Network formation involving epoxide and carboxyl groups

Summary The base catalyzed reaction between epoxide and carboxyl groups was studied using a simple model system phenylglycidyl ether-caproic acid in the presence of triethylamine. The reaction was investigated by mass spectrometry and GPC which provide an overall qualitative and quantitative survey of all the forming reaction products. The addition esterification is followed by etherification and condensation esterification and the main reaction product, monoester, is disproportionated yielding diester and diol. In a polyfunctional system, the latter reaction may cause splitting of the polymer chain and formation of new crosslinks.     

Friction Sensitivity of Nitramines. Part Ⅱ: Comparison with Thermal Reactivity（英）

The friction sensitivity (FS) of five linear and eight cyclic nitramines has been determined.Arrhenius parameters of non-autocatalyzed thermal decomposition of these nitramines were used for comparison...     

New aspects of initiation reactivities of energetic materials demonstrated on nitramines

A brief survey is presented of the author's results obtained from studies of the chemical micro-mechanisms of nitramines initiation from the point of view of organic chemistry. The relationships have been presented and discussed between the characteristics of impact and electric spark sensitivities, detonation and thermal decomposition, on the one hand, and (15)N NMR chemical shifts of nitrogen atoms of nitramino groups, on the other. In the case of the impact sensitivity, the said relationships involve the (15)N shifts of the amino nitrogen atoms carrying the nitro group primarily split off from the molecule. In the case of the initiation by shock, heat and electric spark, the (15)N shifts of nitrogen atoms in the primarily split off nitro groups themselves are involved. Also, the relationships are presented between the characteristics of thermal reactivity and values of the electronic charges at the nitro groups that are primarily split off. It has been stated that the chemical micro-mechanisms of primary fission processes of molecules of nitramines in the initiation by mechanical stimuli (inclusive the detonation course) and electric spark should be the same as in the case of their low-temperature thermal decomposition. It has been found that the electron structure and close neighbourhood of nitrogen atom of the primarily leaving nitro group is a dominant factor in initiation by shock, electric spark and heat. In the case of initiation by impact a key role plays characteristics of amino nitrogen atoms which are carriers of these most reactive nitro groups. Also mentioned is relevance of the modified Evans-Polanyi-Semenov relationship. On the basis of the findings presented it also has been stated that the detonation transformation itself of the nitramines should be preceded by an induction period.     

A New Aspect of Relationships between Electric Spark Sensitivity and Thermal Stability of Some Polynitro Arenes（英）

An ESZ KTTV instrument of a new,relatively simple construction has been applied to determination of electric spark sensitivity of 29 polynitro arenes,expressed as spark energy,EES,required for 50-percent initiation probability.The thermal stability thresholds,Tmax,were calculated from the published Arrhenius parameters of monomolecular thermal decomposition of the studied compounds,predominantly obtained under the conditions of the Russian manometric method.An approximate relationship has been found between the ln EES values and threshold Tmax values.In the sense of this relationship,the compounds studied fall into several sub-groups.The reason of the said diversification lies in the decomposition reaction rate at the temperature of onset of their thermal decomposition.It has been found that in each sub-group increasing thermal stability of polynitro arenes is accompanied by increasing electric spark sensitivity of these substances.This fact must be taken into account if we deal with the problem of electric spark energy transfer into the reaction centre of the molecule.     

Friction Sensitivity of Nitramines. Part Ⅲ: Comparison with Detonation Performance（英）

The friction sensitivities (FS) of five linear and eight cyclic nitramines have been determined.These FS values were compared with the respective detonation velocities,D,and with the dimensionless ratio created by relating the heat of explosion,Qreal,to the activation energy,Ea,of non-autocatalyzed thermal decomposition of the explosives concerned.For the nitramaines studied,these comparisons show a general trend of FS decreasing with increasing energy content.     

The determination of β-ketoamide structures in poly(2-pyrrolidone)

Ketoamide and ketoimide units incorporated in poly(2-pyrrolidone) as a result of side reactions in the anionic polymerization may be quantitatively determined as 1,7-dibenzamido-heptane-4-one (IIa) after the total acid hydrolysis of the polymer and benzoylation of the hydrolyzate. Conditions were found for the quantitative analysis of these structures using liquid chromatography.     

Decomposition of some polynitro arenes initiated by heat and shock Part I. 2,4,6-Trinitrotoluene

Samples of 2,4,6-trinitrotoluene (TNT) exposed to heat or to shock and residues after their detonation have been analyzed chromatographically (LC-UV and LC/MS). It was found that the main identified decomposition intermediates are identical in all the three cases. 4,6-Dinitro-2,1-benzoisoxazole and 2,4,6-trinitrobenzaldehyde are the most reactive from them. It has been stated that the chemical micro-mechanism of the primary fragmentations of shock-exposed TNT molecules and/or its detonation transformation should be the same as in the case of its low-temperature thermal decomposition.     

Decomposition of some polynitro arenes initiated by heat and shock Part II: Several N-(2,4,6-trinitrophenyl)-substituted amino derivatives

Samples of 2,4,6-trinitroaniline (PAM), 2,4,6-trinitro-N-(2,4,6-trinitrophenyl)aniline (DPA), N,N'-bis(2,4,6-trinitrophenyl)-3,5-dinitropyridine-2,6-diamine (PYX) and N,N',N'-tris(2,4,6-trinitrophenyl)-1,3,5-triazine-2,4,6-triamine (TPM) were exposed to heat or to shock and then analysed chromatographically (LC-UV and LC/MS). It was found that the main identified decomposition products of these two incomplete initiations are identical for each of the compounds studied. It has been stated that the chemical micro-mechanism of the primary fragmentations of their low-temperature decomposition should be the same as in the case of their initiation by shock, including fragmentation during their detonation transformation.