive brisant high powerful f rntooun (N) au. coe sos tog thermal strong shows Octogen resistance, asitsmeltingpointrangesfrom278.5°Cto280°C. value. (TNT) trinitrotoluene of (strength) measured in the Trauzl lead block test amounted to 145% a density of 1.84 g/cm at octogen for velocity detonation The J/g. 5679 is explosion of heat the detonation velocity, brisance and thermal stability. The calculated improvesmixtures explosive in octogen of use The (RDX). hexogen with compared as octogen with filled shells (HEAT) warheads tank detecting after better results for octogen armour piercing with high-explosive to anti- paid was attention more that 1960s the in was It For the first time, octogen was identified as a contaminant of hexogen. applications is the beta form of octogen, stable at room temperature. industrial in used one only The properties. physical delta, different having and gamma, beta, alpha, forms: crystal polymorphic four in h itreit pout f h hexamethylenetetramine the of product intermediate The of nitration the in mainly obtained is (HMX) Octogen Summary formula:C Structural formula: 1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane, name: Chemical a is (HMX), cyclotetramethylene-tetranitramine - Octogen Octogen (HMX) is a crystalline white-coloured solid. It occurs It solid. white-coloured crystalline a is (HMX) Octogen ymn MTS Drt PWŁ, nre OZCOSI Adzj AAD – Institute Please citeas:CHEMIK2012,66,1,58-63 – MARANDA Andrzej ORZECHOWSKI, Andrzej POWAŁA, of IndustrialOrganicChemistry, Warsaw Dorota MATYS, Zygmunt Methods forobtainingoctogen(HMX) nr 1/2012 •tom 66 3 is 9124 m/sec. The explosive’s work capacity capacity work explosive’s The m/sec. 9124 is 4 H 8 N 8 O 8 developed bytheInstituteofIndustrialOrganicChemistryinWarsaw. of aceticacidandanhydride. they are ofnopracticalimportance. though DPT, and octogen obtain to hexamethylenetetramine • (DPT) withoutthepresenceofaceticacidanditsanhydride tetramine withtheliberationofanintermediateproduct synthesisofoctogenfromhexamethylene- The two-stage reaction: formed fromhexamethylenetetramine(HMTA): formaldehyde with precise, be to (HMTA), hexamethylenetetramine following: • • following reactions: • • • reactions: with theliberationofanintermediateproduct-DPT. • • Below we present two different methods for producing octogen producing for methods different two present we Below presence the require octogen obtaining for methods known Most than substances initial other using methods also are There without theformationofanintermediateproduct(DPT). h cciain f ier irsmns us n h following the in runs nitrosamines linear of cyclisation The with reacts (DNU) dinitrourea stage next the In the is urea of nitration the during place taking reaction main The oxidisingcrystallisation. the so-called the nitrolysisofDPT the of result a as HMX obtaining in consists stage second The the cyclisationoflinearnitrosamineswithammoniatoformDPT (HMTA) hexamethylenetetramine with (DNU) dinitrourea of reaction the the nitrationofurea The first stage consists in obtaining DPT as a result of the following synthesis two-stage in consists octogen obtaining for method The w -tg otgn ytei fo hexamethylenetetramine from synthesis octogen Two-stage the formationofanintermediateproduct(DPT) with hexamethylenetetramine from synthesis Two-stageoctogen synthesisfromhexamethylenetetramine Direct, single-stage There areafewalternativesoftheoctogensynthesis: • 61

science science 62 • and N a number of linear nitrosamine and gaseous products (including CO (including products gaseous and nitrosamine linear of number a of side reactions leading to the formation of small amounts of hexogen, follows: of thisexplosive. the method under industrial conditions, the plant started the production installation for manufacturing octogen process with this production method. After testing verifying a built has Bydgoszcz in Plant) Chemical form) polymorphic hexamethylenetetramine (HMTA) volume. (per beta % 40 approximately of stable yield percentage a at (the %, 98 than more of content ingredient main a continuousprocess. sour octogenisrinsedwithwateranddried. octogen in acid is cooled down and delivered to a filter. The filtered, nitric acid. Once the dilution process is completed, the suspension dilute of obtain of to water mixture in absorbed and brown extracted are dark oxides, nitric the i.e. decomposition, of products The necessary.as material reacting the heating or cooling and required reactor at a the same into time material stirring it reacting intensely, and keeping the water temperature introducing This in %. consists 50÷55 reaction of range the within acids waste the of keep concentration to added is Water temperature. elevated at water with material nitrated diluting by by-products, decompose and product low Then, at material. theprecipitate to out carried is crystallisation oxidising so-called the the out cooling carried and stirring is intensely nitration by temperature The acid. nitric concentrated in nitrate ammonium of solution the constituting mixture, nitrating the the nitrolysisofDPT. DPT isrinsedwithwateranddried. the DPT suspension formed is filtered. After completing filtration, the Finally,reached. is pH preset the until continues and begins solution ammonia aqueous % 25 of proportioning the then, down; cooled is throughout the process. Once the water operation intensely stirring prepared is (HMTA)while completed, already hexamethylenetetramine the of solution material the to proportioned is material nitrated the Then, nitration. of process the complete to stirred is material reacting material. Once the proportioning is completed, the reacting the intensely cooling and stirring while mixture nitrating the to urea proportioning by out carried is urea of nitration The acid). sulphuric by using a nitrating mixture consisting of nitric acid and oleum (fuming carbon dioxide. decompose with the liberation of gaseous products – nitric oxides and In addition to reactions leading to octogen formation there are a lot as looks DPT of nitrolysis the during running reaction main The ałd Ceize NtoCe” A “ir-hm SA (“Nitro-Chem” SA “Nitro-Chem” Chemiczne Zakłady the having product final the obtains one method this With is one second the periodically, while out carried is stage first The to DPT (adding) proportioning by out carried is reaction The Stage 2 of the production process consists in obtaining octogen by urea of nitration the with begins DPT of synthesis the – 1 Stage products linear the crystallisation oxidising of stage the During 2 O). 2

a aotd n te eerh ok n hs coe production octogen this on method ended. work research the and aborted was concerning the installation for concentrating acetic acid, the concept tests installation offer-based completing After process. the to back subject to denitration be and would it concentration that predicted and was then It 50%. it approx. at of would acid concentration be a acetic waste delivered octogen) raw of kg 1 per kg 18.8 (approx. of assumed. requirements the met obtained product the i.e. tests, scale industrial hexamethylenetetramine (HMTA) volume. more contains stabilisation after per % 70 approx. of yield percentage a at octogen pure of % 98 than that product a obtain described we conditions the above, under out carried synthesis, the of result a As form. alpha polymorphic non-stable its in precipitates method, HMX raw of precipitate the is filtered. then and 20C approximately to down cooled is it where unit another to goes suspension reaction post- the reactor this leaving After heating. to subject is it where reactor.this in From apparatusanother to fed is material the there • • the are proportioned(added): Then, ingredients following the material). where unit another the to directed is (heating material temperature high at reaction the continues where unit another into delivered is material reacting • • • reactors arrangedinacascadesystem.Thefirstreactorisfedwith: linear nitrosamines. are a number of side reactions including the formation of hexogen and an intermediateproduct-DPT. and trioxane(atrimerofformaldehyde). of in nitric acid, in the presence of of hexamethylenetetramine (HMTA) in acetic acid, using the solution (DPT) withthepresenceofaceticacidanditsanhydride tramine withouttheliberationofanintermediateproduct synthesisofoctogenfromhexamethylenete- The two-stage oee, h mto poue eteey ag amounts large extremely produces method the However, completed successfully some perform to used was method This this to according nitrolysis the to subject product, raw The occurs DPT of nitrolysis the in HMX forming of reaction The acetic anhydride. the solutionofammoniumnitrateinnitricacid DPT.– obtained The is product intermediate an apparatus this In acetic anhydride. the solutionofammoniumnitrateinnitricacid added, inaceticacid h slto o hxmtyeeermn (MA wt troxane with (HMTA) hexamethylenetetramine of solution the many of consists that equipment in out carried is process The In addition to the main reaction leading to octogen formation there The reactionofproductformationlooksasfollows: of separation the without continuously out carried is process The n hs ehd coe i otie b a w-tg nitrolysis two-stage a by obtained is octogen method this In nr 1/2012 •tom 66

Summary implemented. where and developed Polandbeen had in production octogen of was method original this the that emphasizing worth is it Therefore, disadvantageous when the process is carried out on an industrial scale. different products from the same raw materials, which seems especially presented atconferencesheldinPoland andabroad. posters and papers 19 publications, process 41 of co-author production the is She explosive testing. and include High interests of research Department Her the . at Chemistry Organic Industrial of Institute the at works she Currently (2010). Institute Mining Central the at dissertation doctoral her Technologydefended of She University Warsaw(2001). the of process ofexplosives. production and synthesis the with mainly dealing years, many for Chemistry Poland and abroad. He has been working at the Institute of Industrial Organic in both symposia and conferences of number a in part taken has He patents. 6 and papers 17 of author Technology.the of is University He Warsaw the Years ofNobelPrize inchemistryforMariaSkłodowska-Curie”. “100 stamps post Polish-Swedish two were presented Also Skłodowska-Curie. Maria of image the with 20 PLN of denomination with banknote collector a circulation into put officially to occasion an also was ceremony The emphasised. he - there” buried was who abroad, from person first the also was She merits. own her of recognition in there buried woman first the was she but there, rest men prominent of wives ParisPantheon.“Many the in buried was Skłodowska-Curie Maria that reminded Fremont Christian cabinet his of director the Sarkozy, Nicolas President French of behalf On participants. the to letters Gronkiewicz-Waltzwrote Minister of Science and Higher Education Zbigniew Marciniak. President Bronislaw Komorowski and the President of Warsaw Hanna Michał Kleiber, vice president of the French Academie des Sciences Philippe Taquet, Senate Speaker Bogdan Borusewicz and Deputy Maria of grandson and Pierre Skłodowska-Curie Curie, biologist Prof.the Pierre Joliot and his wife, the President of by the Polish Academy of Sciences, Prof.attended also was ceremony The Society. Research Radiation Polish the of Medal the received Joliot Langevin- Prof. honours. highest the received and discoveries fundamental made men, by dominated world scientific the in who of nuclear physics reminded Helene that Langevin-Joliot, for many women her grandmother was primarily one of the first feminists, granddaughter, Sklodowska-Curie’s Frenchchemists. among particularly had scientists, Skłodowska-Curie esteem about Professor chemistry,supramolecular of talked fathers the of one considered Prof.Lehn, winner Jean-Marie Prize Nobel 1987 research. and did not come from Poland, he always feels at home here, and that also for him Maria Skłodowska Curie was an inspiration in education Nobel Prize in 1986 for his contribution to the study the dynamics of elementary chemical processes, said that although his ancestors received Maria Skłodowska-Curie Medal, awarded by the Polish Chemical Society. The prof. Tseh Lee Yuan of Taiwan, who received of Polish Independence Day on 144 birthday anniversary of Maria Skłodowska-Curie. During the ceremony, the Nobel Prize winner grandsonattendedtheclosingceremonyyearofPolishof SciencesandMariaSkłodowska-Curie’s scientist. Dorota POWAŁA - Ph.D., (Eng), graduated from the Faculty of Chemistry of Chemistry of Faculty the from graduated Eng., - MATYS Zygmunt of lot a forms it as complex is octogen obtaining of process The Prof. Yonath added that she was particularly moved, when the Polish Ambassador to Israel organized a banquet on the occasion Three Nobel laureates in chemistry, representatives of Polish and French presidents, members of the Polish and French Academy Closing CeremonyoftheYear ofMariaSkłodowska-Curie nr 1/2012 •tom 66 and posterspresentedatnationalinternationalconferences a of co-author five monographs, 20 patents, more than 500 articles, papers and application of explosives, environmental protection. He is an author and technology chemistry, interests: Research Chemistry. Organic Industrial of Institute Technologythe of and University Military the at working is he TechnologyNowadays, of (1971). University Warsaw the at Chemistry of in Poland andabroad. of 46 publications, 24 papers and posters presented at conferences held co-author the is interestsHe testing. and research process production His explosive include Explosives. High of Department the of Head as Chemistry Organic Industrial of Institute the at works he Currently He (1993). Technology of University defended his doctoral Warsawdissertation at the Central Mining the Institute (2005). of Chemistry of Andrzej MARANDA – Professor (Ph.D., Eng), graduated from the Faculty Andrzej ORZECHOWSKI - Ph.D., (Eng), graduated from the Faculty (http://www.naukawpolsce.pap.pl, 15.12.2011) • 63

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