ISSN 2079!9780, Review Journal of Chemistry, 2012, Vol. 2, No. 3, pp. 240262. Pleiades Publishing, Ltd., 2012.

Energetic Plasticizers for Gun & Rocket Propellants1

D. Kumari, R. Balakshe, S. Banerjee, and H. Singh
Department of Applied Chemistry, Defence Institute of Advanced Technology (Deemed University),
Girinagar, Pune!411025, India
e!mail: sharidwar@gmail.com, banerjeess@diat.ac.in
Received November 8, 2011; in final form, March 02, 2012

AbstractEnergetic plasticizers have been used in the propellant industry for improving mechanical
properties of propellant formulations and to boost energy. In modern energetic propellant composi!
tion, conventional plasticizers are being gradually replaced by energetic plasticizers having nitro,
nitroamino, azido and other energetic groups or combination of energetic groups in the same mole!
cule. The present article covers the recent advances in the field of energetic plasticizers with special
reference to their applications in gun and rocket propellants. The paper also covers future scope for
R&D work in this area.
Keywords: energetic plasticizers, gun propellants, rocket propellants, nitramine.
DOI: 10.1134/S207997801203003X
1

CONTENTS
1. Introduction.
2. Classification of plasticizers
2.1. Inert plasticizers
2.2. Energetic plasticizers (EPs)
3. Properties of energetic plasticizers (EPs)
3.1. General properties.
3.2. Migration of plasticizers
4. Synthesis, Physico! chemical properties and applications of EPs
4.1. Azido based plasticizers
4.2. Nitrate ester based plasticizers
4.3. N!Nitramine based plasticizers
4.4. Nitro aliphatic plasticizers
4.5. Nitro aromatic plasticizer
4.6. GLYN dimer plasticizer
4.7. Oxetane plasticizers
4.8. Miscellaneous plasticizers
5. Theoretical evaluation on the performance of energetic plasticizers
6. Future scope of energetic plasticizers
7. Conclusions

1. INTRODUCTION
Propellants are the propulsion power behind rockets, missiles and launch vehicles. These are energetic
materials, ejected as hot gaseous products of combustion from the nozzle to produce forward thrust to pro!
pulsion units [1, 2].
1 The article is published in the original.

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241

Gun propellants are generally composed of nitrocellulose or nitrocellulosenitroglycerine or nitrocel!

lulosenitroglycerinenitroguanidine. Additives used in gun propellants are stabilizer, plasticizer, cool!
ant, surface moderant, surface lubricant, flash inhibitor, decoppering agent and anti wear. Rocket propel!
lants are composed of oxidizers, binders, plasticizers, metallic fuels. Other additives like stabilizers, burn
rate modifiers, high energy additives, opacifier, flame suppressant, combustion instability suppressants,
bonding agents etc. are added to impart desired properties to the propellants [3].
Plasticizers are usually liquid organic compounds that are added to propellants to improve their
mechanical properties. On their addition to propellant they impart lower viscosity for mixing and greater
pot life [4].
Plasticizers when added to polymer significantly reduce the brittleness by penetrating deep inside the
polymer matrix and reducing the cohesive forces between polymers and increase the free volume. This
causes an increase in segment mobility, leading to reduction of Tg. The extent to which plasticizers reduce
the Tg of polymer is used as a measure of plasticizer efficiency [5].
The molecular weight of plasticizers may vary from 200 to 2000, and so are their properties. Low
molecular weight plasticizers tend to be volatile whereas higher molecular weight plasticizers are more vis!
cous in nature. So plasticizers having molecular weight in the range of 4001000 are preferred. Several
other factors like compatibility of the plasticizers with propellant, efficiency, stability and cost play an
important role in selection of plasticizer. Two types of plasticizers namely, primary and secondary plasti!
cizers are well known in industry [6]. Primary plasticizers are the true plasticizers; they interact with the
polymer to increase its flexibility. Secondary plasticizers increase the effectiveness of primary plasticizers,
but are often less compatible with the given resin than the primary plasticizer and thus cause surface tacki!
ness, if used in excess. Secondary plasticizers are generally used in conjunction with the primary plasticiz!
ers to reduce cost and to obtain improvement in electrical and low temperature properties. They are also
known as plasticizer extenders.
Plasticization or gelatinization are two similar terms used to describe the initial physico!chemical reac!
tion of the polymer with energetic plasticizer. In this process, the polymer and the plasticizer form a soft
colloidal dispersion which is used for propellant purposes by the application of the mild heat over a period
of time to form a tough, elastic, rubbery solid. Plasticization or gelatinization mostly takes place by two
means, the internal and external plasticization. Internal plasticization involves chemical alteration of the
polymer matrix and is achieved either by random copolymerization or by side chain grafting. While inter!
nal plasticization tends to increase the flexibility of the polymer, the external plasticization lowers the Tg
value and reduce crystallinity by disrupting physical interactions between polymer chains [7].
2. CLASSIFICATION OF PLASTICIZERS
Plasticizers used in gun and rocket propellant industry could be inert (non!energetic) or energetic.
A brief overview about each of these classes is given below.
2.1. Inert Plasticizers (IPs)
Inert or non!explosive plasticizers are generally high molecular weight esters compatible with nitrocel!
lulose (NC) and nitroglycerine (NG). They are in general high boiling liquids. The inert plasticizers are
used to reduce the sensitivity of NG, improve the mechanical properties of the propellant but degrade the
output of the formulation by reduction of the overall oxygen balance, to adjust the energy level and burn!
rate, and to modify the extrusion/processing characteristics of the propellant. Triacetin (glycerol triace!
tate) or dibutyl phthalate (DBP) is generally used as inert plasticizer in combination with resinous binder
material. Other esters used are diethyl phthalate (DEP), dioctyl phthalate (DOP), dioctyl adipate (DOA)
etc [7]. Molecular structures of few inert plasticizers are given in Fig. 1.
Properties of a few selected inert plasticizers (IPs) used in propellant industry are given in Table 1.
2.2. Energetic Plasticizers (EPs)
Energetic plasticizers are defined as the liquid materials having a positive heat of explosion [8]. Heat
of explosion is the energy released by burning the propellant or ingredient in an inert atmosphere and then
cooling to ambient temperatures in a fixed volume. These contribute to the energy of the system and are
preferred to non!energetic plasticizers in rocket and gun propellants and also enhance flexibility and elas!
ticity. The compatibility of the energetic plasticizer contributes much to the properties of the solid propel!
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O
C 4 H9

C4H9

C8H17

O
Dibutyl adipate

O
O
Dioctyl adipate

O
C4H9

O
C4H9

O
O

C8H17

H3C

O
O

Dibutyl sebacate

C8H17

C8H17

Diisooctyl sebacate

O
O

O
CH3
OCOCH3

O
Isodecyl pelargonate

Triacetin
Fig. 1. Inert Plasticizers.

lant. The energetic plasticizers invariably contain functional groups such as nitro, fluoronitro, fluoroam!
ino, azido etc. Based on the energetic groups present in EPs, they can be broadly classified under following
headings:
Azido based plasticizers

Nitrate ester based plasticizers

N!Nitramine based plasticizers

Nitro aliphatic plasticizers

Nitro aromatic plasticizers

GLYN dimer plasticizers

Oxetane plasticizers

Miscellaneous plasticizers

From the above account, it is obvious that EPs described above contain energetic groups like NO2
(nitro), ONO2 (nitrato), NNO2 (nitramino), N3 (azido), NF (fluoroamino) etc. All of these
groups containing bonds like NN, NO and NF i.e. two or more atoms covalently bonded with non!
bonding electrons present in p!orbitals. This results electrostatic repulsion between the atoms. During
internal redox reaction, these bonds break and produce gaseous products like N2 and CO2 in which the
non!bonding electrons are tied up in stable !bonds thereby producing energy. Each of these energetic
groups is known as explosophore [12]. Energetic groups have high potential to achieve superior perfor!
mance in terms of specific impulse, force constants, high burn rates, superior thermal stability, higher
mechanical properties, higher impact and friction insensitivities etc. Thus, EPs play an important role in
rocket and gun propellant industry.
Table 1. Properties of few selected Inert Plasticizers (IPs)*
Name

Mol.
Formula

Freezing
point, C

Oxygen
balance, %

Hf,
Kcal/mol

Tg, C

Specific gravity
at 25C/20C

Dimethyl phthalate
Diethyl phthalate
Dibutyl phthalate
Dioctyl phthalate
Triacetin
Dibutyl sebacate
Diisooctyl sebacate

C10H10O4
C12H14O4
C16H22O4
C24H38O4
C19H14O6
C18H32O4
C26H50O4

1
3
35
25
50
11
45

173.195
194.594
224.460
258.461
184.615
246.153
274.178

144.33
832.26
721.99
684.98
937.58

77, 76, 80
90.0
90.0, 99.0, 95.5
86.5, 72.0

108.0
104.0, 106.0

1.18
1.12
1.04
0.98
1.15
0.94
0.92

Notes: () means data not available, given values are reported in references, 811.
* The data are already available in the literature but are reproduced as evidence supporting these concepts.
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3. PROPERTIES OF ENERGETIC PLASTICIZERS (EPS)

3.1. General Properties
Introduction of energetic plasticizers as a replacement of commonly used inert plasticizers is another
approach to improve the energy level of propellants. Propellants burn in a controlled manner on combus!
tion and are classified mainly under two broad classes namely, gun and rocket propellants.
Gun propellants are further classified as single base propellant (SBP), double base propellant (DBP),
triple base propellant (TBP), high energy propellant (HEP) containing RDX, HMX and composite pro!
pellant like low vulnerability ammunition (LOVA) propellants. LOVA propellants have essentially
emerged to overcome limitations of conventional propellants and to obtain higher ballistic parameters.
While single base propellants contain NC as major ingredient, DBP uses both NC and NG. TBP use
picrite (nitroguanidine) in addition to NC and NG. TBP have been developed as cooler propellant to
obtain lower flame temperature (Tf) for gun propellants.
Rocket propellants can be classified as double base propellant (DBP), Composite propellant, compos!
ite modified double base (CMDB) propellant, advanced solid propellants, nitramine based propellants
and fuel rich propellants for rocket ramjets. Unlike DBP, which are homogeneous in nature, Composite
propellants (CPs) are heterogeneous in nature and contain powerful oxidizers such as ammonium per!
chlorate (AP), a binder cum fuel like hydroxy terminated polybutadiene (HTPB) or carboxyl terminated
polybutadiene (CTPB) along with metallic fuel like aluminum. CMDB propellants take advantage of both
double base and composite propellant systems and contain NC, NG, AP and Al in addition to energetic
fillers like RDX (1,3,5!trinitro!1,3,5!triazacyclohexane) and HMX (1,3,5,7!tetranitro!1,3,5,7!tetraaza!
cyclooctane).
Besides above two, advanced solid propellants are being developed these days to obtain higher eco!
friendliness by using powerful oxidizers along with energetic binders like GAP (glycidyl azide polymer),
BAMO (3,3!bis(azidomethyl)oxetane) and energetic plasticizers. A plasticizer is usually added to improve
the mechanical properties of the binder itself by lowering its glass transition temperature and ensuring that
the material stays rubbery at the lowest operational encountered temperature and that it never loses its
physical integrity. In order to correctly perform this function, the plasticizer should form a homogenous
mixture with the binder. EPs when added to polymer form colloidal dispersion and when this dispersion
is subjected to heat it forms rubbery solid.
To obtain higher performance, energetic polymers with optimum mass distribution along with low
molecular weight energetic plasticizers meet various requirements. Structural similarity of plasticizers
with the polymer matrix should facilitate incorporation and compatibility. Therefore, recent approach has
been to design plasticizers that resemble more closely to the polymer and are capable of enhancing phys!
ical and chemical compatibility along with minimizing migration from the propellant matrix. Other
important considerations include energy content and safety.
The main role of EPs, in propellant formulations, is to modify their sensitivity, mechanical properties
and to enhance easy processing besides imparting extra energy. This is achieved by softening the polymer
matrix and making it more flexible. To fulfill these roles of ease of processing, improving energetics and
mechanical properties, plasticizers characteristics like chemical and physical compatibility and stability
with other ingredients of propellant formulation, absence of toxicity, high storage life, availability, afford!
ability and cost assume high importance.
Energetic plasticizers tend to be somewhat viscous in nature, and this limits the amount of solids that
can be included in propellant formulations while maintaining good propellant processability. Reducing
the solids loading of a propellant generally results in a lowered propellant impulse. These also act as sur!
face agent by improving the adhesion of the crystalline material to the plasticized binder.
An optimum energetic plasticizer has a low glass transition temperature (Tg), low viscosity, lower abil!
ity to migrate, high oxygen balance, positive heat of combustion (Hcomb) and negative heat of formation
(Hf). It should be thermally stable and have low impact sensitivity.
As discussed before, introduction of plasticizer to a polymeric binder lowers the Tg, which prevents the
binder from getting brittle even at operationally low temperature. Usually inert plasticizers are used for
this purpose, however diminishing the energy output.
Towards the replacement of inert plasticizer with EP, Abou Rachid et al. have deviced a technique to
help in screening of several plasticizer/polymer formulations and studied its application in HTPB
DEGDN system [13]. They have carried out the missicibility assessment of plasticizer/polymer blend and
prediction of the enthalpy of vaporization. Further they have carried out molecular dynamic modeling of
plasticizer/polymer systems comprising of inert and energetic plasticizer.
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3.2. Migration of Plasticizers

Migration is a common property observed for plasticizers. Composite propellants have several mobile
ingredients. Migrations of these ingredients affect the aging process. The phenomena of plasticizer migra!
tion still continue to attract lot of interest. The effect of curing on migration phenomenon was established.
In case of migration of ferrocene!based burn rate catalyst, it is envisaged to deteriorate the burn rate; how!
ever the migration of plasticizer neutralizes the adverse effects. In general the deterioration of mechanical
properties of propellants and mass loss is due to plasticizer depletion [14].
The development of inhibitor to restrict burning on the propellant surface of DBP and CMDB rocket
propellant has been a difficult problem, because of the presence of NG in these propellants and its subse!
quent migration from propellants towards inhibitors. A low plasticizer migration between propellant and
inhibitor is generally beneficial for adhesive bonding between them but extensive migration affects propel!
lant ballistics. It gives lower performance and at the same time, increases combustion of inhibitor, result!
ing in exposure of more of the propellant surface than desired. The inhibitor swells and becomes mechan!
ically weak and soft due to excessive plasticizer migration. This results in defeat of the purpose of inhibi!
tion of rocket propellants as pressure!time profile changes considerably. Excessive NG migration also
results in de!lamination of the inhibitor from propellant. This also leads to coning of the burning propel!
lant, especially in an end!burning (cigarette burning) propellant. Migration of NG from DB and CMDB
can be prevented by various methods like use of chloro resins and compounds of conventional resins/com!
pounds, use of inorganic fillers, and application of barrier coats [15].
A number of concepts, which explain NG migration qualitatively, have been put forwarded [16] based
on an electrostatic force of attraction between NG and inhibitors leading to migration. NG, being small
in size, can easily seep into the structures of polymers and NG migration comes down on addition of fillers
to polymers. The study of kinetics of NG migration to different polymeric materials with different
crosslink densities shows that as the crosslink density increases, diffusion coefficient as well as NG migra!
tion at infinite time decreases.
Provatas has studied the migration of two energetic plasticizers namely, K10 and GLYN oligomer, used
combination with energetic polymer such as polyGLYN [17]. The migration rates of both K10 and GLYN
oligomer were studied by iso!thermal TGA and it was observed that GLYN oligomer has slower migration
rate as compared to K10. Migration rates follow an inverse correlation with molecular weight.
Plasticizers such as NG, in both the coating and the propellants of cast charge would migrate into the
other part respectively. The migration may be the main reason for the change of ballistic performance of
the propellants and the deterioration of the fire retardancy and separation and cracking of the coating dur!
ing storage. Therefore the service life of double base propellant has been considered to be mainly depen!
dent on the physical ageing effect, which resulted from the migration of NG from the propellant into
the coating. The NG migration has often been measured by using polarography, gas chromatography,
weight method and IR analysis etc. While the new method using thermogravimetricderivative thermo!
gravimetric (TGDTG) made it possible. This method has many advantages as simple, rapid, accurate
and small sample size, which would contribute to examine the variation of the content and the rate of NG
migration with time, temperature and thickness during storage and would be benefit able to investigate the
kinetics of NG migration and reveals its regularity [18].
The ability of a solid propellant to perform as insensitive energetic materials depends heavily on the
compatibility of the binder and plasticizer used in its formulations. In order to correctly perform the func!
tion, the plasticizer must be completely miscible with the binder which will offer the desired mechanical
properties. Simulation of polymer/plasticizer explosive blends using molecular mechanics and molecular
dynamics (MD) simulations first been reported in 2001. These have been found useful to accurately pre!
dict the densities of the polymer/plasticizer systems [19].
4. SYNTHESIS, PHYSICO!CHEMICAL PROPERTIES AND APPLICATIONS OF EPs
4.1. Azide based Plasticizers
Azido plasticizers are like ethyleneglycol!bis(azidoacetate) (EGBAA), diethyleneglycol!bis(azidoace!
tate) (DEGBAA), trimethylolnitromethanetriazidoacetate (TMNTA), pentaerythritol!tetrakis(azidoac!
etate) (PETKAA), low mol wt (400700) glycidyl azide polymer (GAP) and an azide terminated glycidyl
azide plasticizer (GAPA), bis(azidodiethyl)phthalate (BADEP), bis(azidodipropyl)phthalate (BADPP),
bis(azidodibutyl) phthalate (BADBP), tris(azidoacetoxymethyl)propane (TAAMP), bis(azidoacetoxy)!
bis(azidomethyl)propane (BABAMP) and di(azidoacetoxy)!di(azidomethyl)propane (PEAA). Molecu!
lar structures of few azido based plasticizers are given below in Fig. 2.
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HO

CH2N3
O

CH2N3
n

N3

GAP

245

O
N3

N3

N3

GAPA

N3

O
O

BAEA

O
N3

EGBAA

N3

N3

CH2OCOCH2N3
O2N C CH2OCOCH2N3
CH2OCOCH2N3
TMNTA

N3
O

DEGBAA

CH2OCOCH2N3
N3H2COCOH2C C CH2OCOCH2N3
CH2OCOCH2N3
PETKAA

COOCH2CH2N3

COOCH2CH2CH2N3

COOCH2CH2CH2CH2N3

COOCH2CH2N3

COOCH2CH2CH2N3

COOCH2CH2CH2CH2N3

BADEP

BADPP

BADBP

CH2OCOCH2N3
H3CH2C C CH2OCOCH2N3
CH2OCOCH2N3
TAAMP

CH2OCOCH2N3
N3H2C C CH2N3
CH2OCOCH2N3
BABAMP

Fig. 2. Azide based plasticizers.

The ester group has a better lubricative effect and azido ester plasticizers generally have good compat!
ibility with normal energetic binder components used in solid propellants, such as azido binder, nitric acid
ester polyols binder. Azido ester plasticizers also have low vapour pressure, high boiling point, low viscosity
and good processability. Furthermore, the azido group is energetically combined with minimum smoke
release in propellants and it is thermally safe. Some recent advances towards the synthesis and applications
of azide based plasticizer are described below.
Low molecular weight GAP is a well known plasticizer used for composite explosives, gun and rocket
propellants. However, the free hydroxyl group present in GAP reacts with the isocyanate groups present
in curing agent whereby its plasticizing effect is diminished. In this regard, Ampleman et al. have reported
a two step method for the synthesis of GAP polymer having diazide terminated glycidyl azide polymer as
shown in Scheme 1 [20].
Polyepichlorohydrin
(PECH)

p!TsCl
Pyridine

PECH!(OTs)2

NaN3
DMF

N3

O
N3

CH2N3
O
n

N3
N3

Scheme 1. Synthesis of GAPA.

The high viscosity attached with energetic plasticizers limits the amount of solid that can be loaded in
propellant formulations. In this regard, Rindone et al. have synthesized methylazide substituted acetals,
formals and ketals for their application as plasticizers [21]. It was found that such compositions have
improved propellant performance, high solid loading and better propellant processability.
Agarwal and co!workers have synthesized the energetic plasticizer bis(2!azidoethyl)adipate (BAEA)
from the starting material bis(2!chloroethyl)adipate as shown in Scheme 2 [22].
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KUMARI et al.

O
OH

HO

H2SO4, PhCH3
(90%)

OH (2 equiv.)

Cl

Cl

Cl

O
NaN3 (72%), EtOH

O
O

N3

N3

O
Scheme 2. Synthesis of BAEA.

Drees et al. have synthesized and characterized four different new azido plasticizers to get good com!
patibility with azidopolymers [23]. These are EGBAA, DEGBAA, TMNTA and PETKAA; all are liquids
and their Tg lies in between 34C to 71C. These compounds have high chemical and thermal stability
also good plasticizing ability. In a test mixture with PolyNIMMO, the azido plasticizer EGBAA shows
promising results with respect to compatibility, stability and processability. Syntheses of all these com!
pounds follow this general Scheme 3.
O
HO

OH +

HO

O
PTSA

Cl

Cl

O
Cl

NaN3
DMSO

N3

N3

Scheme 3. General synthetic route to azido plasticizers.

Gore and co!workers have synthesized and characterized two new energetic azido esters named
TAAMP (1,3!bis(azidoacetoxy)!2!azidoacetoxymethyl!2!ethyl!propane) and BABAMP (1,3!bis(azi!
doacetoxy)!2,2!bis(azidomethyl) propane) that show good compatibility with azido polymeric binders
like GAP, copolymers of 3,3!bis(azidomethyl)oxetane (BAMO) and 3!azidomethyl!3!methyloxetane
(AMMO) [24]. They have low Tg, greater thermal stability, exothermicity as well insensitivity towards
impact and friction. Hence, there is a great scope for their applications in propellant formulations. Syn!
thesis of these two compounds again follows same steps, given in Scheme 4.
CH2OH
O
H3CH2C C CH2OH +
HO
CH2OH

Cl

CH2OH
O
+
N3H2C C CH2N3
HO
CH2OH

PTSA

Cl

CH2OCOCH2Cl
H3CH2C C CH2OCOCH2Cl
CH2OCOCH2Cl
PTSA

CH2OCOCH2Cl
N3H2C C CH2N3
CH2OCOCH2Cl

NaN3
DMSO

NaN3
DMSO

CH2OCOCH2N3
H3CH2C C CH2OCOCH2N3
CH2OCOCH2N3
CH2OCOCH2N3
N3H2C C CH2N3
CH2OCOCH2N3

Scheme 4. Synthesis of TAAMP and BABAMP.

Further studies were done with TAAMP and BABAMP towards their applications in triple base pro!
pellant [25]. It was found that incorporating BABAMP in triple base propellant resulted in an increase in
energy level albeit with higher flame temperature and also better mechanical properties. It was established
that propellant composition containing TAAMP and BABAMP shows better performance than DBP
containing compositions.
In order to raise the nitrogen content of the energetic plasticizer and improve the energy level of the
solid rocket propellant this novel azido ester plasticizers, 1,3!di(azidoacetoxy)!2,2!di(azidomethyl)pro!
pane (PEAA) was synthesized and characterized [26]. The synthesis process includes the esterification
and dehydration of chloroaceticacid and 2,2!bis(bromomethyl)!1,3!propanediol, and then, the interme!
diate product, 1,3!di(chloroacetoxy)!2,2!di(bromomethyl)propane (PEBC) is substituted to PEAA
(shown in Scheme 5).
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CH2OH
O
+
BrH2C C CH2Br
HO
CH2OH

CH2OCOCH2Cl
BrH2C C CH2Br
CH2OCOCH2Cl

PTSA

Cl

247

CH2OCOCH2N3
N3H2C C CH2N3
CH2OCOCH2N3

NaN3
DMF

Scheme 5. Synthesis of PEAA.

PEAA has a high nitrogen content of 47.73%. Physical properties like Tg, DSC and DTA results have
showed that PEAA is thermally stable and suitable candidate for energetic plasticizers in azido solid pro!
pellants. Carbon monoxide, carbon dioxide, nitrogen, hydrocyanic acid, methane and 2!methyl!1,3!
butadiene were identified as the main thermolysis products and only few cross linking products would
probably appear during the degradation.
Dave et al. [27] have described low molecular weight compounds substituted with multiple energetic
groups like azide, nitrato and nitro groups, which may be of high interest as energetic plasticizers and are
building blocks for energetic polymers. The novel polyazido compounds include 2!azido!2!azidomethyl!
1,3!diazidopropane, 2!azidomethyl!2!hydroxy!1,3!diazidopropane, 2!azidomethyl!2!nitrato!1,3!diaz!
idopropane, 2!azidomethyl!2!nitro!1,3!diazidopropane, 2,2!dinitro!1,3!diazidopropane, methallyl!
diazide, 1,3!diazidoacetone, 2!oximido!1,3!diazidopropane etc. These compounds are expected to be
very useful in novel energetic material compositions. The azido groups in these molecules were further
converted to triazole and tetrazole to prepare high nitrogen rich materials of interest for gas generator
applications. The ability of azido groups to undergo 1,3!dipolar cyclo!additions makes these polyazido
compounds useful starting materials for polymeric materials synthesis.
Malwade et al. have synthesized and studied the utility of diazidodiesters like BADEP, BADPP, and
BADBP as energetic plasticizers [28]. It was found that these compounds were stable up to 200C. These
plasticizers are insensitive to friction and also miscible in nitroglycerine. Similarly, Frankel et al. have pro!
vided a novel class of polyazido compound, tetra azido polyester, used as energetic plasticizer for gun and
solid propellants [29]. In order to explore new plasticizers, 2!methyl!2!nitro!1!azidopropane was synthe!
sized from 2!nitropropane by using hydroxymethylation, tosylation and azidation with sodium azide
(Scheme 6). This new plasticizer is a yellow oily liquid and decomposes at 206C, with solidifying point
no higher than 18C [30].
NO2
H3C

HCHO
KOH

CH3

NO2
H3C

OH

NO2

TsCl

CH3

H3C

NO2

NaN3

OTs

H3C

CH3

N3
CH3

Scheme 6. Synthesis of 2!methyl!2!nitro!1!azidopropane.

A new organic azide namely 1,9!diazido!2,2,8,8!tetranitro!4,6!dioxanonane has been synthesized

from its appropriate bis(trinitroethyl)formal Scheme 7). The desired product was achieved by a three step
process. The product has better thermal stability, detonation velocity and sensitivity as compared to its
precursor bis(trinitroethyl)formal [31].
NO2
O2N

NO2
O

NO2

NO2
N3

HO

NO2

N3
NaN3
DMSO/H2O

NO2
O

NO2
OH
NO2
TsCl/Py

NO2

NO2
NO2

NO2

NO2

NO2

N3

NO
NO2 2

(i) H2O2/NaOH
(ii) CH2O/H3+O

NO2
TsO

O
NO2

OTs

NO2
O

OTs
NO2

NO2

Scheme 7. Synthesis of 1,9!diazido!2,2,8,8!tetranito!4,6!dioxanonane.

Another novel class of azido alcohols having difluoro alkyl group was synthesized by Koppe et al. [32].
They have synthesized an energetic alcohol, 2!azido!2,2!difluoroethanol for its use as plasticizer
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(Scheme 8). The presence of fluorine group is to stabilize the azide group, lower the melting point and also
lower the vapor pressure relative to fluoroalkyl groups.
O
H3C

O
Br

NaN3
DMSO

H3C

N3

NaBH4

HO

N3

Scheme 8. Synthesis of 2!azido!2,2!difluoroethanol.

Evaluation of different plasticizers for LOVA gun propellants has been carried out by Sanghavi and co!
workers [33]. They have shown that low molecular weight GAP (~500) is a potential plasticizer for LOVA
propellants [34]. Further Sanghavi et al. have studied a combination of inert and energetic plasticizers for
LOVA to see its impact on energetics, vulnerability and mechanical properties [35].
RDX based propellant with CA and NC as binder plasticized by triacetin and GAP and dinitrotoluene
were evaluated for low vulnerability ammunition. A combination of inert and energetic plasticizers was
studied to evaluate their impact on energetics, vulnerability and mechanical properties of propellants [36].
According to Khire and Singh, LOVA gun propellant based on CA and HTPB and their mixture as
binders with 6% GAP as plasticizer produce high figure of insensitivity of the order of 3040 [37]. Other
energetic plasticizers reported for LOVA propellants include BDNPF/A, alkyl NENAs, DANPE,
TMETN, TEGND, DEGDN, BTTN.
Excessive flame associated with a propellant is detrimental as the gun; rocket or missile involved with
it can be detected. A novel solution to this effect was reported by Witucki et al. [38] whereby they have syn!
thesized 6!azidohexyl!6!azido hexanoate (AHAH) (Scheme 9) which is effective in overcoming the prob!
lem of flames in exhaust gases during the operational phase. AHAH is considerably more attractive than
conventional plasticizers such as triacetin, DBP or FEFO.
O

Br

Cl

NaN3
DMF

N3

N3

Scheme 9. Synthesis of 6!azidohexyl!6!azido hexanoate.

4.2. Nitrate Ester Based Plasticizers

Nitrate ester based plasticizers are like nitroglycerine (NG), trimethylol ethane tri nitrate (TMETN),
ethylene glycol dinitrate (EGDN), diethylene glycol dinitrate (DEGDN), triethylene glycol dinitrate
(TEGDN), 1,2,4!butane triol trinitrate (BTTN), 1,2!propyleneglycol dinitrate (PGDN), pentaerythritol
trinitrate (PETRIN), pentaerythritol tetranitrate (PETN) etc. Molecular structures of few nitrate ester
based plasticizers are given in Figure 3.
Nitrate esters are organic esters of nitric acid. The ONO2 bond of nitrate ester is weaker than C
NO2 and NNO2 bonds which results in higher sensitivity to mechanical and thermal stimuli. Nitrate
esters exhibit excellent plasticizing properties with a variety of polymeric binders and sufficiently high
energetic performance for many propulsive and explosive applications. A significant drawback of these
compounds is their poor thermal stability and high shock sensitivity, which make composition containing
such plasticizers dangerous to handle and extremely prone to accidental detonation.
The first energetic plasticizer used in the propellant industry was nitroglycerine (NG). It was first pre!
pared by Ascanio Sobrero in 1846 by adding glycerol to a mixture of sulphuric acid and nitric acid as shown
in Scheme 10.
OH
HO

OH
Glycerol

H2SO4
HNO3

O2N

ONO2
O

NO2

NG
Scheme 10. Synthesis of NG.

It is one of the most important and frequently used components for gelatinous commercial explosives.
It provides a source of high energy in propellant compositions, and in combination with nitrocellulose and
stabilizers it is the principal component of explosive powders and solid rocket propellants. It is insoluble
in water but readily dissolves in most organic solvents and in a large number of aromatic compounds and
forms a gel with nitrocellulose. It is very sensitive to friction and explodes above 200C. NG is incorpo!
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O2N

ONO2
O

CH3
NO2

O2N

NO2

O2N

NG

NO2

BTTN

O2N

NO2

O2N

ONO2
O

CH2ONO2
NO2
O
CH2ONO2

HO

NO2

PGDN

NO2

NO2

TEGDN

DEGDN

EGDN

H3C

O
CH2
ONO2
TMETN

ONO2

O2N

249

O2N

PETRIN

CH2ONO2
O
NO2
CH2ONO2
PETN

Fig. 3. Nitrate ester based plasticizers.

rated to ensure superior strain capability at subzero temperature and also to facilitate ease of processing of
NCNG based propellants [3].
In order to overcome the problem of shock sensitivity another nitrate ester containing plasticizer like
trimethylol ethane trinitrate (TMETN), being a solid at sub!zero temperature, is used in combination
with BTTN or DEGDN/TEGDN. It has advantages of being relatively insensitive to impact and friction.
TMETN has been synthesized by nitrating 1,1,1!trimethylol ethane at 10C with mixed acid (45% HNO3
and 55% H2SO4) in 93% yield [39]. Shinohara [40] has claimed through a Japanese patent that high
mechanical strength for an NCNG based propellant system at low temperatures can be obtained by part
incorporation of TEGDN and TMETN.
Camp et al. [41] have described an energetic plasticizer for double base propellants comprising of a
mixture of sorbitol tetra!, penta!, and hexa!nitrate (MNS) and polyolpolynitrate (PPN) selected from the
groups consisting of DEGDN, TEGDN, NG, and mixture of these. The advantages of these sorbitol
nitrate mixtures are significant. Their molecules are large and capable of hydrogen bonding. Hence there
is little tendency for sorbitol nitrates to migrate out of the propellant composition. Their molecular
arrangement gives a high density plasticizer as 4% denser than NG. These advantages combined with the
high energy content and low cost make sorbitol nitrate mixtures an excellent energetic plasticizer if the
plasticizing capacity of this mixture is increased to a practical level. Hartman [42] has used mixed plasti!
cizer consisting of NG and BTTN in polyethylene glycol (PEG) prepolymer propellant formulation con!
taining 70!80% solid loading and found non!embrittlement on long temperature cycling (54 to 12C).
To overcome the shock sensitivity associated with NC based gun propellants, Consaga et al. [43] have devel!
oped a novel formulation comprising of solid nitrate ester of cyclodextrin or mixtures of cyclodextrin and
organic nitrate ester plasticizer. These energetic mixtures have applications in gun propellants or explosives.
2,2!Dinitro!1,3!bis(nitrooxy)propane (NPN) is an attractive energetic plasticizer because of its high
oxygen balance and low Tg. Wingborg et al. [44] have studied the ability of NPN to lower the glass transi!
tion temperature of uncured PolyNIMMO as compared other energetic plasticizer like BDNPA/F and
butyl!NENA. However, the thermal stability has been not so encouraging and efforts are on to find a suit!
able stabilizer for NPN.
Urenovitch [45] has described production of LOVA propellants utilizing mixtures of alkyl NENAs and
bis(2!nitroxyethyl)nitramine (DINA) with nitrocellulose. The above composition resulted in lowering of freez!
ing point, decrease in sensitivity, but surpassing energy output realized with currently used NGNC mixtures.
4.3. N!Nitramine Based Plasticizers
N!Nitramine based plasticizers are like alkyl nitrato ethyl nitramine plasticizers (NENA) like methyl!
NENA, ethyl!NENA, propyl!NENA, n!butyl!NENA, pentyl!NENA etc. Molecular structure of
NENA is given in Fig. 4.
Nitramine based plasticizers are an important sub class of energetic plasticizers. The nitroethyl nitra!
mines (NENAs) have excellent plasticizing characteristics to provide high physico!chemical properties to
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N
NO2

NO2

R = Me, Et, Pr, isoPr, n!Bu, n!C5H11

NENA
Fig. 4. Nitramine based plasticizers.

the gun and rocket propellants composition. Significant studies have been reported towards the applica!
tion of these plasticizers in gun and rocket propellants.
Sikder and co!workers [46] have reported a large scale synthesis of nitroethyl nitramines (NENAs),
further they have studied the variation of the compositions of NENAs on the energetic of rocket propel!
lant. Synthesis of n!BuNENA consists of two steps (a) condensation of n!butyl!bromide with ethanola!
mine and (b) nitration of n!butyl!ethanolamine as shown in Scheme 11.
OH

Br + H2N

NaOH
H2O

OH

N
H

HNO3 (98%)
Ac2O, ZnCl2

ONO2

N
NO2

Scheme 11. Synthesis of n!butyl(nitroethyl)nitramine.

As compared to DEP based propellants, n!BuNENA based propellants produce an increase in the spe!
cific impulse from 238 to 246 sec for CMDB class of propellant and 221 to 233 sec for EDB propellant.
The cal!val of propellant formulation increases from 4708 to 4750 J/g for CMDB propellant and from 4549 to
4742 J/g for EDB propellant. Thus, results obtained with n!BuNENA indicate enhanced burning rate, higher
cal!val and superior mechanical properties for propellant formulation. Further, thermal stability and compati!
bility of the n!BuNENA with propellants ingredients have been found to be well within the acceptable limits.
Sitzmann et al. [47] have investigated the insight into the Bu!NENA synthesis pathway. They have
identified potential intermediates and by!products formed during Bu!NENA synthesis (Scheme 12).
These include nitrate salts, acetate ester, nitramine alcohol and free nitrate ester. Further they have also
studied the process of consumption of acetyl nitrate to limit its accumulation.
NO2
N

Bu
ONO2
N!Butyl NENA

NO2
N

Bu
OAc
N!Butyl!N!nitroethanolamine,
acetate ester

Ac2O, 1mole % AcCl

H
N

Bu

OH

98% HNO3

N!Butylethanol!
amine

Bu

H
N

OH

NO3

N!Butylethanol!
amine nitrate salt

Bu

H
N

ONO2 NO3

N!Butyl!N!(2!nitroxyethyl)!
amine nitrate salt

1) CH2Cl2, H2SO4
2) 98% HNO3
3) H2O, Na2CO3

H
N

98%

Bu
ONO2
HNO3
N!Butyl!N!(2!nitroxyethyl)amine
(free amine nitrate ester)
MgO, H2O

Bu

H
N

ONO2

NO3
N!Butyl!N!(2!nitroxyethyl)!
amine nitrate salt
(nitrate salt)

NO2
N

Bu
OH
N!Butyl!N!nitroethanolamine
(nitramine alcohol)
Scheme 12. The Bu!NENA synthesis pathway.
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251

Wide range of studies have been done on the synthesis of Bu!NENA, however a detailed study on
incorporating NENA in single, double and triple based formulations were done by Chakraborthy et al.
[48]. They have found that introducing Bu!NENA in a single base propellant resulted in gain of energy,
without changing the burning rate coefficient. In case of double!base propellant, replacement of DEP
with Bu!NENA resulted in increased energy and comprehensive strength. For triple base propellant, its
replacement resulted in significant decrease in sensitivity and better mechanical properties.
By following the trend of replacing inert plasticizer with energetic plasticizer, Damse et al. [49, 50] have
used Bu!NENA in place of dioctyl phthalate (DOP). They have found by varying the percentage of
NENA in RDX based gun propellant, superior ballistic performance like higher force constant are
obtained as compared to DOP. In addition, the thermal stability increased, and relatively lower sensitivity
was found. Further the composition exhibited higher flame temperature as compared to DOP. Hence they
have envisaged Bu!NENA as a suitable replacement of DOP. However, in order to find a solution to the
high flame temperature associated with NENA, in gun propellant, they have partially incorporated guani!
dinium!5!aminotetrazole (GA) in place of RDX. It was found that the flame temperature decreased mar!
ginally without affecting the force constant much.
Khire & Singh have reported that LOVA gun propellants can be developed for insensitive munitions
(IM) by using mixtures of n!BuNENA as an energetic plasticizer along with cellulose acetate (CA) or
hydroxyl terminated polybutadiene (HTPB) as inert binder [51]. Results obtained by these authors indi!
cate that flame temperature in the range of 2700 to 3320 K resulting in force constant in the range of 1100
1225 J/g. Further they have found that mechanical properties of CA based propellants are better than that
of HTPB based.
Bu!NENA having nitrate and ester moiety is prone to auto catalytic decomposition. A stability analysis
carried out by Wilker [52] has indicated that it is a moderate stable compound and does not require addi!
tional stabilizer. The stability and sensitivity of n!BuNENA as compared with NG, n!BuNENA is much
higher, but like all nitrate esters, it suffers from an inherent instability due to the low ONO2 bond energy.
The decomposition is accompanied by moderate heat generation and gas production. It is also accelerated
by the presence of moisture.
It is important that any propellant ingredient should have sufficiently low volatility to permit long!term
storage of the propellant under a variety of conditions without appreciable changes in composition and
properties. In this regard, Cartwright [53] has measured the volatility of NENA and other energetic plas!
ticizer for their applications in propellants. It was found that volatility of NENA was less than NG and
DEGDN. The results are optimistic for the use of NENA as plasticizer. Another important consideration
while formulating propellant is their integrity at low temperature. In this regard, Flanagan et al. [54] have
reported that energetic azido eutectic propellant composition based on 1,5!dinitrato!3!nitrazapentane
(DINA) and 1,5!diazido!3!nitrazapentane having a eutectic freezing point below 25C. It was found
that when this eutectic mixture combined in a propellant composition along with HMX, GAP and AP
resulted in equivalent Isp to NG based system.
Adams Jr. et al. have prepared 1!fluoro!1,1,5!trinitro!3!oxa!5!aza!hexane (nitro substituted ethers) as
energetic plasticizers [55] (Scheme 13). This compound has fundamental properties similar to those of
FEFO and NG but thermally and chemically more stable than NG and less volatile. It is believed that this
compound will have better plasticizing properties than FEFO due to presence of different energetic moi!
eties, and shall be able to provide better wetting to nitramine fillers by the binder of which it is a compo!
nent. In addition to being a useful plasticizer in its own right, the compound can be used in admixture with
other plasticizers to provide combinations of low melting point.

H3C

NO2
N
OH

O
H3C

Cl

H3C

NO2

NO2
N
O

CH3

OH
NO2

H3C

NO2
N
O

NO2
C
NO2
F

Scheme 13. Synthesis of 1!fluoro!1,1,5!trinitro!3!oxa!5!aza!hezane.

Adam Jr. et al. have prepared bis(2!nitro!2!azapropyl)ether (Scheme 14) with potential plasticizing
properties for polymers like CAB, NC and acrylate elastomers [56]. This plasticizer contributes to lower!
ing of flame temperature.
O
NO2
N
OH + F C
O
3
H3C

CH3

N
NO2

CH3CN

H3C

NO2
N
O

Scheme 14. Synthesis of bis(2!nitro!2!azapropyl) ether.

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Klaptke et al. have used the byproducts formed during the synthesis of RDX as starting materials for
the synthesis of linear energetic nitramines, namely!1,3!diacetoxy!2!nitro!2!azapropane and 1,7!diace!
toxy!2,4,6!trinitro!2,4,6!triazaheptane [57] (Scheme 15). These compounds can be used as energetic
plasticizers to propellant charges.
NO2
N
N
N
N
N
Urotropine

O2N

HNO3
Ac2O

AcO

RDX

AcO

NO2

N
OAc + AcO
NO2

N
N
OAc
NO2 NO2
N
N
N
OAc
NO2 NO2 NO2

HCl

Cl

HCl

N
Cl
NO2

Cl

N
N
N
Cl
NO2 NO2 NO2

NaN3

N3

NaN3

N
N3
NO2
DANP

N3

N
N
N
N3
NO2 NO2 NO2
DATH

Scheme 15. Synthesis of DANP and DATH.

4.4. Nitro Aliphatic Plasticizers

Nitro aliphatic plasticizers which contains poly nitro organic formal/acetal are like bis(2,2!dinitropro!
pyl)acetal (BDNPA), bis(2,2!dinitropropyl)formal (BDNPF), bis(2!fluoro!2,2!dinitroethyl)formal
(FEFO), bis(2,2,2!trinitroethyl)formal (TEFO), 2,2!dinitropropyl!2,2,2!trinitroethylformal (TNEPF),
2,2!dinitropropyl!2,2!dinitrobutylformal (DNPBF), bis(2,2!dinitrobutyl)formal (BDNBF) etc. Molec!
ular structures of few nitro aliphatic plasticizers are given in Fig. 5.
Hammel et al. [58] have described the synthesis and characterization of poly nitro aliphatic plasticizers
for propellants, in view of their low density and high oxygen content. These plasticizers are effective in
decreasing solid loading without any penalty on ballistic performance. Equal weight mixture of bis(2,2!
dinitropropyl)formal/acetal (BDNPF/A) containing 0.16% phenyl!!naphthyl amine inhibitor is as a
promising candidate. This nitro!plasticizer mixture is compatible with all common solid propellant ingre!
dients. Low modulus at cold temperature (54C) can be obtained with non!explosive plasticizer like iso!
decyl pelargonate (IDP) in composite propellants containing APHTPBAl. The preparation of
BDNPF/A can be achieved by ShechterKaplan method [59], as shown in Scheme 16.
NO2

Paraformaldehyde
H2SO4

NO2

1) NaOH (aq)

H3C

NO2

2) NaNO2, 2AgNO3
3) AcOH, CH2O
80%

H3C

H3C

NO2
O

NO2

CH
NO2 3

BDNPF

OH
NO2

NO2
Paraacetaldehyde
BF3 Et2O

H3C

NO2
O

NO2

O
CH3

CH
NO2 3

BDNPA
Scheme 16. Synthesis of BDNPF/A.
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NO2
H3C

NO2
O

NO2

NO2

CH
NO2 3

H3C

NO2
H3C

CH3

NO2
CH3

NO2

H3C

NO2

H3C

NO2

CH3
NO2

BDNBF

NO2
O

NO2

DNPBF

NO2

CH
NO2 3

BDNPA

NO2

NO2

NO2
O

NO2
O

BDNPF

253

NO2

NO2
NO2

O2N

NO2
O

NO2
NO2

NO2

TNEPF

NO2
F

NO2
O

NO2

TEFO

F
NO2

FEFO

Fig. 5. Nitro aliphatic plasticizers.

Thiokol Corporation has developed an environment friendly process which overcomes the use of chlo!
rine [60] as shown in Scheme 17.

H3C

NO2

K3Fe(CN)6
Na2S2O8
NaNO2

NO2
H3C

NO2

NaOH
HCHO

NO2
H3C

NO2
H3C

OH
NO2

NO2

NO2
O

NO2

CH
NO2 3

H3C

NO2
O

NO2

O
CH3

CH
NO2 3

BDNPF/A
Scheme 17. Synthesis of BDNPF/A.

According to Gore et al. [61], replacement of non!energetic plasticizer DEP by eutectic mixture of
BDNPF/A produced positive effects on burning rates and Isp of RDX/AP based CMDB propellants.
Addition of BDNPF/A led to overall increase of 946% in burning rates, and 510 sec in Isp. However,
activation energy was 102 2 kJ/mol for both AP/DEP and AP/BDNPF/A systems. Global kinetics of
the BDNPF/A plasticized propellants suggest that BDNPF/A catalyzes reactions near surface of CMDB
propellant system.
Behrens and co!worker have used mass spectra and ion cyclotron resonance to estimate various prop!
erties of BDNPA and BDNPF. It was found that most of the parts are same but the relative abundance of
some ion fragments is different. Using STMBMS they have found that BDNPA has higher enthalpy of
vaporization and higher vapour pressure. There exist variation in decomposition of BDNPA and BDNPF
as BDNPF decomposes slowly as compared to BDNPA [62].
Adolph [63] has synthesized polynitro organic formals like bis(2!fluoro!2,2!dinitroethyl)formal
(FEFO) and BDNPF as energetic plasticizers in propellant and explosives compositions (Scheme 18).
FEFO has high energy content, but is volatile and toxic and has a relatively higher melting point. BDNPF
is comparatively low in energy and has higher melting point, requiring the use of an energy!decreasing
melting point depressant. Mixtures of FEFO and BDNPF can be used to obtain a lower melting point and
intermediate levels of energy and volatility.
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NO2
H3C

NO2
OH

NO2

NO2
H3C

OH
NO2

+ F

NO2

NO2

O
+

7580%
H2SO4

AlCl3

H3C

O
NO2

H3C

Cl

TiCl4

NO2

F
NO2

NO2

OH
NO2

NO2
O

NO2

NO2

OH

H3C

NO2
O

NO2

F
NO2

Scheme 18. Synthesis of FEFO.

Adolph et al. [64] have described binary and ternary mixtures of BDNPF, bis(2,2,2!trinitroethyl)for!
mal (TEFO), and 2,2!dinitropropyl!2,2,2!trinitroethylformal (TNEPF) as plasticizers for energetic pro!
pellant compositions. The general advantages of the binary and ternary mixtures of TNEPE, TEFO and
BDNPF are low volatility and good thermal stability (better than NG, BTTN) coupled with a relatively
high energy content (higher than BDNPF/A, DEGDN, TMETN). These mixtures can be advanta!
geously used in place of BDNPF/A, TMETN, or BTTN for many propellant applications. They are par!
ticularly suitable for plasticizing polymers like cellulose acetate butyrate (CAB), NC, polyethylene glycol
(PEG), and polycaprolactone (PCP).
In continuation with their research on energetic stable plasticizer, Adolph [65] further invented
another interesting compound 2,2!dinitrobutyl!2,2!dinitropropyl formal (DNBPF) and also energetic
plasticizer having 1:1 eutectic mixture of 2,2!dinitrobutyl 2,2!(dinitropropyl)formal and bis(2,2!dinitro!
propyl)formal (BDNPF). These plasticizers have better thermal and chemical stability as compared to
BDNPF/A.
Adolph et al. [66] have also described energetic plasticizers 3,3!bis(difluoroamino)!1,5!(dini!
trato)pentane (BFDNP) which has Tg of around 87C and onset decomposition starts at 186C and is
used an improved plasticizer with excellent performance potential.
A usual problem encountered during formulation of eutectic mixture of BDNPF/A is to prevent it
from crystallization. In this regard, Cho et al. [67] have invented a eutectic mixture comprising of BDNPF
and BDNPDF wherein BDNPDF prevents crystallization of BDNPF out of the mixture. The process is
efficient and economical. Further they have developed a similar eutectic mixture having bis(2,2!dinitro!
propyl)formal, 2,2!dinitropropyl!2,2!dinitrobutylformal and bis(2,2!dinitrobutyl)formal [68].
4.5. Nitro Aromatic Plasticizer
Nitro aromatic plasticizer is K10 also known as Rowanite 8001. Molecular structure of K10 plasticizer
is given in Fig. 6.
Among nitro aromatic plasticizers K 10 is the most common. It consists of a mixture of 2,4!dinitroethyl
benzene and 2,4,6!trinitro!ethylbenzene in 65:35 ratios and is a clear, yellow/orange liquid. It is manu!
factured by Royal Ordnance in the UK [12, 69].
4.6. GLYN Dimer Plasticizer
GLYN dimer plasticizer (derivative of glycidyl nitrate). Molecular structure of GLYN dimer is given in
Fig. 7.
GLYN dimer plasticizer GLYN dimer has been prepared for plasticization of polyether binder systems
such as polyGLYN and PolyNIMMO. It is prepared by end capping a 1,4!butanediol spacer unit with
GLYN, and then nitrating the terminal hydroxyl groups (Scheme 19). Nitration increases both oxygen
balance and energy content and prevents unwanted reaction of plasticizer with isocyanate crosslinking
agent. It is normally a mixture of oligomers which has a low Tg and impact sensitivity compared with
nitrate esters such as BTTN and TMETN [12], [69].
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Et

255

Et
NO2

O2N

NO2

NO2

NO2
(35%)

(65%)

Fig. 6. Nitro aromatic plasticizer.

O2N

ONO2
O

NO2

ONO2
GLYN Dimer
Fig. 7. GLYN dimer plasticizer.

OH + O

HO

NO2

1) End capping
2) Nitration

O2NO

ONO2
ONO2

ONO2

Scheme 19. Synthesis of GLYN dimer.

Willer et al. have described the synthesis and applications of nitrated poly(glycidyl nitrate) (PGN) oli!
gomer as a plasticizer, to be used in propellants and other energetic compositions [70] (Scheme 20). This
PGN plasticizer offers a number of advantages over traditional nitrate ester plasticizers (TEGDN,
TMETN, BTTN etc.) like excellent miscibility with normal molecular weight PGN, low volatility, low Tg
as compared to normal molecular weight PGN, decreased plasticizer mobility and excellent enthalpies of
combustion and explosion characteristics.

HOCH2CH2OH

NO2

HBF4
CH2Cl2

NO2
O
CH2
HO

HNO3

O
3
CH2

O
NO2

CH2

Ac2O
CH2Cl2

NO2
O
CH2
O2N O

O
3
CH2

PGN

O
NO2

CH2
2

Scheme 20. Synthesis of PGN.

4.7. Oxetane Plasticizers

Oxetane plasticizers are like linear nitratomethyl(methyl)oxetane (NIMMO) oligomers. Linear
NIMMO oligomers (consisting of 110 monomers), having lower Tg than the cyclic NIMMO. Molecular
structures of oxetane plasticizers are given below in Fig. 8.
The most promising energetic plasticizers for use with nitrato substituted polyethers appear to be
NIMMO oligomer and GLYN dimer. Linear NIMMO oligomers (110 monomer units) are used as plas!
ticizer in polyNIMMO binder system. In order to remove the terminal hydroxyl groups, and prevent
unwanted reaction with the isocyanate crosslinking agent, oligomeric NIMMO has been further nitrated
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which also increases the oxygen balance and energy of binder system [12, 69, 71]. Synthesis of this com!
pound is shown in Scheme 21.
ONO2
HO

O
CH3

+ O

>3 mol N2O5

CH3

ONO2

ONO2

ONO2

O2NO

CH2Cl2

CH3

NO2

+ ON
2

O
CH3

NO2

Scheme 21. Synthesis of linear NIMMO.

4.8. Miscellaneous Plasticizers

Miscellaneous EPs not covered above are like 1,5!diazido!3!nitrazapentane (DANPE), 1,5!dinitrato!
3!nitrazapentane (DINA), 1,2,3!tris(1,2!bis(difluoroamino)ethoxy)propane (TVOPA), 2,2!bis(difluo!
roamino)!5!dinitropentyl formal (SYFO), 2,2!bis(difluoroamino)!1,3!bis(fluorodinitroethoxy)propane
(SYPE), 3,3!bis(difluoroamino)!1,5!dinitratopentane (BFDNP), 2,2!dinitro!1,3!bis(nitrooxy)propane
(NPN), bis(2!nitroxyethyl)nitramine, 1!fluoro!1,1,5!trinitro!3!oxa!5!azahexane, dinitro!diaza!alkanes
(DNDA!57), bis(2,2!dinitropropyl)nitramine (BDNPN) etc. which have found application for develop!
ment of advanced gun and rocket propellants of higher force constant. In addition, 2,4!dinitro!2,4!diaza!
6!nitrohexane, 1,5!diazido!3,3!nitroazapentane and 2,2!dinitro!1,3!propanediol diformate (A!diol!difor!
mate or ADDF), 6!azidohexyl!6!azidohexanoate (AHAH), nitrated PGN oligomer, hexakis(2!nitroxy!
ethyl)melamine etc. have also been developed and used to obtain high performance energetic materials.
Molecular structures of few plasticizers are given below in Fig. 9.
Several plasticizers having other energetic functional groups have been summarized as miscellaneous
plasticizers. Compounds containing functional groups such as nitrocarbamate, diformate, difluoroamino,
dinitro methanediamine, melamine, and ether trinitrate used as energetic plasticizers are described below.
Frankel et al. have synthesized a novel family of azido nitrocarbamates and showed their utilization as
energetic liquid plasticizers for advanced solid propellant compositions [72]. In this context, they have
found that 1,3!di!diazido!2!propyl!N!trinitropropyl carbamate (DANTC) extremely effective in over!
coming the problem of smoke in the exhaust gases produced during the operational phase of a solid pro!
pellant composition. DANTC possesses physical properties that make more useful than FEFO.
Vicinal and geminal difluoroamino energetic plasticizers such as 1,2,3!tris(1,2!bis(difluoroamino)!
ethoxy)propane (TVOPA), 2,2!bis(difluoroamino)!5!(dinitropentyl)formal (SYFO), and 2,2!bis(difluoroam!
ino)!1,3!bis(fluorodinitroethoxy)propane (SYPE) are synthesized for aluminized solid propellants [62, 73, 74].
The nitrate ester containing plasticizers like NG suffer from the fact that they are shock sensitive in
nature. In the quest of synthesizing a plasticizer containing both the above mentioned groups but greater sta!
bility and shock sensitivity, Highsmith et al. have synthesized a novel plasticizer 2,2!dinitro!1,3!pro!
panediol!diformate (A!diol!diformate or ADDF) [75] as shown in Scheme 22. ADDF can be mixed with
propellants and explosives for obtaining better performance and incorporating shock insensitive properties.
O

NO2
HO
NO2

OH + H C
3

O
O

Pyridine
CH2Cl2

O
H

NO2
O

NO2
Scheme 22. Synthesis of ADDF.

CH2ONO2
CH3

Cyclic NIMMO

CH2ONO2
OH
CH3 n

Linear NIMMO oligomer

Fig. 8. Oxetane plasticizers.

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ENERGETIC PLASTICIZERS FOR GUN & ROCKET PROPELLANTS

F2N

NF2

O
O

F2N

NO2

NF2

NF2

NF2 F

NO2

TVOPA

O2N

NF2

N
NO2

NO2

N3
N

O
NO2

NF2

N3

NO2

BFDNP

O
H

O2N

H3C

NO2

F3C

NO2

N
O
NO2

N3
N

N
R

1,5!diazido!3,3!
nitroazapentane

H3C

NO2
N
O

NO2
N
CH3

N3
CH3

H3C

NO2
O

NO2

F
NO2

1!Fluoro!1,1,5!trinitro!
3!oxa!5!azahexane

CH2ONO2
O
O
O
O2N
CH2
n
CH2ONO2

Nitrated PGN Oligomer

NO2

NO2 N3

NO2

N3

2,4!dinitro!2,4!diaza!
6!nitrohexane

Fig. 9. Miscellaneous plasticizers.

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NO2

Bis(2!nitro!2!azapropyl) ether

NO2
2!Nitro!2!azapropyl
trifluoroacetate

R = N(CH2CH2ONO2)
Hexakis(2!nitroxyethyl)!
melamine

N3
N3

N
N

H3C

N3

CH2N3
N3

DANTC

N3

NO2
2!Nitro!2!azapropyl acetate

NO2
ADDF

F
NO2

NO2

NO2
CH3

N
O
NH2

CH3
N
NO2
DMED

H3C

1!Fluoro!1,1,5!Trinitro!
3!oxa!5!aza hexane

NO2
NO2

NO2
N

NO2
O

H3C

NF2

NO2

DMMD

NF2

Bis(2!nitroxyethyl) Nitramine

NO2 NO2
N
N
CH3
H3C

NO2

NF2

O 2N

N3

DANPE

NPN

NF2

SYFO

N3

NO2

O2N

NF2

F O2N
NO2
NO2

NF2

DINA

SYPE

O2N

NO2

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O
AHAH

N3

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KUMARI et al.

Gilbert has synthesized an inert plasticizer hexakis(2!nitroxyethyl)melamine by nitration of hexakis(2!

hydroxyethyl)melamine which may have applications in gun propellant. The precursor hexakis(2!hydrox!
yethyl)melamine was synthesized by reacting cyanuric chloride with diethanolamine followed by nitration
as shown in Scheme 9 [76].
R1

Cl
N

H
N

HO

Cl

R1

Cl

R1 = HO

OH

NaOH

R2
N
R1

HNO3

R2
N

OH ; R2 = O2NO

N
R2

ONO2

Scheme 23. Synthesis of hexakis(2!nitroxyethyl)melamine.

Another novel plasticizer N,N!dimethyl!methylenedinitroamine (DMMD) also known as N,N!dimethyl!

N,N!dinitromethanediamine which does not degrade the polymer [77]. This plasticizer is used for nitrocellu!
lose. Beside its plasticizing ability, DMMD is also more stable and safe as compared to other plasticizers.
Carosino et al. have described an efficient method to produce high energy plasticizer composition suit!
able for crosslinked double based rocket propellants [78]. The synthesis of desired plasticizer commenced
by the reaction of glycerol and ethylene oxide by use of an initial catalyzed reaction to obtain intermedi!
ates which was further subjected to suitable conitrator feed. Steps of synthesis are shown in Scheme 24.

Step 1 3 HO

OH +

KHSO4

OH

HO

OH

O
OH

HO

Step 2

HO

OCH2CH2OH
O
GGE

HNO3/H2SO4

OH

O2NO

OCH2CH2OH
O
GGE

OH

OCH2CH2ONO2
O
ONO2

Glycerol glycol ether trinitrate

Scheme 24. Synthesis of GGE trinitrate.

The nitrate derivative of glycerol glycol ether, glycerol glycol ether trinitrate in combination with NG,
is found particularly suitable because of its high energy content and low volatility. Physico!chemical prop!
erties of a few selected energetic plasticizers are given in Table 2.
5. THEORETICAL EVALUATION ON THE PERFORMANCE OF ENERGETIC PLASTICIZER
Theoretical insight into the sensitivity of energetic materials can be obtained by using molecular orbital
and molecular dynamics methods. In this context, significant work has been done by Turker et al. [84].
They have carried out quantum chemical investigations of energetic plasticizer NENA and have found out
that the two types of NO2 groups (NNO2 (nitramine) and ONO2 (nitrato)) present in NENA, the
NO2 group bonded to the ester group is more likely to dissipate energy thermally or by negative electrical
charging than the nitramine NO2. Further they have found out that s!cis conformation of NENA is
slightly more stable than s!trans.
6. FUTURE SCOPE OF ENERGETIC PLASTICIZERS
The present domain of energetic plasticizers range from nitrate esters, azido compounds, azido esters
to N!nitramines. These plasticizers boost the performance of propellants. However the stability of these
energetic plasticizers is a major concern. The future research is directed towards finding low vulnerable
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259

Table 2. Important properties of energetic plasticizers*

Density,
g/cm3

Hf,
kcal/mol

Ecombn,
kcal/mol

Oxygen
balance, %

Nitroglycerine (NG)

1.60

83.97

368.4

+3.5

1,2,4!Butane trioltrinitrate (BTTN)

1.5

99

523

16

65.51

Trimethylol ethanetrinitrate (TMETN)

1.49

99.6

674

34.5

62.67

Triethylene glycoldinitrate (TEGDN)

1.3

149

823

66.6

Ethyl NENA

1.32

34

3549

67.0

Propyl NENA

1.26

37

4132

87.0

n!Butyl NENA

1.21

40

4630

104.0

80

Bis(2,2 dinitropropylformal/acetal
(BDNPF/A)

1.39

142.584
(BDNPF)/
158.268
(BDNPA)

Ethyleneglycol bis(idoacetate) (EGBAA)

1.34

167.36

Diethyleneglycol bis(azidoacetate)
(DEGBAA)

1.00

329

1081.07

100

63.3

Trimethylolnitromethane(triazidoace!
tate) (TMNTA)

1.45

230

1294.04

72

34.1

Pentaerythritol tetrakis(azidoacetate)
(PETKAA)

1.39

215

1714.76

89

35.4

Glycidyl azide polymer (GAP)

1.3

+27.86

121

45

Linear NIMMO

1.26

79.76

114

25

Oligomer GLYN (Glycidyl nitrate) dimer

1.38

188.6

61

64.9

Tris(azidoacetoxymethyl)propan
(TAAMP)

37.5

110.6

47.0

Bis(azidoacetoxy),bis(azidomethyl)pro!
pane (BABAMP)

+144.19

90.8

51.9

Name

796.26

Tg, C
68

51
(BDNPF)/
63
(BDNPA)

65.2

84.15

70.8

Notes: () means data not available, given values are reported in references, [19, 69, 79!83].
* The data are already available in the literature but are reproduced as evidence supporting these concepts.

and more stable energetic plasticizers. Also increasing trend is being observed to theoretically evaluate the
performance of an energetic plasticizer before commencing its synthesis.
7. CONCLUSIONS
It is evident from this review that energetic plasticizers like nitrate esters, azido compounds,
BDNPF/A, NENAs, GAP etc. have played very important and vital role in improving mechanical and
ballistics properties of gun and rocket propellants. In addition to reducing sensitivity (impact & friction),
they enhance burn rates, specific impulse, and force constant. Therefore, research continues to find out
better and superior energetic plasticizers, which are compatible with propellant ingredients, have less
migration to surface, reduce glass transition temperature and do not create ageing related problems. Thus,
there is tremendous scope for R & D work in this important area for the synthesis, characterization and
evaluation of energetic plasticizers in propellant industry. Studies on ageing behavior of advanced propel!
lants containing new energetic plasticizers are also of high technical importance.
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KUMARI et al.

Authors are thankful to Vice Chancellor, DIAT (DU), Pune (India), for granting permission to publish this
manuscript. Please add ER&IPR, DRDO, New Delhi is gratefully acknowledged for funding.Before DK
Thanks CSIR, in acknowledgement. DK thanks CSIR, New Delhi (India) for providing fellowship.
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