Azido Polymers-Energetic Binders For Solid Rocket Propellants.

MARCEL DEKKER, INC.
• 270 MADISON AVENUE • NEW YORK, NY 10016

©2003 Marcel Dekker, Inc. All rights reserved. This material may not be used or reproduced in any form without the express written permission of Marcel Dekker, Inc.
JOURNAL OF MACROMOLECULAR SCIENCEÕ

Part C—Polymer Reviews
Vol. C43, No. 4, pp. 505–545, 2003
Azido Polymers—Energetic Binders for

Solid Rocket Propellants
Bharti Gaur, Bimlesh Lochab, V. Choudhary, and I. K. Varma*
Centre for Polymer Science and Engineering,

Indian Institute of Technology Delhi,
Hauz Khas, New Delhi, India
CONTENTS
1. INTRODUCTION. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 506
2. PREPARATION OF AZIDO POLYMERS . . . . . . . . . . . . . . . . . . . . . . . 508
2.1. Polymerization of Glycidyl Azide (GA) . . . . . . . . . . . . . . . . . . . . . . 508
2.1.1. Derivatization of polyepichlorohydrin (PECH). . . . . . . . . . . 508
2.2. Direct Conversion of Epichlorohydrin to Glycidyl Azide
Polymer (GAP).. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 513
2.3. Simultaneous Degradation and Azidation of PECH and
Its Copolymers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 514
2.4. Block Copolymers of GAP . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 515
2.5. Polymerization of Azidomethyl Oxetanes . . . . . . . . . . . . . . . . . . . . . 515
2.6. Poly(allyl azide) (PAA). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 519
3. PHYSICAL PROPERTIES OF AZIDO POLYMERS . . . . . . . . . . . . . . . 520
4. CURING OF GAP . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 522
4.1. Curing Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 522
4.2. Cure Monitoring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 524
*Correspondence: I. K. Varma, Centre for Polymer Science and Engineering, Indian Institute
of Technology Delhi, New Delhi 110 016, India; Fax: 91-11-26591421; E-mail: ikvarma@
homail.com.
505
DOI: 10.1081/MC-120025976 1532-1797 (Print); 1532-9038 (Online)

Copyright & 2003 by Marcel Dekker, Inc. www.dekker.com
MARCEL DEKKER, INC. • 270 MADISON AVENUE • NEW YORK, NY 10016
506 Gaur et al.
4.3. Problems of GAP-Isocyanate Cure . . . . . . . . . . . . . . . . . . . . . . . . . 525

4.4. Characterization of Cured Network. . . . . . . . . . . . . . . . . . . . . . . . . 525
4.5. Curing of Azido Polymers with Dipolarophiles. . . . . . . . . . . . . . . . . 526
5. THERMAL BEHAVIOR OF AZIDO POLYMERS. . . . . . . . . . . . . . . . . 528
5.1. Uncured Azido Polymers—Linear and Branched . . . . . . . . . . . . . . . 528
5.2. Uncured BAMO And AMMO Polymer . . . . . . . . . . . . . . . . . . . . . . 532
5.3. Thermal Behavior of Cured Azido Polymers . . . . . . . . . . . . . . . . . . 533
6. PHOTODECOMPOSITION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 535
7. FORMULATIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 536
7.1. Plasticizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 536
7.2. Oxidizers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 537
7.3. Pyrolants. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 539
7.4. Ballistic Modifiers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 539
8. CONCLUSION AND FUTURE OUTLOOK . . . . . . . . . . . . . . . . . . . . . 540
ACKNOWLEDGMENT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 540
REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 540
Key Words: Energetic binders; Azide polymers; Poly(allylazide); Oxidizers;

Thermal behavior.
1. INTRODUCTION
High-energy solid rocket propellants are composite materials having a

binder [hydroxy terminated polybutadiene (HTPB)], high-energy additives
[e.g., ammonium perchlorate (AP)], and pyrolants (metallic powder). HTPB is an
inert binder, which has been used in cast-cure propellant systems. Substitution of
HTPB by a more energetic binder may lead to an enhancement in performance of
such propellants.
Ammonium perchlorate, the high-energy additive, has its own inherent disad-
vantages, as it produces chlorine rich combustion products (30%), which have
potential environmental implications.[1] Further, it produces white smoke trails,
which are disadvantageous for specific applications demanding smokeless plume.
Ammonium nitrate (AN) has long been considered a highly desirable oxidizer for
solid-fuel rocket propellants because of its extremely low cost, low sensitivity, low
signature, and absence of halogens. However, it has a crystalline phase stability
problem that causes unpredictable ballistic performance in some cases and cata-
strophic rocket motor failure in others. This has limited the use of AN without
the phase stabilizers.[2]
A new generation of propellants and explosives for missiles and space applica-
tion is being developed worldwide these days. The operational trends for future
applications of these energetic materials are to improve performance, satisfy insen-
sitive munitions, comply with environmental aspects, and reduce costs.
The use of energetic additives, mainly binders and plasticizers, is considered
to be one of the practical ways to improve the energy level and other
Azido Polymers 507
technical performances of solid propellants. Recent advances in propellants

research, therefore, are aimed at developing high energy binders which give better
performance than the commonly used HTPB and which are compatible with the eco-
friendly oxidizers ammonium nitrate (AN), hydrazinium nitroformate (HNF), or
ammonium dinitramide (ADN).
Azido polymers have attracted researchers’ attention for the past two decades
since the azido group contributes a positive heat of formation of 313–397 kJ/mol.
This is evident from a comparison of heat of formation of ethanol (278.5 kJ/mol)
and 2-azidoethanol, N3CH2CH2OH (þ104 kJ/mol). Compatible propellants with
acceptable physical properties could be formulated from azide-containing ingredi-
ents.[3] These polymeric azides include poly(glycidyl azide) (GAP) and its copoly-
mers, poly(bis-azidomethyl oxetane) [poly(BAMO)] and its copolymers, and
poly(azidomethyl methyloxetane) [poly(AMMO)].[4] These polymers contain azide
groups along the polymer chain as pendant groups, which make them highly
energetic. The exothermic scission of these –N3 bond releases energy of the
order 685 kJ/mol.[5] The GAP prepolymer is cured by reacting the terminal
hydroxy groups with isocyanates, as is done in the state-of-the-art hydroxy termi-
nated binder.[6,7] These propellants, in addition to being fuel rich, liberate large
amounts of carbon monoxide, and hydrocarbon on their burning, and are greatly
insensitive to impact, and provide high burn rates.
The traditional method used for propellant formulation is to mix liquid
GAP polymer (Mn<3000) (binder) with curing agents (diisocyanate) and chain
extender, trimethylol propane (TMP), high-energy additives, and metallic
powder. However, the energy output of such propellants will be significantly
reduced due to inert properties of diisocyanates and TMP. Another disadvantage
of isocyanate cured hydroxy terminated GAP is that the propellant would not
be recyclable, as the crosslinks are irreversibly formed covalent chemical bonds,
and thus recovery of energetic ingredients and binders is not possible. Therefore,
an elastomeric GAP with Mn>1.4 105 has been developed to overcome this
problem. The synthesis and use of recyclable thermoplastic elastomer (TPE)
based on azido polymers is gaining importance in the field of energetic binders.
An attractive approach to high energy, low sensitivity propellants involve the
use of energetic oxetane prepolymers. New gun propellants have been developed
which utilize the thermoplastic elastomer (TPE) [i.e., poly(3,3-bis(azidomethyl),
oxetane (BAMO)–3-azidomethyl-methyl oxetane (AMMO)] as the binder and the
energetic solid trimethylenetrinitramine (RDX). These TPE based propellants
have many desirable properties including the ability to be reused, recycled, and
reclaimed, an excellent balance of flame temperature and the performance.[8]
Oxetane TPE propellants can readily be mixed and extruded in a twin-screw
extruder without aid of any solvents.[9] These binders act as energy partitioning
agents by allowing an energetic formulation to maintain a constant energy level at
a lower solids percentage.[10]
Although considerable work has been done on high-energy azido plasticizers
(molecular weight 500) and binders, a comprehensive review dealing with the
state-of-the-art of these polymers has not been published. This article reviews the
synthesis, characterization, physicochemical, thermal, and mechanical properties of
polymeric binders containing pendant azido groups.
508 Gaur et al.
2. PREPARATION OF AZIDO POLYMERS
2.1. Polymerization of Glycidyl Azide (GA)
The starting monomer, GA is prepared by reacting epichlorohydrin (ECH) with

hydrazoic acid to give 1-azido-3-chloro-2-propanol, which is cyclized in the presence
of a base (Sch. 1).
The polymerization of glycidyl azide (GA) was then attempted to be carried out
using the carbocationic method. However, this procedure was unsuccessful as the
monomer was found to be unreactive.[3]
2.1.1. Derivatization of Polyepichlorohydrin (PECH)
An alternative route, based on the polymerization of ECH to polyepichloro-

hydrin (PECH), followed by the conversion of PECH to GAP by nucleophilic
displacement of chloride by azide is more successful. Linear or branched hydroxy
terminated polyepichlorohydrin has been prepared by ring opening polymerization
of the oxirane group in ECH in the presence of a diol (ethylene glycol) or a triol
(1,2,3-propane triol). Azido substitution reaction has been accomplished by reacting
with sodium azide using dimethyl formamide or dimethyl sulfoxide as solvents lead-
ing thereby to formation of GAP-diol or GAP-triol (Schs. 2 and 3).
The details of reaction conditions used for the synthesis of these polymers are
described below.
NaN3 OH -
CH2 CHCH2Cl N3CH2CHCH2Cl N3CH2CH CH2
HOAc
O OH O
ECH GA
Scheme 1. Synthesis of GA.
H O CH CH2 O CH2CH2O CHCH2O H

n H2C CH CH2Cl + HOCH2CH2OH
CH2Cl CH2Cl
O n n
PECH -DIOL
NaN3
H O CH CH2 O CH2CH2O CHCH2O H
CH2N3 CH2N3
n n
GAP-DIOL
Scheme 2. Preparation of GAP-diol.

Azido Polymers 509
HOCH2CHCH2OH O CH CH2 OCH2CHCH2O CH2CHO H

H2C CH CH2Cl + H
OH CH2Cl n CH2Cl n
O
Propanetriol
O CH2CHO H
CH2Cl n
PECH-TRIOL
NaN3
H O CH CH2 OCH2CHCH2O CH 2CHO H
CH2N3 CH2N3
n n
O CH2CHO H
CH2N3 n
Scheme 3. Preparation of GAP-triol.
(a) Synthesis of Polyepichlorohydrin
Polyepichlorohydrin has been synthesized by carrying out the polymerization

of ECH. The conversion depends on the nature of initiator system, monomer to
initiator ratio, solvents, reaction temperature etc. Bronsted acids (e.g., CF3SO3H)
as well as Lewis acids (protogens or cationogens) have been used as initiators.[11]
Generally a monomer: initiator ratio in the range of 40 4:1 has been used. The
percentage conversion was low when Bronsted acids were used as initiators.
Hydrocarbons (toluene), ethers (dioxane, diethyl ether), or chlorinated hydro-
carbons (1,2-dichloroethane) have been used as solvents in this polymerization.
The effect of catalysts (such as SnCl4, BF3-etherate, or CF3SO3H), solvents,
reaction time, and reaction temperature on the percentage yield has been inves-
tigated (Table 1).
The polymers thus prepared had low molecular weight and a wide molecular
weight distribution. The molecular weight distribution obtained from the GPC
chromatograms is given in Table 2.
As is obvious from Table 2, the product distribution is dependent upon the
initiators used. Product obtained when BF3-etherate was used as an initiator had
molecular masses in the range of 200–2000. When SnCl4 was used as an initiator the
molecular mass was considerably high as compared to CF3SO3H or BF3-etherate.
When 1,2-dichloroethane or toluene was used as solvent, the reaction was rapid and
the molecular weight distribution was wide. It was noted that as much as 60% of the
tetramer was obtained in the system with BF3-etherate in 1,2-dichloroethane. With
ethereal solvents, the reaction was slow. High basicity of ethereal solvents is expected
510 Gaur et al.
Table 1. Effect of reaction parameters on percent yield of polyepichlorohydrin (data adapted

from Ref.[11]).
Sample Monomer/initiator Time Yield

designation Initiator Solvent ratio (h) (%)
A-1 BF3OEt2 1,2-Dichloroethane 44:1 4.0 98

A-2 Dioxane 42:1 4.0 11
A-3 Toluene 36:1 4.0 88
A-4 Ethyl ether 36:1 4.0 5
A-5 1,2-Dichloroethane 36:1 4.0 19
B-1 SnCl4 1,2-Dichloroethane 54:1 3 75
B-2 Dioxane 43:1 2.5 50
B-3 Toluene 44:1 23.5 73
C-1 CF3SO3H 1,2-Dichloroethane 44:1 7.0 2
C-2 Dioxane 38:1 23.0 12
Temperature 5 C (with dioxane 15 C).
Table 2. Molecular weight distribution of PECH synthesized under different reaction

conditions (sample designation same as Table 1) (data adapted from Ref.[11]).
Sample
designation n¼2 n¼3 n¼4 n¼5 n¼6 n¼7
A-1 2 0 43 14 6 35
A-2 18 1 4 22 20 35
A-3 1 0 26 12 7 54
A-4 3 2 13 22 19 41
A-5 5 0 60 31 4 0
B-1 5 0 9 11 7 68
B-2 15 0 5 6 6 68
B-3 9 0 12 12 11 56
C-1 45 0 8 21 16 10
C-2 32 0 13 17 14 24
n is the degree of polymerization.
to suppress the propagation reaction and promote a backbiting reaction to produce

low molecular weight cyclic oligomers according to reaction (Sch. 4).
As opposed to typical chain end mechanism mentioned above, the polymeriza-
tion of ECH could also proceed in the presence of glycols by activated monomer
mechanism (AMM), which involves the concept of living polymerization that has no
termination or transfer process. In AMM, an activated i.e., protonated or positively
charged monomer molecule inserts into a growing polymer chain having an -OH
group at the chain-end (Sch. 5).[12,13] This mechanism leads to a polymer having two
-OH groups at the chain ends. Here Mn ¼ [ECH]/[glycol]. Side reactions, including
cyclization, are strongly suppressed in the polymerization by AMM and well-defined
linear products are obtained. The activated monomer mechanism operates at low
Azido Polymers 511
CH2Cl A - CH2Cl CH2Cl CH2Cl A

- CH2Cl
+ propagation +
OCHCH2 O OCHCH2-OCHCH2 O polymer
CH2Cl
propagating chain
:O
back-biting
CH2Cl
ClH2C
CH2Cl H2
-
A + CH C ECH
CH CH2
O O O O + propagating
O..
O+ chain
C CH
H2C CH CH2Cl H2 CH2Cl
CH2Cl
volatile dimer
Scheme 4. Chain growth and backbiting reaction during ECH polymerization.
Initiation:
+ +
R OH + H O R O OH + " H "
Propagation:
+ +
... OH + H O ... O OH + " H "
The notation ‘‘Hþ’’ means that the proton is not located on any specific oxygen
atom, but is rapidly exchanging between various sites.
Scheme 5. Activated monomer mechanism for synthesis of PECH.
monomer concentration, which requires slow addition of monomer to the reaction

mixture. The PECH-diols obtained under these conditions, had controlled molecular
weight up to Mn 2500 g/mole and with Mw/Mn<1.2. The content of cyclic oligo-
mers did not exceed 0.7%. PECH of Mn 2000 was synthesized by using boron
trifluoride–ethylene glycol as catalyst while aluminium triethyl–ethylene glycol
yielded PECH of Mn more than 100,000.[12]
(b) Azidation of PECH
Azidation of PECH to GAP has been carried out in an organic or an aqueous

solvent,[3,14] using an ionic azide such as lithium azide, sodium azide, or potassium
azide. A molar excess of ionic azide is needed for this purpose.[14] Complete conver-
sion of polyepichlorohydrin to GAP with sodium azide in dimethyl sulphoxide
(DMSO) is reported to occur at 90–95 C within 12–18 h, whereas the reaction in
512 Gaur et al.
water, in the presence of a phase transfer catalyst (methyl tricapryl ammonium

chloride) required seven days for completion at the same temperature.
Nevertheless, both processes yielded GAP of a comparable quality based on elemen-
tal analysis, equivalent and molecular weight determination, and thermal behavior.
The conversion of PECH to GAP can be easily monitored by IR spectroscopy by
following the disappearance of the absorption band at 748 cm1 (due to -CH2Cl
group) and appearance of the 2099 cm1 band (due to azido group) (Fig. 1). Fast
Figure 1.
Azido Polymers 513
neutron activation analysis of nitrogen and chlorine in the final product has also
been used to monitor the conversion of PECH to GAP.[15]
In the above-mentioned azidation reaction, carried out in solution, one of the
problems is the slowing of the reaction rate above 90% conversion. This decrease
in rate, which more than doubles the reaction time from the initial rate, is a con-
sequence of the association of the metal cation (e.g., Naþ or Liþ) of the azide salt
with the solvent medium, in which it has limited solubility. In a molten salt method,
quaternary ammonium azide such as tetrabutyl ammonium azide and trace amount
of water is mixed with PECH and heated at 105 C for about 0.33 h. The resulting
liquid product on washing with water and drying showed 85–90% conversion of
PECH to GAP.[16]
Low molecular weight GAP (500), which could be used mainly as an energetic
plasticizer, can be prepared by a one-step method, which involves direct conversion
of ECH to GAP.[17] The plasticizer helps in processing of the propellants based on
GAP and enhances the stability and mechanical properties. However the hydroxy
end-groups of these glycidyl azide polymers react with the isocyanate curing agent
leading thereby to a loss of plasticization effect. A diazide terminated azide polymer
has, therefore, been developed to overcome this difficulty. Tosylation of hydroxy
terminated polyepichlorohydrin with p-toluene sulfonyl chloride (in presence of pyr-
idine) followed by replacement of chlorine and tosyl group by azide (sodium azide in
DMF) is a convenient approach for the synthesis of such polymers (Sch. 6).
Azido terminated glycidyl azide polymers (GAP-A) have also been prepared by
nitration of hydroxy terminated polyepichlorohydrin and subsequent reaction with
sodium azide[18] (Sch. 7).
2.2. Direct Conversion of Epichlorohydrin to

Glycidyl Azide Polymer (GAP)
A single step process for preparation of hydroxy terminated GAP

(Mn 500 g/mol) has been described,[19] which is less time consuming and more
cost effective. In this method sodium azide was gradually mixed with ECH (1:1
molar ratio), DMF, and EG and the contents were initially stirred at 70 C. Since
the reaction was exothermic in the initial stages, the temperature was controlled
p-toluenesulfonylchloride
H O CH CH2 O CH2 CH2 O CH2 CH O H PECH(OTs)2
CH2Cl CH2Cl pyridine
n n
NaN3
PECH(OH)2
DMF
N3 CH CH2 O CH CH2 O CH2 CH2 O CH2 CH O CH2 CH N3

CH2N3 CH2N3 CH2N3 n-1 CH2N3
n -1
Scheme 6. Tosylation of PECH followed by azidation.

514 Gaur et al.
H O CH CH2 O CH2 CH2 O CH2 CH O H

CH2Cl CH2Cl n
n
Hydroxy terminated PECH
HNO3 / H2SO4
O2N O CH CH2 O CH2 CH2 O CH2 CH O NO2
CH2Cl CH2Cl n
n
Polyepichlorohydrin nitrate
NaN3
N3 CH CH2 O CH CH2 O CH2 CH2 O CH2 CH O CH2 CH N3

CH2N3 CH2N3 CH2N3 n-1 CH2N3
n -1
Scheme 7. Nitration of PECH followed by azidation.
during the first 30 min. The reaction temperature was then raised to 90 C and stirring
was carried out at this temperature for 15 h. The yield was high (90%).
2.3. Simultaneous Degradation and Azidation of PECH

and Its Copolymers
Branched GAP or copolymer of GAP (70%) with ethylene oxide (30%) (GEC)
having variable molecular weight (500–40,000) has been synthesized directly
through a simultaneous degradation and azidation process by reacting a high
molecular weight rubbery poly(epichlorohydrin) (PECH) or poly(epichlorohydrin-
co-ethylene oxide) (PEEC), with the epichlorohydrin (ECH) monomer and sodium
azide (NaN3).[20,21] Degradation and azidation of a commercial rubbery PECH or
PEEC with NaN3 and lithium methoxide (basic cleaving agent) in the presence of a
polyol at 120 C in polar organic solvents (DMSO, DMAc, DMF, etc.,) without the
use of ECH monomer has also been reported.[22–24] The polyols used in this synthesis
were 1,2,3-propane triol (PPT), trimethylol propane (TMP), and pentaerythritrol
(PE) (Table 3). DMSO is preferred over the other solvents due to the quality of
the final product.
Azido Polymers 515
Table 3. Solution properties of GAP and copolymers prepared by simultaneous degradation

and azidation in presence of polyols (data adapted from Ref.[20]).
Polymer Polyol [n] (dL/g) Mn Mw
GAP homopolymer PPT 0.122 10,600 18,100

TMP 0.125 11,000 18,500
PE 0.141 11,400 22,700
GEC copolymer PPT 0.185 10,400 20,900
TMP 0.216 14,700 28,500
PE 0.183 11,600 20,400
The observed polydispersity index (Mw/Mn) is between 1.70 and 2.10. This type
of molecular weight distribution may be considered relatively low for polymers
resulting from a degradation process. GEC had a higher viscosity than GAP with
a similar molecular mass. This may be attributed to the presence of ethylene oxide
groups in the polymer chain.
2.4. Block Copolymers of GAP
A triblock copolymer poly(glycidylazide-b-butadiene-b-glycidyl azide) (GAP-

PB-GAP) has been reported by Vasudevan and Sundarajan[25] (Sch. 8). In the
synthesis of this block copolymer, HTPB was used as an alcohol and boron trifluo-
ride etherate (BF3-etherate) as catalyst. Epichlorohydrin was added to the catalyst
mixture dropwise. The polymerization was carried out at 0 C for 12 h and then for
4 h at room temperature (30 C) under nitrogen atmosphere. Epichlorohydrin adds to
both the hydroxyl groups of HTPB leading to the formation of a secondary alcohol,
which is able to react with epichlorohydrin by the same pathway to yield poly-
(epichlorohydrin) blocks. Ring opening polymerization was followed by conversion
of the -CH2Cl group into -CH2N3 group using sodium azide in DMSO at 105 C
for 10 h.
2.5. Polymerization of Azidomethyl Oxetanes
Polymerization of substituted four membered oxetanes can produce polymers

with higher molecular weight and higher elongation as compared to GAP.[26] The
functionality and molecular weight of the resulting polymer may be controlled easily
as compared to epoxides. Therefore, polymers and copolymers of oxetanes contain-
ing azido groups, such as 3-methyl-3-azidomethyl oxetane (AMMO) and 3,3-bis-
azidomethyl oxetane (BAMO) have been investigated in the past.[26] The synthesis
of poly(BAMO) has been carried out using two different procedures. In one of the
methods, 3,3-bis(chloromethyl) oxetane (BCMO) was treated with sodium azide in
dimethyl formamide (DMF) at 85 C for 2 h. The bisazidomethyl oxetane obtained
was then homopolymerized or copolymerized with tetrahydrofuran (THF) by
carbocationic ring opening polymerization using BF3-etherate as catalyst in the
516 Gaur et al.
HO OH
n
2 CH 2 Cl
BF 3 -etherate
O
HO CHCH 2 O O CH 2 CH OH
n
CH 2 Cl CH 2 Cl
n CH 2 Cl
O
HO CHCH 2 O CHCH 2 O O CH 2 CH O CH 2 CH OH
n n n
CH 2 Cl CH 2 Cl CH 2 Cl CH 2 Cl
Na N 3 , DMSO
1 05ºC, 10h
HO CHCH 2 O CHCH 2 O O CH 2 CH O CH 2 CH OH
n n n CH 2 N 3
CH 2 N 3 CH 2 N 3 CH 2 N 3
Scheme 8. Preparation of block copolymer poly(GAP-b-PB-b-GAP).
presence of butanediol as an initiator at 5 C. The other method involved the ring
opening polymerization of BCMO or copolymerization with THF using
butanediol as initiator and BF3-etherate as catalyst at 5 C. The polymer or the
copolymer obtained was then treated with sodium azide in DMF (solvent) at 90 C
(Sch. 9). The starting material, BCMO is easily obtained by ring closure of trichloro
derivative of pentaerythritol.[27]
Quasi-living cationic polymerization of 3-azidomethyl-3-methyloxetane
(AMMO) was achieved with a bis(chlorodimethylsilyl)benzene/Ag hexafluoroanti-
monate (AgSbF6) initiating system in methylene chloride at 78 C. The average
molecular weight (Mn) increased linearly with an increasing monomer/initiator
([M]/[I]) ratio and a linear Mn vs. [M ]/[ I] ratio plot passed through the origin.[28]
Both ends of the difunctional initiator are activated.[29]
Block copolymers of BAMO with other cyclic ethers have been synthesized with
an aim of developing energetic thermoplastic elastomers (TPE). The TPE thus
prepared have high molecular mass, low polydispersity index, low Tg, and good
energetic characteristics. Block and random copolymers of THF and BAMO have
been prepared by using triflic anhydride (CF3SO2)2O as a bifunctional initiator.[30]
Azido Polymers 517
CH2N3
CH2Cl DMF CH2N3 BF3.etherate
+ NaN3 O O CH2 C CH2
O
CH2Cl 85ºC , 2 h CH2N3 butanediol CH2N3 n
CH2Cl
BF3.etherate NaN3
CH2Cl
O O CH2 C CH2
CH2Cl butanediol n DMF, 90ºC
CH2Cl
Scheme 9. Synthetic route for the preparation of poly(BAMO).
Homo as well as block copolymers of low polydispersity index (1.23–1.28) could be

prepared by using this initiator. In random copolymerization of THF and BAMO, r1
and r2 values were found to be 0.33 and 1.12 respectively, showing thereby higher
reactivity of BAMO.
Novel energetic oxetane derivatives 3-nitratomethyl-3-methyl oxetane (NMMO)
and AMMO could be polymerized by triflic anhydride [(CF3SO2)2O]. The living
cationic characteristics of the polymerization confirmed via a 19F NMR technique.
Novel polymers of the A-B-A type with various molecular weight (Mw ¼
14,320–40,660) and low polydispersity index (PDI ¼ 1.11–1.29) were obtained.[31]
Analysis of the polymer by different techniques (NMR, IR spectroscopy,
and DSC) showed that the structure of the polymer was composed of a two-phase
domain structure of amorphous poly(NMMO) phases and crystalline poly(AMMO)
phases.
The synthesis of triblock copolymer of BAMO, AMMO, and bis-ethoxymethyl
oxetane (BEMO) with center block composed of BAMO and AMMO has been
reported by Murphy et al.[32] The copolymerization required 1,4-butanediol and
BF3-etherate in the ratio of 1:2. A solution of monomer (AMMO or BAMO) in
methylene chloride was added drop wise to the catalyst system at 10 C. A new
monomer (BAMO or AMMO) was added when more than 95% conversion of the
previous block is reached. The block copolymers are thus sequentially polymerized
in a ‘‘living polymer’’ manner according to activated monomer mechanism.
Synthesis of BAMO and nitratomethyl methyloxetane (NMMO) block copoly-
mers has been reported by using 1,4-butanediol/BF3-etherate initiating agent.[33]
A triblock copolymer BAMO–NMMO–BAMO was prepared by using p-bis(a,
a-dimethylchloromethyl)benzene ( p-DCC) with silver hexafluoroantimonate
(AgSbF6) as initiator.[34] The propagating chain end is a carboxonium ion. The
polymerization has been carried out in nitrogen atmosphere at low temperature
(70 C) using methylene chloride as solvent. The centre block of NMMO is
prepared first, according to Sch. 10.
The cationic copolymerization of AMMO was initiated by a mixture
of BF3OEt2 and diethylene glycol. The copolymerization of AMMO with
3-(azidomethyl)-3-(2,5-dioxaheptyl)oxetane and 3-(azidomethyl)-3-(2,5,8-
trioxadecyl)oxetane(II) was investigated in order to obtain (for solid propellants)
518 Gaur et al.
CH3 CH3 AgSbF6 CH3 CH3
Cl C C Cl +C C+
CH3 CH3 CH3

CH3
CH3 CH3 CH3

CH3 CH3 CH3
+ +C C O CH2NO2
+C C+ :O +
CH2NO2 CH3 CH3
CH3 CH3
NMMO
NMMO
CH3 CH3 CH3 CH3

+
C C O CH2 C CH2 O
CH2NO2
CH3 CH3 CH2NO2
Propagating chain
Scheme 10. Preparation of triblock copolymer BAMO–NMMO–BAMO.[34]
materials with less of a crystalization tendency and a lower glass transition tem-
perature, (Tg) than poly(AMMO), for example, when AMMO was copolymerized
with 15 wt.% II, it was possible to obtain bifunctional oligomers with Tg 50 to
60 C, without significant loss in the nitrogen content.[35]
Linear ABA triblock and (AB)n segmented block copolymers of energetic mono-
mers were synthesized. The rigid and soft blocks are prepared from AMMO and
NMMO respectively. Polymerization of AMMO initiated by triethyloxonium tetra-
fluoroborate and by spiro (benzoxasilole)/propanediol produced a-mono-
hydroxy-poly-AMMO, and o,o0 -dihydroxy-poly-AMMO of number average
molecular weight-16,000 and 2000, respectively and a,o-dihydroxy-poly-NMMO
(Mn ¼ 13,000).[36] A spiro(benzoxasilole) catalyst, 3,3,30 ,30 -tetrakis(trifluoro-
methyl)-1,10 -(3H,3H)-spirobis(1,2-benzoxasilole), was used to polymerize 3,3-R,R0 -
oxetanes: (R,R0 ¼ ethoxymethyl; R ¼ azidomethyl, R0 ¼ Me; R ¼ nitratomethyl,
R0 ¼ Me; and R,R0 ¼ azidomethyl) with descending rates in this order. 31P NMR
spectra of polymerization mixtures quenched using Bu3P were consistent with an
oxonium ion propagating species.[37]
New energetic azide group-containing polyesters have recently been
reported. These are prepared from 2,3-dibromosuccinic acid and 1,2-propanediol
and 3-chloropropanediol and succinic/malonic acid. These hydroxyl terminated
polymers had a functionality of approximately 2.0. The number average molecular
Azido Polymers 519
weight of the bromopolyester and chloropolyesters of malonic/succinic acid were

found to be 1280, 1079, and 825, respectively. These halogenated polyesters were
converted to the corresponding azido polyesters via reaction with sodium azide. The
decomposition temperatures of these azido polyesters were around 235, 210, and
228 C respectively.[38]
Several new energetic polymer systems poly(BAMO-co-GAP) and poly(BAMO-
co-glycidyl nitrate (PGN)) and poly(BAMO-co-AMMO) have been evaluated as
energetic thermoplastic elastomeric binders for composite rocket propellants.
BAMO-GAP had moderately high density, high heat of formation, and high burning
rate, which should make it attractive in formulations requiring high-burning-rate
compounds. BAMO-PGN had a very high density, a favorable oxygen balance,
and a reasonably high heat of formation. These properties make BAMO-PGN
and BAMO-GAP ideally suited as binders for high-performance energetic
compounds.[39]
2.6. Poly(Allyl Azide) (PAA)
Azidation of poly(allyl chloride) (PAC) is a convenient route for the preparation

of poly(allyl azide). However allyl chloride during free radical polymerization under-
goes degradative chain transfer yielding polymers of relatively low molecular masses.
Poly(allyl chloride) having molecular mass in the range of 2000 g/mol could be
obtained by following the cationic route. Allyl chloride (0.5 mol) was polymerized
in our laboratories using Lewis acids such as anhydrous TiCl4/FeCl3/AlCl3 and
aluminium powder.[40] The concentration of the catalyst was varied from 0.7 to
3.2 mol % of the monomer. The quantity of aluminium powder was kept constant
(2 g). The reaction was carried out at low temperatures (0–20 C) and brown-colored
viscous polymer was formed.
Chlorine in poly(allyl chloride) samples was found to be in the range of 35–40%,
which is lower than the calculated value of 46.05%. On the other hand, the carbon
content was higher than the expected value. A discrepancy in chlorine and carbon
content of the polymers may be explained on the basis of branching of poly (allyl
chloride) (Sch. 11).
1
H NMR spectrum of poly(allyl chloride) is shown in Fig. 2. The chloromethyl
protons in poly(allyl chloride) were observed at 4.03 ppm. The vinyl proton reso-
nance signals of allyl chloride at 5.22, 5.32, and 5.94 ppm were absent in poly(allyl
chloride). Additional resonance signals were observed at 0.88–2.27 ppm. The inte-
gration of the resonance signals at 0.88–2.27 ppm did not correspond to the number
of methyl and methylene protons in the polymer backbone for a linear-chain poly-
mer. The loss of chlorine, as indicated by elemental analysis results, also suggests the
formation of a branched polymer. Therefore, on the basis of elemental analysis and
1
H NMR it was concluded that poly(allyl chloride) was a branched polymer. The
azidation of poly(allyl chloride) was carried out using sodium azide and dimethyl
sulphoxide as solvent at 100 C for 12 h. The conversion of PAC to PAA was mon-
itored by IR spectroscopy by following the decrease in the intensity of 736 cm1
absorption band due to -CH2Cl and appearance of a strong band due to -CH2N3 at
2095 cm1 (Fig. 3).
520 Gaur et al.
AlCl3 or FeCl3 - -
CH 2 CH CH 2 CH CH 2 CH CH 2 CH + AlCl4 or FeCl4
CH 2 Cl CH 2 Cl + CH 2 CH 2 Cl
CH 2 CH CH 2 Cl
CH 2 CH CH 2 CH
CH 2 CH 2 Cl
CH 2
CH
CH 2 Cl
Scheme 11. Probable side reaction during the synthesis of poly(allyl chloride).
Figure 2.
3. PHYSICAL PROPERTIES OF AZIDO POLYMERS
Depending on the backbone structure and molecular mass, the Tg of linear azido
polymers range from 20 to 70 C. The glass transition temperature of GAP was
found to be 45 C. Tg of branched GAP and branched glycidyl azide-ethylene oxide
copolymer is in the range of 60 to 70 C.[20] The physical properties of various
glycidyl azide polymers are given in Table 4.[41,42] Since GAP is in a rubbery state at
Azido Polymers 521
Figure 3.
temperatures above Tg, which is lower than the lowest operational temperature
(40 C) for rocket monitors, it can be considered a mechanically safe binder for
composite propellant.[43] Tg values of GAP increased with increase in the quantity
of decomposed -N3 groups. Branched GAP cured with IPDI has a Tg 23 3 C.
522 Gaur et al.
Table 4. Characteristics of azide polymers (data adapted from Refs.[41,42]
Sample designation
GAP-DIOL GAP-TRIOL GAP-A

hydroxy hydroxy azide
Properties terminated terminated terminated
Hf (kJ/g) 1.170 1.170 2.299

Hr (kJ/g) 1.839 1.630 —
Density (g/cc) 1.29 1.29 1.27
Appearance Light yellow Light yellow Light yellow
liquid liquid liquid
Tg ( C) 45 45 56 to 69
Hf ¼ heat of formation, Hr ¼ heat of reaction.
The presense of ethylene oxide units in branched GAP reduced the Tg to

40 2 C.[21]
The Tg of poly(AMMO) (molecular weight 2800–6700 g/mol) was determined by
DSC and was in the range 51.5 to 45.5 C.[44] Poly(AMMO-b-NMMO-b-
AMMO) had a Tm ¼ 82 C and Tg ¼ 3 C was phase separated in the melt. This
copolymer decomposed at 224 C evolving 0.69 kJ/g of heat. It has excellent
mechanical properties with elongation of 683% at break, 5.25 MPa stress, and
82% recovery. The poly(AMMO-b-NMMO)n copolymer has similar thermal prop-
erties and spectroscopic characteristic, but is inferior to tri block copolymer in all
rheological and mechanical properties.[36]
BAMO homopolymer has a Tg of 28 C and Tm of 76–80 C.[26] The Tg is
reduced to 60 C in the copolymers of BAMO and THF.[26] The viscosity is in
the range of 500–5000 cps, depending on the molecular mass (500–5000 g/mol).
The functionality of the linear polymer is 1.5–2.0 and for the branched version it
varied from 5.0–7.0. The burning rate of GAP is very sensitive to the amount of the
curing agent. The material (88.5% GAP) self-extinguishes at ambient pressure and
burns at 1.96 cm/s at 6.89 MPa.[3]
A maximum burn rate of 1.68 cm/s has been reported for GAP cured with TDI
or isophorone diisocyanate.[6] Burning rate of BAMO polymer is less than that
of GAP.[4]
4. CURING OF GAP
4.1. Curing Agents
Hydroxy terminated azido polymers are cross-linked by polyisocyanates via a

urethane forming reaction. Functionality greater than two must be used to ensure
reticulation. In such systems, different mechanical properties of the binder can be
obtained by adjusting the parameters of the curing reaction and the component
concentrations, which result in varying cross-link density of the matrix. A schematic
Azido Polymers 523
representation of the preparation of polyurethanes by such a polyaddition procedure

is shown in Sch. 12.
The choice of an appropriate curing agent is of prime importance to meet the
minimum strain, stress, and hardness levels of mechanical properties, which
crucially affect the performance of the propellant.[45] Commonly used isocyanates
are isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), 4,40 -diisocyanato
diphenylmethane (MDI), 4,40 -dicyclohexyl methane diisocyanate (H12MDI),
Desmodur N-100. The molecular formulae of some of these curing agents[7,46] are
given in Sch. 13.
The polyol reactants, coupling agents or chain extenders, which are generally
explored in the synthesis of polyurethanes, are triethanolamine, hexanetriol,
trimethylol propane,[47] glycerol, pentaerythritol , pyrogallol.[21] Their main function
n HO R OH + n OCN R' NCO

NCO
HO R O O C N H R' NH C O O R O O C N H R' N C O
n -1 NCO
NH C O O R
Scheme 12. Urethane network formation.
OCN NCO
OCN NCO
H 3 C CH 2 NCO H 12 MD I
IPDI
NCO NCO
N N
H
NCO
N O
H
Desmodur N-100
CH 3 CH 3
NCO OCN NCO
80% + 20% TDI
NCO
Scheme 13. Structure of polyisocyanates used for curing azido polymers.

524 Gaur et al.
O
O GAP OCOHN HN N
NHOCO O
OCOHN HN O
O O
Scheme 14. Network structure of cured GAP using Desmodur N-100.
is to make the PU well cured. They have a noticeable effect on the curing reaction
of azido polymer with the isocyanate and thus affect the mechanical properties.[23]
The network structure obtained by reacting glycidyl azide polymer (GAP) with
Desmodur N-100 and pentaerythritol can be schematically represented as follows
(Sch. 14).
Catalysts are often required to obtain complete curing and also to speed up the
reaction, although the amount and type of catalyst depends on the nature of reac-
tants. The most common types of catalysts used are organometallics (e.g., organotin
compounds) and tertiary amines (triethyl amine, TEA). Dibutyltin dilaurate (DBTL)
is known to be the most suitable catalyst for the urethane formation between long
chain diols including GAP[41] and isocyanates. The curing time of GAP is reduced
from three weeks to 5–6 days at 60 C in the presence of DBTL (30–75 ppm).[48]
When composite catalyst, triphenyl bismuth (TPB) and DBTL are used for curing
GAP-diisocyanate in the presence of trimethylol propane (TMP), curing time of 3–4
days is required.[47–49] This composite catalyst suppresses CO2 formation and
promotes cross-link density.
4.2. Cure Monitoring
The curing of GAP is a slow process. The mixtures having a NCO/OH ratio of 0.7
or 0.8 require a longer curing time (about three weeks) for a complete curing than do
the samples with higher NCO/OH ratio (0.9–1.2) (about two weeks). The curing
reaction has been monitored by gel-time determination, viscosity and hardness mea-
surements, FTIR spectroscopy, and DSC studies. Gel-time, which determines the pot
life of a propellant and is related to the extent of cross-linking, affects the processing of
an uncured propellant. Propellant slurry should have a reasonably low viscosity and
long enough pot life to make it castable. Gel-time can be determined by viscosity
measurements and is strongly dependent on the amount of curing catalyst,[48] nature
of isocyanate, and ratio of NCO/OH. 4,40 -Diisocyanato diphenylmethane (MDI),
exhibited highest rate of curing while IPDI reflected lowest rate of reaction.[21]
The hardness increases as the curing reaction proceeds and reaches a plateau of
constant value, thereby indicating the completion of curing reaction of GAP. The
ultimate hardness of the cured GAP increased with an increase in NCO/OH ratio.
The propellants become harder upon solid loading. The binder with a NCO/OH
ratio of 0.8 had the lowest value of hardness and therefore may be considered to be
more suitable for composite propellant applications.[49] Monitoring the hardness
gives an apparent curing completion but not a true chemical completion. There
Azido Polymers 525
might be a significant number of unreacted GAP molecules, which could not

participate in curing due to the diffusion-controlled nature of the reaction.
The Tg of pure GAP, which is around 45 1 C[48] increases on curing by 6–9

C and depends on the NCO/OH ratio. An increase in the extent of curing (by
increase in NCO/OH ratio) leads to an increase in Tg values. Addition of plasticizers
(i.e., bis-2,2-dinitropropyl acetal and bis-2,2-dinitropropyl formal (BDNPA/F) did
not affect the curing reaction but reduced Tg to 47 C which is low enough to
produce a rubbery propellant.[48]
Kinetics of polyurethane formation between GAP and N-100 of catalyzed as
well as uncatalyzed reaction has been studied in the bulk state by quantitative FTIR
spectroscopy by following a decrease in the intensity of NCO stretching band at
2270 cm1 and appearance of new band at 1726 cm1. The enthalpy and entropy of
activation for uncatalyzed reaction were found to be 44.1 0.5 kJ/mol and
196 2 J/K mol, respectively. The rate constant for the catalyzed and uncatalyzed
reaction at 60 C was found to be 4.37, and 3.88 106 L mol1s1 respectively. A
significant rate enhancement is observed in the presence of a catalyst at operating
conditions.[45]
4.3. Problems of GAP-Isocyanate Cure
There are certain problems, which are encountered while using isocyanates
as curing agents for hydroxy-terminated binders. The first and the most serious
problem is the gas evolution, when GAP is cured with diisocyanates, because the
-N¼C¼O group, reacts rapidly with water to release CO2 and forms numerous voids
in the cured explosive, resulting in a decrease of loading density, mechanical
strength, performance, and safety. Hydroxyl terminated GAP, itself has inherent
trapped moisture due to hydroxyl groups, which is needed to be expelled before
curing with isocyanates in order to prevent bubble formation. Void-free propellants
require de-gassing before curing. Addition of deflagerating additives eliminates this
de-gassing step.[50] A second problem is a significant decrease in the energy output of
plastic bonded explosives (PBXs) or propellants, because of the inert properties of
diisocyanates and chain extenders (TMP). A third problem is the loss of plasticizing
effect during curing of the hydroxyl groups of GAP with isocyanates. Curing causes
an increase in Tg of GAP and it increases with increasing in NCO/OH ratio.[50]
In order to avoid this problem, it is desirable either to add a plasticizer or to provide
a plasticizer without hydroxyl groups i.e., azide terminated GAP (GAPA). In
order to keep both high-energy density and improved mechanical properties, use
of elastomeric GAP (average molecular weight>1.4 105) along with multi-
hydroxy-functional branched GAP (B-GAP) has been reported.[47]
4.4. Characterization of Cured Network
Network structure of elastomers can be characterized by swelling, solubility, and

mechanical measurements. The average molecular mass of the chain sections
between cross-links, Mc, was calculated using Flory-Rehner equation from the swel-
526 Gaur et al.
ling studies of GAP elastomers (Desmodur N-100, IPDI/TMP, and H12MDI/TMP)

in tetrahydrofuran solvent at room temperature. The volume of the swollen network
prepared with the same ratio of NCO/OH depended on the structure of isocyanates
and was highest with IPDI and lowest with Desmodur N-100. Desmodur N-100
cured elastomers for the same ratio of NCO/OH have smaller values of Mc than
those of IPDI/TMP and H12MDI/TMP cured elastomers. A linear relationship
between sol fraction and Mc values was observed.[7]
In order to assess the effect of residual DMSO in B-GAP on the properties of
cured energetic binders, small amounts of DMSO (2, 4, and 6% w/w) to that of
B-GAP were intentionally added to the curing mixtures NCO/OH ratio as 1.2
using TDI as the curing agent. The cured samples containing 6% (w/w) of
DMSO, appeared less transparent and much softer than the other samples. This
has been attributed to some degree of phase separation caused by the presence of
DMSO.[21]
NCO-terminated energetic azide can itself be used as a curing agent for OH-
terminated aliphatic polymers to obtain an elastomer for solid rocket propellants.[51]
4.5. Curing of Azido Polymers with Dipolarophiles
Curing of azido polymers has also been done with multifunctional dipolaro-
philes e.g., multifunctional acrylic or acetylenic esters (dimethylene glycol diacrylate,
tetraethylene glycol diacrylate, ethylene glycol diacrylate, hexanediol diacrylate,
pentaerythritol tri/tetraacrylate, hexane diol diacrylate) or acrylic amide molecules
(hexane diamine bis-acrylamide, methylene bis-acrylamide).
Azides are 1,3-dipolar compounds and readily undergo a [3 þ 2] cycloaddition
with olefinic or acetylinic esters and amides to yield a five-membered heterocyclic
ring (e.g., 1,2,3-triazoline or 1,2,3-triazole.[52] The kinetics and mechanism of such
cycloaddition has been reported in the literature.[53] A concerted nonsynchronus
mechanism with partial charges at the transition state (charge imbalance) has been
suggested for such cycloaddition which are always cis and usually regiospecific.[54,55]
The triazoline thus synthesized is thermally labile and looses N2 to yield aziridines.
Therefore, the reactions are carried out at low temperatures and may take weeks for
completion. Rigid alkenes such as norbornene, react with azide on heating to form
exo-adduct. For example, norbornene: aryl azide adducts have been prepared by
refluxing in petroleum ether (60–90 C) for 3–4 h.[55]
The use of highly functional dipolarophiles can reduce the relative amount of
cross-linking agent required to achieve a desired degree of cross-linking, thereby
maintaining a higher percentage of high energy chemical moieties in the cross-
linked polymer network. Further reaction between an azido polymer and a multi-
functional dipolarophile is not stoichiometrically limited by the amount of hydroxy/
azido groups contained in the azido polymer. An azido polymer has a relatively large
amount of pendant azido groups, and a multifunctional dipolarophile can react with
some or all of these azido groups. This allows for extensive control of the degree of
cross-linking of the azido polymer thus providing reaction products having a variety
of morphologies and/or hardness properties.[50] The typical reaction between an
azido group and a multifunctional dipolarophile[56] is depicted in Sch. 15.
Azido Polymers 527
O O
2 Polymer N3 + HC C C O R O C C CH
O O
H H
C O R O C
Polymer N N N N Polymer
N N
Scheme 15. Reaction scheme for cross-linking of azido polymers by difunctional
dipolarophiles.
CH3 O O CH3
P olym er N3 + CH2 C C O CH2 CH2 O C C CH2
CH3 O O CH3
CH2 C C O CH2 C H2 O C C CH2
P olym er N N N N P olym er
N N
Scheme 16. Curing of PAA using EGDMA.
The above-mentioned reaction is insensitive to moisture and hence there is no

need to avoid moisture in reactants (e.g., drying of fillers etc.). Dipolarophiles have
advantages in producing cross-linked high-energy materials. Cross-linking at azido
groups with these dipolarophiles changes the azido group to a triazoline or a triazole
group, which can ensure stability[56] and enhances the burn rate of the cross-linked
polymer.[51] Azido polymers with improved burn rate have been prepared by using
azido polymers, an acrylic and an acetylenic ester or amide groups.[56]
The curing of poly(allyl azide) (PAA) using ethylene glycol dimethacrylate
(EGDMA) has also been reported.[40] The reaction can be depicted according to
the reaction (Sch. 16).
528 Gaur et al.
Preferred amounts of the multifunctional dipolarophile are in the range of

20–100 pph (parts by weight of an ingredient/100 parts by weight of the azido poly-
mer). Such an additional reaction can be easily carried out at ambient conditions in
about 1–24 h. The reaction can be carried out in the temperature range of 0 C to
about 90 C. However, it is preferable to use temperatures between 25–40 C. The
reaction rate is typically hindered by the presence of solvent.[50]
Azides are known to react readily with both electron-deficient as well as
electron-withdrawing dipolarophiles. Therefore, studies on highly electron-deficient
dipolarophiles such as bismaleimides, bisitaconimides, or endo-5-norbornene-2,3-
dicarboximide (bisnadimides) with allyl azide and glycidyl azide were carried out
by Varma et al.[57] The curing of azide could be carried out at 40–60 C to yield
flexible products with improved thermal properties.
5. THERMAL BEHAVIOR OF AZIDO POLYMERS
Thermal stability and degradation of uncured and cured azido polymers has
been investigated by DSC and thermogravimetric analysis in nitrogen atmosphere.
Analysis of gases generated by the decomposition has been done by gas chromatog-
raphy and IR spectroscopy.
5.1. Uncured Azido Polymers—Linear and Branched
In the DSC scans of GAP a single exothermic peak is observed in the tempera-
ture range of 186–273 C with exothermic peak temperature 247 5 C due to elim-
ination of nitrogen from the azide group.[57] The energy liberated at this stage is
around 1.9 kJ/g.[58,59] Sahu et al.[59] however have reported a bimodal exotherm in
GAP polymers of molecular weight 1150 and 2150 g/mol, with exothermic peak
temperatures at 218, 242, and 222 C, 262 C, respectively. The DSC scan (Fig. 4)
of poly(allyl azide) showed an exothermic transition in the temperature range of
155–274 C, with the exothermic peak temperature at 231 C. The energy liberated
was 1.099 kJ/g.[40]
The thermal decomposition of polyglycidyl azide (GAP) and bis(azidomethyl)-
oxetane-tetrahydrofuran copolymer (BAMO/THF) showed overall first-order
kinetics. Additonal azide groups at the terminal positions in GAP decomposed
independently and increased the rate of decomposition. However, the decompositon
kinetics was less affected by the additional azide groups in the main chain. The
decompositon properties of aged polymer samples were the same as those of
unaged ones.[60]
The DSC traces of azido polymers have also been recorded using different ramp
rates (0.2–10 C/min). A ramp rate higher than 5 C/min causes violent detonation in
the DSC cell (Fig. 5). Such explosions are also observed when more than 5 mg of
sample is used.[40]
In the TG trace of GAP recorded in nitrogen atmosphere, two mass loss steps
were observed. The first decomposition corresponds to nearly 36% mass loss in
the temperature range of 210–270 C. The second stage is completed around
Azido Polymers 529
Figure 4.
Figure 5.
410 C. The temperature of the maximum rate of mass loss in the first step of
decomposition was 250 C, which coincides with the exothermic peak temperatures
in DSC scans. Therefore, the first step of mass loss in TG can be attributed to
elimination of N2, which theoretically should have been around 30% in GAP.
530 Gaur et al.
Figure 6.
However, a mass loss of 36% was observed and may be due to breakdown of
polymer backbone at higher temperature.
The thermal decomposition of poly(allyl azide) also proceeded in two steps.[40]
The first step of the decomposition occurred in the temperature range of 160–322 C.
This decomposition corresponded to 28.3% mass loss (Fig. 6). The exothermic
transition (observed in DSC) and accompanied by a mass loss (28%) in the TG
trace can be attributed to the breakdown of azido group. Theoretically the decom-
position of the azido group in a linear PAA should have resulted in a mass loss of
33.7%. The poly(allyl azide) thus had lower azido content, which may be attributed
to the branched structure of PAA (Sch. 11).
Major mass loss in GAP and PAA was observed above 400 C (59%) and
was due to breakdown of the polymer backbone leading to the formation of
hydrogen, carbon monoxide, carbon dioxide, methane, ammonia, hydrogen
cyanide gas, and other higher hydrocarbons.[61] Small molecules are formed by
BAMO and GAP, but some large fragments are evolved by AMMO.[61] A char
residue of 15% at 600 C and 7% at 800 C was obtained and was attributed to
the formation of cross-linked structure by imine intermediate (inter- as well as
intra-molecular) (Sch. 17).
The N3 group elimination in GAP has been followed by IR spectroscopy. A
decrease in the intensity of N3 groups at 2100 and 1280 cm1 was observed on
heating to 170 C and new peaks appeared at 1529 (NH bending), 1677
(C¼N-C-H stretch), 1725 (C¼N-C-C stretch), and 3350 cm1 (NH stretching).
The intensity of the C-O-C (ether) at 1410 cm1 remained unchanged during
the initial stages of decomposition supporting the view that in the initial stages
of decomposition only the side chain breakdown was the main process. Intra- and
intermolecular bridge formation (Sch. 17) has been proposed to account for the
Azido Polymers 531
HO (CH2 CH O CH2 CH O) H HO (CH2 CH O CH2 CH O) H + 2n N2

n
n
CH2 CH2 C-H C-H
N3 N3 N-H N-H
Intramolecular
Intermolecular crosslinking
CH2 CH O CH2 CH O crosslinking
CH2 CH2
N N CH2 CH O CH2 CH O
CH CH CH CH
CH2 CH O CH2 CH O N N
Scheme 17. Intra- and inter-molecular reactions of the imino groups.
CH2N :
(I) H O CH CH2 O NH3 + CH2O + HCCO
CH2N:
(II) CH CH2 HCN+ C2H 4
CH2N :
(III) O CH CH2 HCN + CO + CH4
CH2N :
(IV) O CH CH2 O NH3 + CO + CH2 CO
Scheme 18. Decomposition patterns of the nitrene backbone after N2 has been liberated
from GAP.
insolubility of partially degraded samples and for the appearance of -C¼N-C-

type of structures in IR.[58]
After the elimination of N2 from azido group of GAP further reaction of nitrene
intermediate proceed according to Sch. 18.[61]
The combustion characteristics (burning rates, temperature profiles) and kinetic
parameters (order of reaction, activation energy, pre-exponential factor of rate con-
stants) for the thermal decomposition of GAP together with the composition of the
products of both the combustion and decomposition of uncrosslinked GAP (with a
molecular weight of 350 or 2000) and cured GAP were studied. The final tempera-
ture of a flame of GAP was measured at 1000 to 1100K. However, approximately
47% of the mass of the combustion products was volatile gases N2, H2, CO, CO2,
CH4, C2H4, C2H6, NH3, H2O, acetonitrile, acrylonitrile, and furane, as obtained by
mass-spectrometry by using freezing/thawing in a liquid nitrogen trap.[62]
532 Gaur et al.
5.2. Uncured BAMO and AMMO Polymer
A mass spectroscopic study on the thermal decomposition of BAMO and

other azide polymers was made by Faber and Srivastava.[63] During isothermal
experiments, the melting temperature of BAMO was found to be 75 C. Slight
decomposition began at 130 C, and at that temperature the release of N2 from
azide groups was observed to be the primary decomposition path, where the rate
of N2 release increased as the temperature is increased. The three-carbon backbone
of the polymer remains intact until a higher temperature, approximately 160 C,
when the mass spectrometer (MS) showed fragments of HCN, H2, CH2, CH3, O,
OH, H2O, H2CO, CH2OH, and NO2 in addition to N2. These species showed the
initiation of secondary decomposition. BAMO monomer and polymer were investi-
gated by Brill and his coworkers[64,65] with the rapid scanning Fourier infrared
(RSFTIR) technique to characterize the slow (5K/min) and rapid (50–255K/min)
thermolysis of these compounds and with the simultaneous mass and temperature
change (SMATCH)/FTIR spectroscopy to determine the kinetics of mass-loss
process of the compounds.
The TGA data revealed that the first stage mass loss occurred rapidly at about
187 C and was completed at about 247 C with the approximately 35% mass loss.
This stage was predominantly related to the elimination of N3 bond in the infrared
(IR) spectra of the sample. The second stage mass loss process occurred slowly
without heat liberation and was caused by the decomposition of remaining frag-
ments as detected by the strong IR absorption of C¼N, C-H, C-O bonds. The rate of
gradual weight loss was compared under isothermal and nonisothermal conditions
for AMMO, BAMO, and GAP by TGA during the initial 20–40% of mass loss
where decomposition of the azide group dominates.[65] Isothermal rate constants, k,
obtained for different azide polymers are given in Table 5. The following order of
rates of isothermal decomposition was observed: GAP>BAMO>AMMO. BAMO
polymer and copolymer with tetrahydrofuran (THF) were studied by Miyazaki and
Kubota.[66]
Thermal stability of aged THF copolymers with AMMO or NMMO decreased
in the order poly(THF)>poly(AMMO-THF-AMMO,) poly(NMMO-THF-
NMMO.[67] DSC studies revealed that the copolymers of THF with BAMO,
AMMO, NMMO have low Tg and large decomposition enthalpies which were
brought about by attached azido groups.[68] NMMO based polymers exhibited
lower thermal stability and relatively higher decomposition enthalpies. Thermal
Table 5. Isothermal TGA rate constants (s1) for azide polymers (data adapted from
Ref.[65]).
180 C 185 C 190 C 195 C 200 C 205 C 210 C

Polymer (x 106) (x 106) (x 106) (x 106) (x 106) (x 106) (x 106)
AMMO — 4.85 8.21 13.00 19.27 33.36 50.20

BAMO — 12.76 24.13 38.65 64.88 85.62 138.10
GAP 12.98 22.88 35.18 59.50 82.45 133.10 —
Azido Polymers 533
stability of these polymers was further improved by curing with isocyanate

and pentaerythritol. Poly(BAMO) and poly(BAMO-THF) degrade exothermically
with Tmax of 237 C and 241 C respectively; and the activation energy of 39 and
40 kcal/mol.[29]
5.3. Thermal Behavior of Cured Azido Polymers
The TGA showed a two-stage decomposition pattern in the case of poly (allyl
azide).[40] A mass loss of 20–25% was observed in the temperature range of
161–324 C and may be due to the elimination of nitrogen from the azido group.
The second stage decomposition was in the temperature range of 313–525 C
accounting for the mass loss of 52–61%. This is due to the thermal degradation of
the main chain along with the 1,2,3-triazoline group formed by the cross-linking
reaction of poly(allyl azide) with ethylene glycol dimethacrylate (EGDMA)
(5–45 phr). The TG trace of poly(allyl azide) cured with EGDMA is given in
Fig. 7. Violent detonation was observed when a high heating rate and sample
mass of more than 5 mg was used (Fig. 8).
The combustion wave structure and thermal decomposition process of GAP
propellent, cured with hexamethylene diisocyanate and crosslinked with trimethylol-
propane to formulate the propellant were studied to determine the parameters that
control the burning rate. The burning rate of the propellant is high even though the
adiabatic flame temperature is less than that of conventional solid propellants. The
energy released at the burning surface of this propellant is caused by the scission of
N–N2 bond which produces gaseous N2. The heat flux transferred back from the gas
phase to the burning surface is very small compared with the heat generated at the
burning surface. The activation energy of the decomposition of the burning surface
of this propellant was 87 kJ/mol.[69]
Figure 7.
534 Gaur et al.
Figure 8.
The Arrhenius activation energies (Ea) of decomposition of uncrosslinked and

cured GAP are mostly clustered in the 150.5–183.9 kJ/mol range, which is similar to
the RN–N2 bond strength of 146.3–171.4 kJ/mol (Table 6).
An attempt has been made to address several of the discrepancies in the
chemistry of GAP. There is broad consistency among the global values of Ea for
decomposition of GAP and general agreement that the rate is dominated by the
decomposition of the azide group, discrepancies exist in the occurrence of later stage
products. For example, the decomposition of the alkane imine or nitrene after the
release of N2 is found to produce NH3 and HCN in significant amounts in several
studies. It is found that NH3 content increases with the -OH content of GAP, which
suggests that end-chain azide groups mostly form NH3. The HCN/NH3 ratio
increases with increasing temperature. However, NH3 is also formed in isocyanate
cured GAP and GAP plasticizer, which possess no -OH groups. Some differences are
expected from the use of different types of samples, e.g., different MW, terminal
groups, or cure. The activation energy obtained from DSC and TGA for branched
GAP (B-GAP) is in the range of 138–145 kJ/mol, which is lower than that for GAP-
TRIOL (160–178 kJ/mol), indicating that B-GAP decomposes more easily as
compared to GAP-TRIOL.[74]
The burning rate and thermochemical measurements have been conducted to
obtain information on the effects of pressure, initial temperature, and catalyst on
ammonium perchlorate/3-azidomethyl-3-methyloxetane polymer (AP/AMMO) and
ammonium perchlorate/hydroxy-terminated polybutadiene propellants. Pressure
insensitive burning (i.e., plateau burning) was observed when the HTPB binder
was replaced with the AMMO binder for the AP composite propellants. The
Azido Polymers 535
Table 6. Literature Arrhenius kinetics for the decomposition of GAP (data adapted from
Ref.[61]).
Method Ea (kJ/mole) A (s1) Temp. range (K) Comments Ref. no.
DSC 166–177 7 1015– 520–540 uncured 43, 70&71
8.9 1015
DSC 152.1 2 1013 520–535 cured 70
DSC 178 5.0 1017 — cured 43

65, 72&73
TGA 154–164 — 400–473 —
A is the frequency factor.
temperature sensitivity of both AP/AMMO and AP/HTPB propellants increases as

pressure increases. The addition of ferric oxide accelerates the burning rate of both
AP/AMMO and AP/HTPB propellants. The temperature sensitivity of the gas-phase
reaction is increased significantly when the HTPB binder is replaced with the
AMMO binder.[70]
Measurements of gaseous species and temperature profiles for RDX/BAMO
pseudo-propellants were performed by Lee et al.[76] The propellants were made
from a physical mixture of RDX and BAMO in weight ratio of 80:20.
Experiments were conducted at atmospheric pressure in argon with heat fluxes of
100 and 400 W/cm2 delivered by a CO2 laser. The products of each ingredient, RDX
and BAMO, were found to exist simultaneously throughout the gas phase; however,
primary reaction chemistry in the gas phase was dominated by RDX.
The accelerated aging of BAMO-HMX propellent was conducted at 347K for
several weeks. BAMO-HMX propellants for a very low cross-linking ratio formed a
cavity between HMX and BAMO binder by evolution of N2, CO2, and H2O during
accelerated aging. An exotherm, generated by the decomposition of azide binder,
initiated and accelerated the thermal decomposition of HMX. The burning rate of
BAMO-HMX propellant was larger than those of BAMO binder and HMX, respec-
tively. However, the propellant could not maintain the combustion at low pressure,
at which its burning rate was equal to that of BAMO binder.[77]
6. PHOTODECOMPOSITION
Photosensitivity of polymers with pendant azide groups is well known. Such

polymers are used as negative photoresists mixed with an unsaturated hydrocar-
bon polymer under intense UV radiation.[59] The azide group undergoes decom-
position, producing a nitrene radical, which quenches by abstracting H from
another polymer, reacting with itself forming an azo group or by reacting with
a double bond of another polymer forming an aziridine linkage. In photoresist
applications, the advantage of aziridine formation by nitrene is generally realized
leading to cross-linking and photo insolubility. Scheme 19 describes the photo-
decomposition of the azide group and the reactions of the nitrene radical thus
formed.
536 Gaur et al.
R N3 R N : + N2
2 R N: R N N R
R N: + H C R NH C
R N: + H C R NH + .C
R N: + R N
Scheme 19. Photodecomposition of azido polymer under UV irradiation.
Acceleration of the photoinsolubility of GAPs can be achieved by the addition

of an unsaturated hydrocarbon polymer [e.g., poly(ethylene-propylene-ethylene-
norbornene)], where the nitrene radical of GAPs reacted with >C¼C< resulting
in cross linking through the formation of an aziridine ring.
7. FORMULATIONS
As mentioned earlier, a typical propellent formulation comprises of several

ingredients. For example, a solid rocket motor propellant consists of 70–85 wt%
solids chosen from energetic solids and oxidizers and 15–30 wt% of a binder such
as polyoxetane (poly(BAMO/AMMO)) or GAP and an isocyanate curing agent. The
details of these ingredients are described in the subsequent text. A plasticizer, such as
triethylene glycol dinitrate (TEGDN), N-butyl-2-nitratoethyl nitramine (BuNENA),
trimethylolethane trinitrate (TMETN), and butanetriol trinitrate (BTTN), is used
with the polyoxetane binder, preferably at a 0–3.0:1 plasticizer–polymer weight ratio.
The energetic solids and oxidizers can include such material as particulate NH4ClO4,
Al, HMX, etc. A propellant formulation with acceptable mechanical properties
contained BAMO-AMMO-Desmodur N 100 copolymer 12.5, TEGDN 12.5,
ammonium perchlorate 48.0, HMX 5.0, and Al 22.0 wt%.[78]
7.1. Plasticizers
The curing and solid loading increases the Tg of the polymers. Therefore, for
being used as binder in composite propellants, the Tg of GAP should be lowered to
compensate the reverse effect of curing and solid loading on the Tg. The Tg values
of gum stocks upon curing can be compensated by using a plasticizer. Various
plasticizers which are used in order to improve the poor mechanical properties of
GAP at low temperature are iso-decyl pelargonate (IDP), dioctyl adipate (DOA),
Azido Polymers 537
dimethylene glycol dibenzoate (DMGDB),[21] dioctyl azelate (DOZ), dioctyl seba-

cate (DOS), diethyl phthalate (DEP), 1,2,4-butanetriol trinitrate (BTTN), trimethyl-
olethane trinitrate (TMETN), polyethylene glycol (PEG), bis-2,2-dinitropropyl
acetal and bis-2,2-dinitropropyl formal (BDNA/F).[42] The plasticizer had no effect
on the decomposition characteristics of GAP. The addition of a plasticizer affects the
mechanical properties (e.g., ultimate hardness) of the gum stocks significantly.
The Tg of GAP is decreased from 45 to 65 C with bis-2,2-dinitropropyl
acetal/formal (BDNPA/F) and to 48.4 C with dioctyl adipate (DOA) at a 25/75
plasticizer/polymer weight ratio. The decomposition properties remain practically
unchanged, while the Tg increased to 36.8 C upon curing.[43]
Nitroplasticizer (BDNA/F) has been found to be more compatible with ener-
getic binder GAP than PEG.[79] Nitrate plasticizer, TMETN, played an important
role in improvement of not only combustion properties but also insensitivities of
GAP/AN propellants.[80]
Low molecular mass GAPs can be exploited as an energetic plasticizer.[18] GAP
with a molecular mass of 500 would be useful as a plasticizer in composites and
propellant compositions.[17] An azide-terminated azido polymer (GAP-A) acts as
plasticizer for propellants.[18] The replacement of nitroglycerin plasticizer by GAP
in composite-modified double-base propellants results in greater safety in handling,
reduced detonation sensitivity, higher burning rate and specific impulse, and
improved mechanical properties.[81]
Cycloaddition of azido group containing polyoxyalkylenes by reaction with
diethenyl benzene to form triazole crosslinked, energetic plasticizers for composites
propellants has been reported recently. Thus, repeating units of GAP, (AMMO),
(BAMO-NMMO), and (BAMO-AMMO) are effective as energetic plasiticizers
when cross-linked with 1,4-bis(ethynyl)benzene, 1,4-bis(ethynylcarbonyl)benzene,
or 1,3-bis(cyanoethynyl) benzene.[82]
7.2. Oxidizers
The primary function of an oxidizer in a propellant is to provide oxygen for

the combustion of hydrocarbon fuel species. Higher loading of oxidizer increases the
specific impulse (Isp) of a propellant but simultaneously it adversely affects the
mechanical properties.[1] Positive oxygen balance, high heat formation, high density,
and high thermal stability are the other important criteria for an energetic
oxidizer. Most commonly used oxidizers are crystalline fine particles of ammonium
perchlorate (AP), ammonium dinitramide (ADN), glycerol trinitrate (NG), cyclote-
tramethylene tetranitramine (HMX), cyclotrimethylene trinitramine (RDX),
(TAGN), hydrazinium nitroformate (HNF), hexanitro hexaaza iso-wurzitane, or
HNIW (CL-20). Sorguyl, bicyclo HMX, and tetranitro-bicyclononanone (K56) are
some examples of nitraza polycycles, which are gaining importance. Sorguyl and
K56 are hydrolytically unstable whereas bicyclo HMX is extremely difficult to
synthesize.
AP and HMX are two solid ingredients often used in modern solid propellants,
either composite propellent or composite modified double base propellants. During
the past decade, the search for more energetic propellants has led to the development
538 Gaur et al.
of CL-20, ADN, HNF, etc. Formulation of BAMO/AMMO with CL20, RDX and
the combination of the two leads to potentially attractive high energy TPE gun
propellants.
Structure and characteristics of some of these oxidizers are given in Sch. 20 and
Table 7, respectively.
ONO2 NO2
O2N NO2
N
N N
ONO2
N N
O2N NO2 N N
ONO2 O2N NO2
NG RDX HMX
O2N NO2
N N N NO2
NO2
NH4+ N-
NH2NH3+ C NO2
NO2 NO2
N
N N
O2N NO2
CL-20 ADN HNF
NO2 NO NO2 NO
2 2 NO2 NO
N N N N 2
O N N
O
N N N N O
N N
NO2 NO2 NO2 NO2 NO2 NO2
Bicyclo HMX Sorguyl K56
[83,84]
Scheme 20. Representative structure of oxidizers.
Table 7. Characteristics of oxidizers (data adapted from Refs.[83,85])
Mol. wt. Density Hf

Oxidizer Formula (g/mol) (g/cm3) (kJ/mol)
AP ClH4NO4 117.5 1.95 296

AN H4N2O3 80 1.72 365
ADN H4N4O4 124 1.81 150
HNF CH5N7O6 183 1.86–1.93 71 to 72
RDX C3H6N6O6 222 1.805 þ70
HMX C4H8N8O8 296 1.91 þ84
Bicyclo HMX C4H6N8O8 294 1.87 þ125
Sorguyl C4H2N8O8 322 2.035 292
K56 C5H6N8O9 322 1.975 144
CL-20 C6H6N12O12 438 1.92–2.04 þ339 (g,a,b)
þ372 (")
Azido Polymers 539
Ammonium perchlorate is the most widely used oxidizer in composite and com-
posite modified double base (CMDB) rocket propellants. AP has two inherent dis-
advantages, (1) it produces chlorine rich combustion products (30%), posing
environmental hazards such as ozone depletion and acid rain and (2) it produces
white smoke trail during inclemental weather, which is detrimental for specific appli-
cations demanding smokeless plume. Among other oxidizers, AN and ADN offers
chlorine free formulations. However, AN has drawbacks of hygroscopic nature and
multiple transition phases in the temperature range of practical importance and
comparatively low energy. ADN and HNF have attracted global attention. CL-20
is also being evaluated as a rocket propellant component.[41,83] HNF has certain
advantages over ADN such as its simple method of synthesis, nonhygroscopic
nature, higher density, and melting point. The addition of crystalline particles
such as AP and nitramine particles decreases the burning rate of GAP significantly
even though the combustion temperature increases.[86] The particle size of the oxidi-
zer also plays an important factor in determining the performance of the propel-
lants.[83,85,87] The energetic composites of GAP/nitroplasticizer (BDNA/F) and
polyethylene glycol with HMX in various particle sizes have been studied and
compared with HTPB composites.[79]
The flame structure of GAP propellants is altered by the nature of the oxidizer.
The flame is highly heterogeneous in GAP/AP propellants but homogeneous in
GAP/HMX and GAP/TAGN propellants.[85]
7.3. Pyrolants
The addition of metal particles i.e., Al, Mg, Ti, B, Zr, etc., to GAP
forms energetic materials (GAP/metal pyrolants). These are also called fuel material
particulates. The metal particles mixed within GAP react with the nitrogen, C, CO
produced by the thermal decomposition of GAP. The most probable chemical reac-
tions, which are likely to take place are formation of aluminium or magnesium
nitride (AlN, Mg3N2) and titanium carbide (TiC). GAP-coated amorphous-boron-
based fuel-rich propellants exhibit more vigorous phenomena, high burning rates,
and a lesser extent of residue agglomeration than the uncoated baseline propellant.
Moreover, reaction mechanisms were proposed to elucidate the combustion pro-
ducts.[33] However, the reaction process is highly dependent on the type of metal
particles mixed. Thus the burning rates and thermal decomposition vary with the
type of metals mixed. Though GAP contains no oxidizer fragments in its products,
addition of metal particles increases the energy of GAP.[89]
The flame temperatures of GAP/metal pyrolants increases with increase in con-
centration of pyrolants. The addition of B or Al generates higher flame temperature
compared with Mg, Ti, or Zr.
7.4. Ballistic Modifiers
In general, ballistic modifiers bring down the maximum decomposition tempera-

ture. They are also known as burning rate modifiers. Their main function is to
540 Gaur et al.
catalyze the burn rates. Commonly exploited ballistic modifiers are copper chromite
(Cu(CrO2)2), ferric oxide, butyl ferrocene, catocene (C27H32Fe2). The mixture of
catocene and copper chromite in BAMO/NMMO copolymers augmented the burn-
ing rate 1.6 times with decreasing temperature sensitivity.[33] The combustion rate of
GAP-HMX propellant was increased by addition of 2% lead citrate and 0.6% C.
New molybdenum oxide/vanadium oxide burning modifiers, with pure AN
(atomized from melt) has resulted in improved combustion behavior and stability
of GAP/AN-propellants.[84]
8. CONCLUSION AND FUTURE OUTLOOK
Energetic fuel binders based on cyclic ethers (oxirane, oxetane derivatives) and
having pendant azido group have been investigated in the past two decades for gun
and rocket propellants. These polymers (e.g., GAP, BAMO, AMMO) are promising
candidates for energetic binders in future composite propellants having minimum
smoke, reduced pollution, and sensitivity. Such propellants in addition to being fuel
rich, liberate large amounts of H2, N2, CO, and gaseous hydrocarbons on burning in
the primary chamber, are insensitive to impact and provide high burn rates.
Inspite of all the advantages mentioned above, there are certain limitations of
these azide binders. The decomposition products of cured GAP contain HCN, which
is highly toxic. Attempts have to be made to suppress the HCN evolution. The Tg of
GAP increases on curing and by presence of oxidizers, pyrolants, etc. There is a need
to develop energetic binders with lower Tg.
Energetic binders based on hydrocarbon polymers containing pendant azide
group may provide an alternative approach for achieving this goal.
This review focused on the synthesis, characterization, physical properties, and
thermal behavior of these energetic azido binders. Preliminary studies on poly(allyl
azide) have also been included. It is obvious that one can tailor the properties of
these polymers by changing their backbone structure and by copolymerization.
More studies are needed for developing energetic binders using structural
modifications.
ACKNOWLEDGMENT
The Armament Research Board, Government of India, Ministry of Defence

is gratefully acknowledged for providing the financial assistance for carrying out
this work.
REFERENCES
1. Aggarwal, J.P.; Walley, S.M.; Field, J.E. High speed photographic study of
the impact response of ammonium dinitramide and glycidyl azido polymer.
J. Propulsion and Power 1997, 13, 463.
2. Borman, S. Advanced energetic binders for military and space applications.
Military Technology 1994, 72, 18.
Azido Polymers 541
3. Frankel, M.B.; Grant, L.R.; Flanagan, J.E. Historical development of

GAP. J. Propulsion and Power 1992, 8, 560.
4. Kubota, N.J. Combustion of energetic azide polymers, Propulsion and Power
1995, 11, 677.
5. Madhavan, A.; Ramasubramanian, T.S.; Hariharasubramanian, A.; Kannan,
K.G.; Ninan, K.G. A Redox Method for the Estimation of Nitrogen in
Glycidyl Azide Polymer. In Second International High Energy Materials
Conference and Exhibit IIT-Chennai, India, Dec. 8–10, 1998.
6. Sahu, S.K.; Chavan, M.K.; Thakur, J.V.; Kulkarni, S.G.; Panda, S.P.
Performance Evaluation of Glycidyl Azide Polymers as Integrated Ram
Rocket Propellants. In Second International High Energy Materials
Conference and Exhibit IIT-Chennai, India, Dec. 8–10, 1998.
7. Eroglu, M.S.; Guven, O. Characterisation of network structure of poly(glycidyl
axide) elastomers by swelling, solubility and mechanical measurements.
Polymer 1998, 39, 1173.
8. Braithwaite, P.C.; Sanderson, A.C.; Wardle, R.B.; Peters, S. Optimization of
BAMO-AMMO for gun propellants, (JANNAF 29th Propellant Development
& Characterization Subcommittee Meeting, 2000), CPIA Publication 2000, cf
CA 2000, 135, 109317.
9. Braithwaite, P.C.; Haaland, A.C.; Wardle, R.B.; Harris, L.E.; Manning, T.;
Prickett, S. Development of improved artillery gun propellants. International
Annual Conference of ICT, cf CA 1999, 131, 118115.
10. Wardle, R.B.; Braithwaite, P.C.; Haaland, A.C.; Hartwell, J.A.; Hendrickson,
R.R.; Lott, V.; Wallace, I.A.; Zisette, C.B. High energy oxetane/Hnw propel-
lants, International Annual Conference of ICT 1996, 27th(Energetic Materials),
52.1–52.7.
11. Ito, K.; Usami, N.; Yamashita, Y. Cationic oligomerisation of epichlorohydrin.
Polym. J. 1979, 11, 171.
12. Panda, S.P.; Sahu, S.K.; Thakur, J.V.; Kulkarni, S.G.; Kumbhar, C.G.;
Sadafule, D.S. Synthesis and characterisation of hydroxyl terminated poly-
epichlorohydrin and polyglycidyl azide. Def. Sci. J. 1996, 46, 399.
13. Biedron, T.; Kubisa, P.; Penczek, S. Polyepichlorohydrin diols free of cyclics:
synthesis and characterization. J. Polym. Sci.: Part A: Polym. Chem. 1991, 29,
619.
14. Frankel, M.B. Aqueous process for the quantitative conversion of polyepi-
chlorohydrin to glycidyl azide polymer US Patent 4,379,894, 1990.
15. Panda, S.P.; Kulkarni, S.G.; Sahu, S.K.; Bhoraskar, V.N.; Dokhale, P.A.J. Fast
neturon activation analysis of high energy materials and polymers. Energetic
Materials 1998, 16, 309.
16. Wagner, R.I. Glycidyl azide polymer synthesis by molten salt method. US
Patent 5,055,600, 1991.
17. Ampleman, G. Synthesis of a diazido terminated energetic plasticizer. US
Patent 5,124,463, 1992.
18. Wilson, E.R.; Frankel, M.B. Azide-terminated azido compound as energetic
plasticizer for propellants. US Patent 4,781,861, 1988.
19. Ahad, E. Process for the preparation of allyl azide substituted hydroxyl termi-
nated polyethers. US Patent 4, 891, 438, 1990.
542 Gaur et al.
20. Bui, V.T.; Ahad, E.; Rheaume, D.; Raymond, M.P. Energetic polyurethanes
from branched glycidyl azide polymer. J. Appl. Polym. Sci. 1996, 62, 27.
21. Bui, V.T.; Ahad, E.; Rheaume, D.; Whitehead, R. Evaluation of banched
glycidyl azide polymer purified by solvent extraction. Ind. Eng. Chem. Res.
1997, 36, 2219.
22. Ahad, E. Branched azido copolymers. US Patent 5, 130, 381, 1992.
23. Ahad, E. Branched energetic polyether elastomers. US Patent 5, 214,110, 1993.
24. Nazare, A.N.; Asthana, S.N.; Patwardhan, S.S.; Singh, H. Comparative studies
on GAP formed from degradation of high molecular weight PECH and one
stage conversion from ECH. In 4th International Symposium on Explosive
Technology and Ballistics (NIXT-92), South Africa, 1992.
25. Vasudevan, V.; Sundarajan, G. Synthesis of GAP-PB-GAP triblock copolymer
and application as modifier in AP/HTPB composite propellant. Propellants,
Explosives and Pyrotechnics 1999, 24, 295.
26. Ou, Y.; Chen, B.; Yan, H.; Jia, H.; Li, J.; Dong, S. Development of energetic
additives for propellants. J. Propulsion and Power 1995, 11, 838.
27. Nair, J.K.; Satpute, R.S.; Polke, B.G.; Mukundan, T.; Asthana, S.N.; Singh, H.
Synthesis and characterisation of bis-azido methyl oxetane and its polymer and
copolymer with tetrahydrofuran. Def. Sci. J. 2002, 52, 147.
28. Talukder, M.A.H. Ring-opening polymerization of oxetanes by cationic
initiators: polymerization of 3-azidomethyl-3-methyloxetane with bis(chlorodi-
methylsilyl)benzene/silver hexafluoroantimonate initiating system. Makromol.
Chem., Macromolecular Symposia 1991, 501.
29. Talukder, M.A.H. Ring-opening polymerization of oxetanes by cationic
initiators: polymerization of azidomethyloxetane with bis(chlorodimethylsilyl)-
benzene/silver hexafluoroantimonate initiating system. ACS Polymer Preprints
(Division of Polymer Chemistry), 1990, 31, 93.
30. Hsiue, G.; Liu Y.-L.; Chiu, Y.-S. Triblock copolymer based on cyclic ethers:
preparation and properties of tetrahydrofuran and 3,3-bis(azidomethy) oxetane
triblock copolymers. J. Polym. Sci.: Part A: Polym. Chem. 1994, 32, 2155.
31. Liu, Ying-Ling; Hsiue, Ging-Ho; Chiu, Yie-Shun. Studies on the polymeriza-
tion mechanism of 3-nitratomethyl-3-methyloxetane and 3-azidomethyl-3-
methyloxetane and the synthesis of their respective triblock copolymers with
tetrahydrofuran. J. Polym. Sci.: Part A: Polym. Chem. 1995, 33, 1607.
32. Murphy, E.A.; Ntozakhe, T.; Murphy, C.J.; Fay, J.J.; Sperling, L.H.
Characterization of poly[3,3-bis(ethoxymethyl)oxetane] and poly[3,3-bis(azido-
methyl)oxetane] and their block copolymers. J. Appl. Polym. Sci. 1989, 37, 267.
33. Kimura, E.; Oyumi, Y. Effects of copolymerization ratio of BAMO/NMMO
and catalyst on sensitivity and burning rate of HMX propellant. Propellants,
34. Talukder, M.A.H.; Lindsay, G.A. Synthesis and the preliminary analysis of
block copolymers of 3,30 -bis(azidomethyl)oxetane and 3-nitratomethyl-30 -
methyloxetane. J. Polym. Sci.: Part A: Polym. Chem. 1990, 28, 2393.
35. Cheradame, H.; Gojon, E. Synthesis of polymers containing pseudohalide
groups by cationic polymerization. 2. Copolymerization of 3,3-bis(azidomethyl)-
oxetane with substituted oxetanes containing azide groups. Makromol. Chem.
1991, 192, 919.
Azido Polymers 543
36. Xu, B.; Lin, Y.G.; Chien, J.C.W. Energetic ABA and (AB)n thermoplastic
elastomers. J. Appl. Polym. Sci. 1992, 46, 1603.
37. Xu, B.; Lillya, C.P.; Chien, J.C.W. Spiro(benzoxasilole)catalyzed polymerization
of oxetane derivatives. J. Polym. Sci.: Part A: Polym. Chem. 1992, 30, 1899.
38. Athar, J.; Borah, P.; Mukundan, T.; Sarwade, D.B.; Asthana, S.N.
Spiro(benzoxasilole) catalyzed polymerization of oxetane derivatives. J.
Polym. Mater. 2002, 19, 183.
39. Braithwaite, P.; Edwards, W.; Sanderson, A.J.; Wardle, R.B. The synthesis and
combustion of high energy thermoplastic elastomer binders. International
Annual Conference of ICT, 2001, cf CA 2001, 135:373693.
40. Gaur, B.; Lochab, B.; Choudhary, V.; Varma, I.K. Thermal behaviour of
poly(allylazide). J. Therm. Anal. Cal. 2003, 71, 467.
41. Finck, B.; Graindorge, H. New Molecules for High Energetic Materials. In 27th
Int. Annu. ICT Conf. (Energetic Materials) 1996, 23.
42. Nazare, A.N.; Asthana, S.N.; Singh, H.J. Glycidyl azide polymers (GAP)—An
energetic component of advanced solid rocket propellants—A review. Energetic
Materials 1992, 10, 43.
43. Selim, K.; Ozkar, S.; Yilmaz, L. Thermal characterization of glycidyl azide
polymer (GAP) and GAP-based binders for composite propellants. J. Appl.
Polym. Sci. 2000, 77, 538.
44. Mitarai, Y.; Anan, T.; Irie, A.; Ohuchi, S.; Tamura, N. Physicochemical prop-
erties of AMMO polymer, Kogyo Kayaka 1990, 51, 240; cf CA 1991, 114,
188532.
45. Keskin, S.; Ozkar, S. Kinetics of polyurethane formation between glycidyl azide
polymer and a triisocyanate. J. Appl. Polym. Sci. 2001, 81, 918.
46. Panda, S.P.; Sahu, S.K.; Thakur, J.V.; Kulkarni, S.G.; Kumbhar, C.G.;
Sadafule, D.S. On decomposition mechanism and explosive properties of
GAP based RAM rocket propellants. American Institute of Aeronautics and
Astronautics 1996, IS-267, 1,
47. Wang, P.; Xia, Z.; Zhou, Y.; Li, C. Investigation of High Molecular Weight
GAP. In 27th Int. Annu. ICT Conf. (Energetic Materials) 1996, 25.
48. Kasicki, H.; Pekel, F.; Ozkar, S. Curing characteristics of glycidyl azide poly-
mer-based binders. J. Appl. Polym. Sci. 2001, 80, 65.
49. Russel, R., Jr.; Chan, L.M. Propellant binders cure catalyst. US Patent
4,379,903, 1983.
50. Russel, R., Jr.; Chan, L.M. Glycidyl azide propellant with antigassing addi-
tives. US Patent 5,092,945, 1992.
51. Frankel, M.B.; Wilson, E.R.; Woolery, D.O. Energetic azido curing agents. US
Patent 4,96,2213, 1990.
52. Katritzky, A.R.; Singh, S.K. Synthesis of C-carbamoyl-1,2,3-triazoles by
microwave-induced 1,3-dipolar cycloaddition of organic azides to acetylenic
amides. J. Org. Chem. 2002, 67, 9077.
53. Al-Sader, B.H.; Kadri, M. Kinetics and mechanism of the 1,3-dipolar cyclo-
addition of phenyl azides to methyl 3-pyrrolidinoacrylate. Tetrahedron Letter
1985, 26, 466.
54. Huisgen, R. Mechanism of 1,3-dipolar cycloadditions. Reply, J. Org. Chem.
1968, 33, 2261.
544 Gaur et al.
55. Scheiner, P.; Schomaker, J.H.; Deming, S.; Libbey, W.I.; Nowack, G.P. The
addition of aryl azides to norbornene. A kinetic investigation. J. Am. Chem.
Soc. 1965, 87, 306.
56. Manzara, A.P. Azido polymers having improved burn rates. US Patent
5,681,904, 1997.
57. Varma, I.K.; Choudhary, V.; Gaur, B.; Lochab, B.; Oberoi, S. A process for the
production of energetic binder (azide polymer), Indian Patent Appl. 1316/Del/
2002, December 31, 2002.
58. Eroglu, M.S.; Guven, O. Thermal decomposition of poly(glycidyl azide) as
studied by high-temperature FTIR and thermogravimetry. J. Appl. Polym.
Sci. 1996, 61 (5), 201.
59. Sahu, S.K.; Panda, S.P.; Sadafule, D.S.; Kumbhar, C.G.; Kulkarni, S.G.;
Thakur, J.V. Thermal and photodegradation of glycidyl azide polymers.
Polym. Degrad. and Stab. 1998, 62, 495.
60. Oyumi, Y. Thermal decomposition of azide polymers. Propellents, Explosives,
Pyrotechnics 1992, 17, 226.
61. Arisawa, H.; Brill, T.B. Thermal decomposition of energetic materials 71:
Structure-decomposition kinetics relationships in flash pyrolysis of glycidyl
azide polymer (GAP). Combustion and Flame 1998, 112, 533.
62. Korobeinichev, O.P.; Kuibida, L.V.; Volkov, E.N.; Shmakov, A.G. Mass spec-
trometric study of combustion and thermal decomposition of GAP.
Combustion and Flame 2002, 129, 136.
63. Faber, M.; Srivastva, R.D. Mass spectrometric kinetic studies on several azido
polymers. Combustion and Flame 1984, 55, 203.
64. Oyumi, Y.; Brill, T.B. Thermal decomposition of energetic materials 12;
Infrared spectral and rapid thermolysis studies of azide containing monomers
and polymers. Combustion and Flame 1986, 65, 533.
65. Chen, J.K.; Brill, T.B. Thermal decomposition of energetic materials. 54.
Kinetics and near-surface products of azide polymers AMMO, BAMO, and
GAP in simulated combusion. Combustion and Flame 1991, 87, 157.
66. Miyazaki, T.; Kubota, N. Energetics of BAMO polymer. Propellants,
67. Chang, T.C.; Wu, K.H.; Chen, H.B.; Ho, S.Y.; Chiu, Y.S. Thermal degradation
of aged polytetrahydrofuran and its copolymers with 3-azidomethyl-30 -methyl-
oxetane and 3-nitratomethyl-30 -methyloxetane by thermogravimetry. J. Polym.
Sci.: Part A: Polym. Chem. 1996, 34, 3337.
68. Liu, Ying-Ling; Hsiue, Ging-Ho; Chiu, Yie-Shun. Thermal characteristics of
energetic polymers based on tetrahydrofuran and oxetane derivatives. J. Appl.
Polym. Sci. 1995, 58, 579.
69. Kubota, N.; Sonobe, T. Combustion mechanism of azide polymers.
Propellants, Explosives, Pyrotechnics, 1988, 13, 172.
70. Goshgarian, J.E.; Beckstead, M.W. Air Force Rocket Propulsion Laboratory:
Edwards AFB, CA, June, 1982.
71. Lengelle, G.; Fourest, B.; Godon, J.C.; Gain, C. In 29th Propulsion Conference
Monterey, CA, 1993, AIAA-92-2413.
72. Mishra, I.B.; Juncau, G.P.; Groom, T. 11th JANNAF Propulsion Meeting,
1984, 7.
Azido Polymers 545
73. Dhar, S.S.; Asthana, S.N.; Singh, H.; Natu, G.N. Fizika Goreniya iVzryva,
Thermal decomposition of GAP and GAP based double base propellents.
Combustion, Explosives and Shock waves, 29 (3), 276, 1993, CfCA 119:229468.
74. Feng, H.T.; Mintz, K.J.; Augsten, R.A.; Jones, D.E.G. Thermal analysis of
branched GAP. Thermochim. Acta 1998, 311, 105.
75. Bazaki, H. Combusion mechanism of 3-azidomethyl-3-methyloxetane
(AMMO) composite propellants. Progress in Astronautics and Aeronautics
2000, 185, 439.
76. Lee, Y.; Tang, Ching-Jen; Litzinger, T.A. Thermal decomposition of RDX/
BAMO pseudo-propellants. Combustion and Flame 1999, 117, 795.
77. Oyumi, Y.; Inokami, K.; Kiyotaka, Y.; Kazuhiro, M.K. Thermal decomposi-
tion of BAMO/HMX propellants. Propellants, Explosives, Pyrotechnics 1993,
18, 62.
78. Hatch, R.L.; Wardle, R.B.; Lund, G.K.; Hamilton, S.R. Solid rocket
propellant formulations contg. isocyanate-cured (azidomethyl)methyloxetane-
bis(azidomethyl)oxetane [BAMO/AMMO] copolymer energetic binders. PCT
Int. Appl. 1995, 21. WO 94-US 7945 19940714; cf CA 1995, 123, 87608.
79. Shen, S.M.; Leu, A.L.; Chen, S.I.; Yeh, H.C. Thermal characteristics of GAP,
GAP/BDNPA/BDNPF and PEG/BDNPA/BDNPF and the energetic compo-
sites. Thermochim. Acta 1991, 180, 251.
80. Oyumi, Y.; Kimura, E. IM characteristics of GAP/AN composite propellants.
Kayaku Gakkaishi 1996, 57.
81. Sayles, D.C. Non nitroglycerin-containing composite-modified double-base
propellant. US Patent 4,707,199, 1987.
82. Reed, R., Jr. Cycloaddition of azide group-containing polyoxyalkylenes by
reaction with aryl diacetylenes to form triazole-crosslinked energetic plasticizers
for composite propellants. US 97-880 710; cf CA 2000, 133, 152741.
83. Golifier, M.; Graindorge, H.; Longevialle, Y.; Mace, H. New Energetic
Molecules and their Applications in Energetic Materials. In 29th Int. Annu.
ICT Conf. (Energetic Materials), 1998, 3.
84. Nielsen, A.T. In ‘‘Chemistry of Energetic Materials’’, ‘‘Polycyclic Amine
Chemistry’’; ed. G. Olah and D. R. Squire, Academic Press Inc. 1991,
Chap. 5, pp 95.
85. Dendage, P.S.; Sarwade, D.B.; Asthana, S.N.; Singh, H. Hydrazinium nitro-
formate (HNF) and HNF based propellants: A review. J. Energetic Materials
2001, 9, 41.
86. Kuwahara, T.; Takizuka, M.; Onda, T.; Kubota, N. Combustion of GAP based
energetic pyrolents. Propellants, Explosives, Pyrotechnics 2000, 25, 112.
87. Martin, W.B.; William, D.V. Azide polymers derivatized with dipolarophiles
for aqueous coatings producing transparent films. Eur. Patent 6,33,280, 2000.
88. Kubota, N.; Sonobe, T.; Yamamoto, A.; Shimizu, J. Burning rate character-
istics of GAP propellants. Propulsion and Power 1990, 6, 686.
89. Klaus, M.; Jutta, B.-M.; Hiltmar, S. Propellants, Explosives, Pyrotechnics
1996, 21, 139.
Copyright of Journal of Macromolecular Science: Polymer Reviews is the property of Taylor & Francis Ltd and
its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's
express written permission. However, users may print, download, or email articles for individual use.

Azido Polymers-Energetic Binders For Solid Rocket Propellants.

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Azido Polymers-Energetic Binders For Solid Rocket Propellants.

Uploaded by

Copyright:

Available Formats

MARCEL DEKKER, INC.

• 270 MADISON AVENUE • NEW YORK, NY 10016

JOURNAL OF MACROMOLECULAR SCIENCEÕ

Azido Polymers—Energetic Binders for

Bharti Gaur, Bimlesh Lochab, V. Choudhary, and I. K. Varma*

Centre for Polymer Science and Engineering,

DOI: 10.1081/MC-120025976 1532-1797 (Print); 1532-9038 (Online)

506 Gaur et al.

4.3. Problems of GAP-Isocyanate Cure . . . . . . . . . . . . . . . . . . . . . . . . . 525

Key Words: Energetic binders; Azide polymers; Poly(allylazide); Oxidizers;

High-energy solid rocket propellants are composite materials having a

Azido Polymers 507

technical performances of solid propellants. Recent advances in propellants

508 Gaur et al.

2. PREPARATION OF AZIDO POLYMERS

2.1. Polymerization of Glycidyl Azide (GA)

The starting monomer, GA is prepared by reacting epichlorohydrin (ECH) with

2.1.1. Derivatization of Polyepichlorohydrin (PECH)

An alternative route, based on the polymerization of ECH to polyepichloro-

Scheme 1. Synthesis of GA.

H O CH CH2 O CH2CH2O CHCH2O H

H O CH CH2 O CH2CH2O CHCH2O H

Scheme 2. Preparation of GAP-diol.

Azido Polymers 509

HOCH2CHCH2OH O CH CH2 OCH2CHCH2O CH2CHO H

H O CH CH2 OCH2CHCH2O CH 2CHO H

Scheme 3. Preparation of GAP-triol.

(a) Synthesis of Polyepichlorohydrin

Polyepichlorohydrin has been synthesized by carrying out the polymerization

510 Gaur et al.

Table 1. Eﬀect of reaction parameters on percent yield of polyepichlorohydrin (data adapted

Sample Monomer/initiator Time Yield

A-1 BF3OEt2 1,2-Dichloroethane 44:1 4.0 98

Temperature 5 C (with dioxane 15 C).

Table 2. Molecular weight distribution of PECH synthesized under diﬀerent reaction

n is the degree of polymerization.

to suppress the propagation reaction and promote a backbiting reaction to produce

Azido Polymers 511

CH2Cl A - CH2Cl CH2Cl CH2Cl A

Scheme 4. Chain growth and backbiting reaction during ECH polymerization.

monomer concentration, which requires slow addition of monomer to the reaction

(b) Azidation of PECH

Azidation of PECH to GAP has been carried out in an organic or an aqueous

512 Gaur et al.

water, in the presence of a phase transfer catalyst (methyl tricapryl ammonium

Azido Polymers 513

2.2. Direct Conversion of Epichlorohydrin to

A single step process for preparation of hydroxy terminated GAP

N3 CH CH2 O CH CH2 O CH2 CH2 O CH2 CH O CH2 CH N3

Scheme 6. Tosylation of PECH followed by azidation.

514 Gaur et al.

H O CH CH2 O CH2 CH2 O CH2 CH O H

O2N O CH CH2 O CH2 CH2 O CH2 CH O NO2

N3 CH CH2 O CH CH2 O CH2 CH2 O CH2 CH O CH2 CH N3

2.3. Simultaneous Degradation and Azidation of PECH

Azido Polymers 515

Table 3. Solution properties of GAP and copolymers prepared by simultaneous degradation

Polymer Polyol [n] (dL/g) Mn Mw

GAP homopolymer PPT 0.122 10,600 18,100

2.4. Block Copolymers of GAP

A triblock copolymer poly(glycidylazide-b-butadiene-b-glycidyl azide) (GAP-

2.5. Polymerization of Azidomethyl Oxetanes

Polymerization of substituted four membered oxetanes can produce polymers

180 C 185 C 190 C 195 C 200 C 205 C 210 C