Reactions in the System Nitro-cellulose/ Diphenylamine with Special Reference to the Formation of a Stabilizing Product Bonded to Nitro-cellulose

The methods HPLC, microcalorimetry and FTIR together with chemometry, provide good analytical tools to follow the degradation of nitro-cellulose.The degradation products formed from diphenylamine (DPA) during storage can be followed with HPLC. FTIR, together with chemometry, also gives the precision needed for safety control of propellants.Nitro-cellulose (NC) containing DPA obtained a green colour already after 1 day storage at 70°C. About 10% of the stabilizer, and its derivatives, added were not extractable giving an extended time to autocatalysis. This time could be extended up to 70 days at 70°C for an extracted sample compared to about 3 days for non-stabilized NC. This was not shown before.Aged and extracted NC samples contained a non-extractable nitro compound. The most likely compound is 2,4´-dinitroDPA, probably bonded to NC via the amine nitrogen. The bonding to NC occurs after the formation of NNODPA. This is something not described before.Using another batch of nitro-cellulose to find out if a chemical bonding occurs gave inconclusive results as a blue NC was formed. Low molecular NC with high stability was obtained. A chemical bonding probably occurs when using NNODPA as a stabilizer, indicating NNODPA plays a key role.The use of FTIR/chemometry is a promising method to use when studying small chemical changes. The described methodology should be used to find out more about the compound(s) being bonded to NC.

[1]  P. Welzel.  Die thermische Spaltung einiger Diarylnitrosamine und -nitramine , 1971 .

[2]  R. Phillips,et al.  The Kinetics of the Thermal Decomposition of Nitrocellulose. , 1955 .

[3]  P. Mischke,et al.  Cellulose and its derivatives , 2002 .

[4]  A. Sharples.  CHAPTER 2 – CELLULOSE AND ITS DERIVATIVES , 1963 .

[5]  A. Bergens.  Decomposition of diphenylamine in nitrocellulose based propellants-II. Application of a numerical model to concentration-time data determined by liquid chromatography and dual-wavelength detection. , 1995, Talanta.

[6]  F. Volk.  Determining the Shelflife of Solid Propellants , 1976 .

[7]  R. Prud’homme,et al.  A nonisothermal fourier transform infrared degradation study of nitrocelluloses derived from wood and cotton , 1987 .

[8]  A. Roche,et al.  Organic Chemistry: , 1982, Nature.

[9]  N. Eisenreich,et al.  Kinetic modelling of the stabilizer consumption and of the consecutive products of the stabilizer in a gun propellant , 1997 .

[10]  T. Urbański,et al.  Chemistry and technology of explosives , 1984 .

[11]  A. J. Bellamy,et al.  Stabilizer reactions in cast double base rocket propellants. Part VI: Reactions of propellant stabilizers with the known propellant decomposition products NO2, HNO2, and HNO3 , 1995 .

[12]  M. Bohn.  Kinetic Modelling of the Concentrations of the Stabilizer DPA and Some of Its Consecutive Products as Function of Time and Temperature , 2001 .

[13]  F. Volk.  Determination of the Lifetimes of Gun Propellants using thin‐layer chromatography , 1976 .

[14]  K. Trueblood,et al.  Chromatographic Investigations of Smokeless Powder , 1949 .

[15]  Manfred A. Bohn,et al.  Aging behavior of propellants investigated by heat generation, stabilizer consumption, and molar mass degradation , 1992 .

[16]  K. Kuo.  Chemistry of Nitrate Ester and Nitramine Propellants , 1984 .

[17]  G. W. Small.  Spectrometric Identification of Organic Compounds , 1992 .

[18]  R. Drago,et al.  The Reaction of Nitrogen(II) Oxide with Various Primary and Secondary Amines , 1961 .

[19]  R. W. V. Dolah,et al.  The Chemistry of Nitrate Esters , 1955 .

[20]  M. Bohn,et al.  Determination of Chemical and Mechanical Properties of Double Base Propellants during Aging , 1987 .

[21]  W. Fernelius.  The Inorganic Chemistry of Nitrogen. , 1964, Science.

[22]  P. Rogasch,et al.  Determination of Derivatives of Diphenylamine in Australian Gun Propellants by high performance liquid chromatography , 1987 .

[23]  N. J. Curtis.  Isomer distribution of nitro derivatives of diphenylamine in gun propellants : nitrosamine chemistry , 1990 .

[24]  Kenneth K. Kuo,et al.  Fundamentals of Solid-Propellant Combustion , 1984 .

[25]  R. Danielsson,et al.  Decomposition of diphenylamine in nitrocellulose based propellants-I. Optimization of a numerical model to concentration-time data for diphenylamine and its primary degradation products determined by liquid chromatography with dual-amperometric detection. , 1995, Talanta.

[26]  K. Kishore,et al.  Mechanism of thermal decomposition of double base propellants , 1983 .

[27]  F. Volk,et al.  Determination of the Decomposition Behavior of Double‐Base Propellants at Low Temperatures , 1985 .

[28]  J. Bellerby,et al.  Stabilizer reactions in cast double base rocket propellants. Part II: Formation and subsequent reactions of N-nitroso derivatives of para-nitro-N-methylaniline and 2-nitrodiphenylamine in mixed-stabilizer propellants aged at 80°C and 90°C , 1991 .

[29]  J. Bellerby,et al.  Stabilizer reactions in cast double base rocket propellants. Part I: HPLC Determination of Stabilizers and their derivatives in a propellant containing the stabilizer mixture para‐nitro‐N‐methylaniline and 2‐nitrodiphenylamine aged at 80°C and 90°C , 1991 .

[30]  L. Phillips.  Thermal Decomposition of Organic Nitrates , 1947, Nature.