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10.1002/cplu.201800531
ChemPlusChem
FULL PAPER
Synthesis and Properties of 3-Azido-2, 2-bis (azidomethyl) propyl
2-azidoacetate: A Potential Azido Ester Plasticizer
Dr. Yinglei Wang*, Yajing Liu, Dr. Tingting Lu, Fulei Gao, and Dr. Baodong Zhao
Abstract: This study reports the synthesis and characterization of a
novel azido ester plasticizer 3-azido-2, 2-bis (azidomethyl) propyl 2-
azidoacetate (ABAMPA) with good yield and high purity. The density,
impact sensitivity, friction sensitivity, thermal decomposition
temperature and the glass transition temperature were 1.326 g·cm-3,
16 J, 324 N, 235.9 oC and -50.4 oC, respectively. The plasticizing
abilities effect of ABAMPA on glycidyl azide polymer (GAP) was
calculated by molecular dynamics, the solubility parameter difference
value was 1.7(J·cm-3)0.5, and the glass transition temperature of GAP
was reduced from -35 oC to -43 oC when the weight ratio of ABAMPA
and GAP was 50:50. Our compound exhibits high energy, remarkable
thermostability and good compatibility with GAP, which indicated that
it would have potential application in the explosive and propellant
formulations.
stability, lower sensitivity and glass transition temperature.[18-20]
Previous work have reported the synthesis and properties of
some energetic azido-ester plasticizers such as bis(2-azido-1-
(azidomethyl)ethyl)
malonate
(BAEM),
bis(2-azido-1-
(azidomethyl) ethyl) glutarate (BAEG), 1,3-bis(azidoacetoxy)-2,2-
bis(azidomethyl)propane (BABAMP) and triazidopentaerythrite-
12, 21-24]
acetat (TAP-Ac) (Scheme 1).[4,
However, the most
conspicuous drawback of these azido ester plasticizers is their
low level of nitrogen content, oxygen balance, density and energy.
Introduction
Plasticizer is one important ingredient in explosive and propellant
formulations. The function of plasticizer is to increase safety and
improve mechanical properties.[1-2] Ideal plasticizers should be
highly compatible with polymers, stable at high and low
temperatures, sufficiently lubricating over a wide temperature
range, insensitive to ultraviolet radiation, leaching and migration
resistant, inexpensive and should fulfill health and safety
regulations.[3-4]
Scheme 1. Some reported energetic azido-esters.
In this work, one novel nitrogen-rich azido ester plasticizer 3-
azido-2,2-bis(azidomethyl) propyl 2-azidoacetate (ABAMPA) was
designed and synthesized with two steps and fully characterized
1
by H NMR, 13C NMR, 14N NMR, 15N NMR, FTIR spectroscopy,
elemental analysis and differential scanning calorimetry (DSC).
The detonation properties, the solubility parameter and the glass
transition temperature of GAP and ABAMPA were also calculated
by using the molecular dynamics and the B3LYP functional with
the 6-31G* basis set.
Inert (non-energetic) and energetic plasticizers are all used
in propellant formulation.[5] However, inert plasticizers have the
disadvantage of reducing the energy output of the system.
Energetic plasticizers (EPs) are often preferred to inert
plasticizers because EPs perform
a dual task: retaining
reasonable sensitivity, suppressing chemical reactivity, and
ensuring a high thermal stability as one approaches oxygen
balanced materials, creating the densest material possible. In
order to increase the energy level of propellants, energetic groups
such as nitro-, di-fluoramino-, nitramino-, and azido-groups are
introduced into some molecular structures to design novel high
energetic plasticizers.[6-12]
Organic azido compounds are one of the application
prospect energetic plasticizers, which have the advantage of
delivering extra energy on combustion combined with minimum
smoke and good mixing compatibility with established energetic
binders, like glycidyl azide polymer (GAP) and poly(3-nitrato
methyl-3-methyloxetan) (polyNIMMO).[13-17] Compared with
general organic azido compounds, energetic azido-ester
plasticizers provided with better lubricant effect and thermal
Results and Discussion
Energetic properties
The structure formula, nitrogen content, oxygen balance (OB),
density, heat of formation (ΔHf), and detonation velocity (D) of
ABAMPA was listed in Table 1. The reliability of the adopted
methods to calculate these data has been proved by previous
studies.[25] For comparison, the calculated and experimental
detonation properties of other azido plasticizers such as TAP-Ac,
[24] , BAEM [4, 12] and BAEG [4, 12] are also summarized in Table 1.
As shown in Table 1, ABAMPA exhibits good density at 1.326
g·cm-3, which is higher than the other listed azido plasticizers.
Oxygen balance is an important parameter to identify the potential
of an energetic material as an explosive or oxidizer, and ABAMPA
has an negative oxygen balance of -92.52%, which is better than
the listed azido plasticizers expect BAEM. ABAMPA also has high
nitrogen content at 57.12%, which indicates that it can be used as
the N2 source of the gas generator.
[*]
Y. Wang, Y. Liu, T. Lu, F. Gao, B. Zhao
Applied Chemistry
Xi’an Modern Chemistry Research Institute
Zhangbadonglu 168, Xi’an, Shanxi 710065, China
E-mail: wangyl204@163.com
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