Amino, nitro ve azido grupları içeren tek ve iki halkalı aromatik enerjik maddelerin kromatografik yöntemlerle analizlerinin araştırılması

Calismada pikril klorur ve simetrik yapili diaminler kullanilarak azotca zengin 14 tane enerjik madde hazirlanarak element analizi, IR spektroskopi, kutle spektroskopi, 1H nukleer magnetik rezonans, 13C-nukleer magnetik rezonans yontemleri ile karakterizasyonu yapilmistir. Ayrica calismaya konu olan enerjik maddelerin termal ozellikleri termogravimetri ve diferensiyel taramali kalorimetri ile analiz edilerek patlama entalpileri olculmustur. Hazirlanan enerjik maddeler pikril klorur ile simetrik amin olan hidrazin, etilendiamin, 1,3-propandiamin, 1,4-butandiamin, 1,7-heptandiamin, 1,2-fenilendiamin, 1,4-fenilendiamin, bis-N,N’(2-aminoetil)amin, tris-N,N’,N’’(2-aminoetilamin) tepkimeleri ile hazirlanmistir. Bunun yaninda simetrik olmayan enerjik maddeler ise pikril klorur ile 2-nitroanilin ve 4-nitroanilinin tepkimesinden elde edilmistir. Ayrica pikril klorur ile 3,5-dinitrosalisilaldehitin kondensasyon tepkimesinden de azotca zengin enerjik madde bu calisma kapsaminda incelenmistir. Calismanin hedefleri arasinda bu enerjik maddelerin yuksek basincli sivi kromatografi yontemi ile analiz sartlarinin arastirilmasi bulunmaktadir. Bu amacla hazirlanan enerjik maddelerin cesitli aprotik ve amfiprotik tasiyici faz karisimlari ile ODS kolondaki davranislari incelenmistir. Yuksek basincli sivi kromatografisi ile yapilan calismalarda ozellikle asetonitril-su tasiyici fazinda, %60-%40 veya buna yakin kompozisyonlarda pikril grubunun bir parca hidroliz olmasina ragmen ayirmanin mumkun oldugu gozlenmistir. Ek olarak MeOH gibi amfiprotik cozuculeriiikullanildiginda ayirmanin mumkun olmadigi gozlenmistir. Su oraninin artirilmasinin (tasiyici fazin polaritesini artirmasindan dolayi) ise ayirmayi olumlu etkiledigi gozlenmistir. Ancak su orani arttikca hidrolizin artmasindan ve % 55 oranindan daha yuksek oldugu durumlarda enerjik maddelerin cozunmeyip coktugu gozlenmistir. Calismanin hedefleri dogrultusunda soz konusu maddelerden sadece 3 tanesi X-isinlari kirinimi yontemleri ile incelenebilecek uygun kristaller olusturmustur ve bu 3 maddenin molekuler modelleri bulunarak kristal ozelliklerinin termal bozunmaya olan etkileri arastirilmistir. Her bir maddenin kutle spektroskopi yontemi ile elde edilen parcalanma fragmentlerinden yola cikilarak termal parcalanma mekanizmasi hakkinda yorum yapilmis ve parcalanmanin 4,6-dinitrobenzofuroksan ara basamagi uzerinden oldugu sonucuna varilmistir. Ayrica hazirlanan enerjik maddelerin Gaussian 09 paket programi yardimiyla teorik standart olusum entalpileri hesaplanmasi da calisma kapsami icine alinmistir. Ancak molekul kutleleri buyuk oldugundan sadece bir tanesinin Gaussian 09 yardimi ile standart olusum entalpisi teorik olarak belirlenmis ve bulunan deger kullanilarak (Hess Yasasi uyarinca) teorik patlama entalpisi hesaplanmistir. Bu teorik deger ile diferansiyel taramali kalorimetri yonteminden bulunan deneysel degerler uyum gostermistir.AbstractIn this thesis, 14 nitrogen rich, high energy materials were synthesized from symmetrical diamines and picryl chloride. They were characterized by elemental analysis, IR spectroscopy, mass spectroscopy, 1H and 13C nuclear magnetic resonance spectroscopy. Thermal characteristics, especially explosion enthalpies of these materials were elucidated by thermogravimetry and differential scanning calorimetry. The symmetrical products were prepared by the reaction of hydrazine, ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,7-heptanedimine, 1,2-phenylenediamine, 1,4-phenylenediamine, bis-N-N'(2aminoethylamine), tris-N,N',N''(2-aminoethylamine) with picryl chloride, whereas non-symmetrical materials were prepared from 2-nitroaniline and 4-nitroaniline. In addition, the energetic compound (N(3,5-dinitrosalisiliden)-2,4,6-trinitrofenilhidrazin), obtained by the condensation reaction of picryl chloride and 3,5-dinitrosalicylaldehyde, was also investigated. The determination of optimal analysis conditions for these compounds were carried out by high performance liquid chromatography. For this purpose, their behaviours in an ODS column were investigated with various aprotic and amphiprotic mobile phase compositions. The best medium for the seperation of the materials was 60:40 acetonitrile:water mixture despite the fact that the picryl groups are hydrolized in the presence of water. However amphiprotic solvents like MeOH did not yield satisfactory results. Increasing the water ratio improves seperation but it also increases hydrolysis and decreases the solubility ofvthe materials. The compounds tend to precipitate in mobile phases with water ratio over 55%. Only the molecular sizes of three of the compounds synthesized were adequate for X-Ray diffraction. Their molecular models obtained were used in the interpretation of the effect of crystal properties upon thermal decomposition process. A thermal decomposition mechanism was proposed based on the electron impact mass spectroscopy data. It was deducted that the decomposition took place through 4,6-dinitrobenzofuroxane adduct. In addition, calculation of the theroretical standard formation enthalpies of the materials were carried out by the use of Gaussian 09 package software. However, the simulations were not succesful due to the big size of the molecules. It was only possible to determine the theoretical enthalpy value for the smallest molecule. The calculated value was then used to determine the theoretical explosion enthalpy according to Hess' Law. This value was seen to be in good compliance with the experimental results.