Propellants, Explosives, Pyrotechnics 21, 43-50 (1 996)
Hydrogenated Hydroxy-Terminated Polyisoprene
as a Fuel Binder for Composite Solid Propellants
Akira Iwama, Kazuo Hasue, and Terue Takahashi
The Institute of Space and Astronautical Science, Ministry of Education, Culture and Science, 3-I-1-Yoshinodai,
Sagamihara, Kanagawa 229 (Japan)
Kiyoshi Matsui
Harima Plant, Daicel Chemical Industries, Co. Ltd., 805 Umaba Ibokawa-cho, Ibogun, Hyogo 671-16 (Japan)
Kazunari Ishiura
Kashima Laboratories, Kuraray Corporation, 36 Higashi-wada, Kamisumachi, Kashima-gun, Ibaragi 3 14-02 (Japan)
Hydriertes Polyisopren mit endstiindigen OH-Gruppen als
Brennstofminder fur Komposit-Festtreibstdfe
Versuche zur Synthese von hydriertem Polyisopren mit endst&-
digen OH-Gruppen (HHTPI) zur Anwendung als Binder fur Kom-
posit-Festtreibstoffe wurden durchgefihrt. Ein HHTPI-Prapolymer
wurde hergestellt durch Hydrierung von Polyisopren mit endstiindi-
gen OH-Gruppen (HTPI) in Gegenwart von Nickel- und Zirco-
nium-Katalysatoren an Kieselgur mit Wasserstoff bei einem Druck
von 2.0 MPa, bei 443 K-453 K warend 24 Stunden. Ein Prapoly-
mer mit einem mittleren Molekulargewicht von 2500-3800 er-
brachte den f i r den Einsatz als Binder erforderlichen Viskositlits-
bereich, so daB damit die Festtreibstoffe wahrscheinlich direkt im
GieRprozeB hergestellt werden konnen. Die thennische Stabilitat
und Alterung der HHTPI-Elastomeren gegenuber Umgebungsein-
fliissen ist der von HTPB-Treibstoffen uberlegen. Einige Weichma-
cher und Haftvermittler konnen brauchbare mechanische Ei-
genschaften hervorbringen bei Treibsatzen, die hauptsachlich aus
HHTPI, Ammoniumperchlorat und Aluminiumpulver bestehen. Die
lineare Abbrandgeschwindigkeit von HHTPI-haltigen Treibstoffen
hat dieselbe GroBe wie bei den HTPB-haltigen. Jedoch verschiebt
sich die Zusammensetzung der HHTPI-Treibstoffe bei maximaler
Leistung um 1-2 Gew.% auf die Brennstoffseite im Vergleich zu
dem entsprechenden Brennstoffgehalt bei HTPBl APl A1 mit
12 Gew.%. Die HHTPI-Treibstoffe zeigten anliche lineare Ab-
brandgeschwindigkeiten wie die HTPB-Treibstoffe trotz der ver-
gleichsweise geringen Zundf&igkeit. Dennoch wurden statische
Tests bei Forschungsraketen mit einem Durchmesser von 100 mm
erfolgreich unter Druck durchgefuhrt. Die ballistischen Leistungen
sind nicht niedriger als bei den HTPB-Treibstoffen.
Summary
The synthesis and application of hydrogenated hydroxy-termi-
nated polyisoprene (HHTPI) to a fuel binder of composite solid
propellants were attempted. An HHTPI prepolymer was synthe-
sized through the hydrogenation for the hydroxy-terminated poly-
isoprene (HTPI)in the presence of nickel and zirconium catalysts
over kieselguhr in 2.0 MPa hydrogen and at 443 K-453 K for
24h. A prepolymer of a number-averaged molecular weight
2500-3800, provided a viscosity level required for the use of a
fuel binder from which solid propellant can be possibly made by
means of direct casting method. Thermal stability and aging char-
acteristics of HHTPI elastomer against environmental attacks are
superior to those of HTPB. Some plasticizers and bonding agents
0 VCH Verlagsgesellschaft, 0-6945 1 Weinheim, 1996
43
Polyisoprhe hydrogin6 B terminaison OH c o m e liant com-
bustible pour des propergols solides composites
Des essais ont Ctt rtalists en vue de synthttiser du polysioprhe
hydrogtnt B terminaison OH (HHTPI) utilist en tant que Iiant pour
des propergols solides composites. Un prtpolym&re HHTPI a t t t
synthktist par hydrogtnation de polyisoprhe 8 terminaison
OH (HTPI) en prtsence de catalyseurs nickel et zirconium sur de
la diatomite dans de l’hydrogtne B 2,O MPa, ? i K-453 K pen-
443
dant 24 heures. Un prtpolym2re posstdant un poids moltculaire
moyen de 2500-3800 a donnt le niveau de viscosit6 ntcessaire
pour I’utilisation en tant que liant, B partir duquel les propergols
solides peuvent &trevraisemblablement fabriquts par un processus
de coulte directe. La stabilitt thennique et le vieillissement des
tlastomtres HHTPI contre les agressions exttrieures sont suptr-
ieurs B ceux des propergols HTPB. Certains plastifiants et agents
adhksifs peuvent donner des proprittts mtcaniques utiles aux prop-
ergols composts essentiellement de HHTPI, perchlorate d‘ammo-
nium et poudre d’aluminium. La vitesse de combustion lintaire de
propergols ? base
i de HHTPI se situe au m2me niveau que celle
des propergols 8 base de HTPB. Toutefois, h puissance maximale,
la composition des propergols HHTPI est d6caEe de 1-2% en
poids du cStt combustible par rapport 8 la teneur en combustible
correspondante de 12% en poids pour HTPBIAPIAl. Les proper-
gols HHTPI ont donne des vitesses de combustion linkaires sembl-
ables 8 celles des propergols HTPB en dtpit de leur amorqabilitt
proportionnellement plus faible. Toutefois, des tests statiques ont
Ct6 rtalists avec succi.s sous pression sur des fusees-sondes de
diamktre 100 mm. Les performances balistiques ne sont pas inf6r-
ieures B celles des propergols HTPB.
can bring about the acceptable mechanical properties to the propel-
lant grains mainly composed of HHTPI, ammonium perchlorate
and aluminium powder. The linear burning rates of HHTPI-based
propellants are at the same level with that of HTPB-based propel-
lants. However, the composition that gives the maximum perfor-
mance with HHTPI-based propellants, shifts to 1-2 wt% fuel-rich
side from the most adequate fuel content 12 wt% in HTPBIAPIAl.
The HHPTI propellants indicated the similar burning rate as
HTPB-based propellants in the linear burning rates in spite of the
comparatively poor ignitability. Nevertheless, the static tests of
100 mm dia. sounding rocket motors are successfully performed
by an ignition operation at the pressurized condition. The ballistic
performances are not inferior to those of the HTPB-based propel-
lants.
0721-3115/96/01/02-043$10.00+.25/0
44 A. Iwama, K. Hasue, T. Takahashi, K. Matsui, and K. Ishiura
1. Introduction
Full saturation of the double bonds in the diene polymer
type fuel binders would lengthen the service life, and im-
prove the thermal and aging stability. It may increase in the
ballistic performance and lower the vulnerability in the ap-
plication to solid propellants and plastic bonded explosives.
Staudinger(') and Pummerer(2)early in 1922 tried a hydro-
genation for natural rubber of which ingredient is mostly
cis-polyisoprene. Thomas(3)pointed out that chemical unsa-
turation, in spite of its importance from a stand point of
permitting the vulcanization to take place, induces a great
weakness of the natural rubber concerning the aging pro-
blem. Long time exposure of unsaturated fuel binder in air
would cause the addition of oxygen atoms or hydroxyl
groups to the double bonds; this would bring about the de-
terioration in mechanical properties and court the combus-
tion instability on making the motor firing. The inclusion of
any anti-aging agent in such a propellant as practiced for
butadiene polymer -based propellants are indispensable.
Joned4) first reported that, when non-functional polybuta-
diene and copolymers of butadiene and the other com-
pounds are hydrogenated leaving the residual unsaturation
to the extent not higher than 50%, the polymers and copo-
lymers convert to the thermoplastics having a strong oil-
resistance and high tensile strength with their glass transi-
tion point maintained at low values. Nearly 100% hydroge-
nation for the polybutadiene including high fractions of
trans- and cis-microstructures would form the polybuta-
diene inelastic even at room temperature. Jones also studied
the hydrogenation of non-functional polybutadiene and de-
scribed the synthetic process and the results of the analysis
and mechanical property measurements of hydrogenated
polybutadiene. His study avoided a complete hydrogenation
because the product would become a waxy state. At pre-
sent fully hydrogenated products of 1,4-polybutadiene
(HTPB) are provided by Mitsubishi Chemical Industries
Co. in Japan.
Nisso Chemical Industries Co. is providing almost com-
pletely hydrogenated hydroxy-terminated polybutadiene
(HHTPB) with vinyl microstructure. This prepolymer is a
highly viscous fluid as it indicates a viscosity of 55 P a . s
at 318 K. This value is near the critical viscosity to make
the direct casting of propellant dough possible barely.
Thus, vinyl group pendant from every monomer retains a
better fluidity and lowers the glass transition temperature,
and results in a better processability of the dough made
from 1,ZHHTPB. Linear polymers of fully saturated hy-
drocarbons have a higher glass transition temperature, and
the addition of a side arm plays a role to lower the glass
transition temperature. Therefore, we expected that the in-
troduction of hydrogen atoms to the double bonds in hy-
droxy-terminated polyisoprene (HTPI) should not make
viscosity increase till the directs casting becomes difficult.
2. Production of HTPI and HHTPI Prepolymers
Hydroxy-terminated polyisoprene (HTPI) was synthe-
sized through a similar procedure to that of HTPB: radical
Propellants, Explosives, Pyrotechnics 21, 43-50 (1996)
polymerization of isoprene monoiners was conducted : hy-
drogen peroxide, 1.2 g-12 g for isoprene monomer, 100 g,
and isopropyl alcohol being used as reaction initiator and
solvent, respectively. The reaction temperature of 400 K
and reaction time of 6 h yielded a polymer of the number-
averaged molecular weight, M,, 3800, hydroxyl group con-
tent of 0.73meq/g and hydroxyl number of 2.19. The
mean molecular weight was varied by adjusting the initia-
tor fraction for monomer and reaction temperature. The vi-
nyl-microstructure content less than 7.2% in the product
can insure such a liquid property as HTBP prepolymer.
The hydrogenating operation of HTPI under 2.0 MPa and
443 K-453 K for 24 h in tetrahydrofuran solvent has satu-
rated up to 98% in the presence of nickel-over-kieselguhr
catalyst and zirconium co-catalyst.
Varying the synthesis condition, we can provide the fob
lowing prepolymers available for propellant and explosive
binders,
CH3
I
OH-(CH2-CH-CH2-CH2),-OH n = 28-54.
3. Characteristics and Modification of HHTPI
Elastomer for the Application to Liner/Insulation
Table 1 shows the fundamental properties of HTPI and
HHTPI prepolymers that are suitable for propellant applica-
tions at present. Herein, TH-1 and TH-21 are Kurary Com-
pany's products, and recently, Atochem-Idemitsu Petro-
chem Company, Japan participated in the production of
HHTPI, EP-25 that has a longer curing time with a combi-
nation of isophorone diisocyanate.
The HTPI and HHTPI (TH-21) prepolymer indicate the
viscosities higher by 6 and 16 times, respectively, than that
of HTPB prepolymers for the similar mean molecular
weight. However, the propellant dough whose fuel binder
is either HTPI or HHTPI (TH-21) prepolymer, has not dis-
turbed the mixing and casting operation even in case of
high solid filler 86-88.5 wt%. It is because a better dough
fluidity is obtained owing to the more uniform distribution
of atomized solid fillers and the addition of conventional or
particular plasticizers. Further, at elevated temperatures,
340 K-350 K, we noted the viscocity of TH-21 lowers
down to the similar value to that of HTPB as shown in
Fig. 1. The HHTPI prepolymer which we aim to use for
extrudable propellants, expresses favorable viscosity also
for the application to plastic bonded explosives.
Remarkable characteristic of HHTPI consists in a high
H/C atom number ratio 2.0 whereas H/C of HTPB is 1.5.
The high hydrogen content contributes to an increase of the
specific impulse effectively without an elevation of com-
bustion temperatures. As shown in Table 2, the perform-
ance calculation according to NASA standard computer
program(5)demonstrates that the suitable HHTPI fuel-bin-
der content is 13-14 wt% for AP-based propellants with
fixed aluminum content 18-20 wt%. These composition
shifts apparently to fuel rich side compared to the HTPB
propellant for which the most suitable fuel-binder content
is around 12 wt%. Therefore, to some degree a casting dif-
Propellants, Explosives, Pyrotechnics 21, 43-50 (1996) Hydrogenated Hydroxy-Terminated Polyisoprene as a Fuel Binder 45

Table 1. Liquid Prepolymers of Hydroxy-Tenninated Polyisoprenes

Name TL-20 TH-1 TH-21 EP-25

CH3
Molecular Structure I
HO-(CH2-C=CH-CH2),-OH OH- -(CH2-CH-CH2 -CH2), -OH
Densit at 289 K, 910 860 860 860
[kglm 1
Y
Number Averaged 2600 3800 2700 2500
Molecular Weight(')
OH Value(2' 62.8 32.8 56.1 50.1
(ms KOH/g)
OH Number per one 2.9 2.2 2.6 2.25
Molecule
Viscosity at 308 K, 15 310 40 38
[Pa . s](~)
Heat of Formation, +18.1 -20 -560 -350
AHf [kJ/kg]
Glass Transition 218 218 218 21 8
Temperature, [K]

(1) Vapor pressure osmosis

(2) Acetylation method
(3) Broodfield/Lockwood type viscometer

Table 2. Performance Comparison among HHTPI-, HTPI- and HTPB-Based Propellants

Mixing Ratio by Combustion Combustion Mean Characteristic Nozzle Specific

Weight Pressure Temperature Molecular Velocity Coefficient Impulse
Weight
[MPal IKI Wmo11 [m/sl [SI

HHTPI HHTPI/AP/Al 5.0 3364 27.00 1581 1.567 252.7

= 13/69/18 7.0 3389 27.08 1585 1.616 261.2
HHTPI/ AP/AI 5.O 3287 26.30 1582 1.565 252.5
= 14/68/18 7 .O 3309 26.37 1586 1.613 260.8

HTPI HTPI/ AP/ A1 5.0 3440 27.90 1574 1.594 251.6

= 12/70/18 7.0 3469 27.99 1578 1.634 260.1
HTPI/AP/ A1 5.0 3369 27.23 1574 1.566 25 1.4
=12/68/20 7.0 3395 27.31 I579 1.614 259.8

HTPB HTPB /APIA1 5.0 3486 28.85 1560 1.570 249.7

= 12/70/18 7.0 3517 28.95 1.564 1.619 258.2
HTPBl AP/ A1 5.0 3514 29.17 1559 1.572 249.8
= 12/68/20 7.0 3546 29.29 1563 1.621 258.3

ficulty due to the poor fluidity of HHTPI can be relaxed in
practice.
For surveying the appropriate compositions for linerlin-
sulation applications, aluminum oxide filled and unfilled
HHTPI elastomers were tentatively produced and tested. At
first, since OH functionality of 2.6 in TH-21 is too many
to apply to the linerhsulation, the four different diols are
blended in the HHTPI prepolymer: 1,4-butanediol (BD),
3-methyl-l,5-pentanediol (MPD), 1,9-nonanediol (ND),
and 2-ethyl-1,3-hexanediol (EHD). Figure 2 shows the
stress-strain curves of the dumbbells made from the mix-
tures of prepolymer(TH-21)-isophorone diisocyanate-diol,
1 :3 :2 by mole ratio. The mixing operation was conducted
by one shot method in vacuum condition less than 1 Tom
and the curing for one hour at 393 K. As a diol for smoke-
less liner or insulation EHD can be recommended, and
polybutylene adipate (M,, = 500) gives a good mechanical
property but generates smoke slightly. Conventional plasti-
cizers such as dioctyl adipate, dioctyl phthalate, polybu-
tene, non-functional HHTPI prepolymer can improve the
elasticity at low temperatures. A composition of the
HHTPI-based elastomer has such a good bonding strength
as its peeling test for the sheet sample bonded to a stain-
less steel plate indicated 1000-1500 g/in at 300 K and
300mm/min of peeling rate. As many kinds of hydrocar-
bons, ethers, esters, and ketones dissolve HHTPI elasto-
mers, it is not difficult work to remove the liner/insulator
from motor case.
An emphasized merit of HHTPI polymer is the possibi-
lity that it can provide a binder for smokeless liner/insula-
tor. Figure 3 is thennogravimetry curve to show the prop-
erty that HHTPI decomposes completely at the
46 A. Iwama, K. Hasue, T. Takahashi, K. Matsui, and K. Ishiura Propellants, Explosives, Pyrotechnics 21, 43-50 (1996)

200 r temperatures less than 770 K, and no carbonaceous residue

is left. On the other hand, HTPB generates smoke and
leaves 3%-4% residue to the original sample amount. Ac-
cordingly, HHTPB may be a material to develop smokeless
liner/insulator and HHTPI-based propellant would not gen-
erate a great deal of soot even in fuel rich compositions or
when used as a fuel composition of hybrid propellant.

4. Thermal and Aging Properties of HHTPI

It is presumed that HHTPI exhibits an intensive resis-

tance against thermal attack and degradative oxidation be-
cause of its saturated molecular structure. We compared
HHTPI and HTPB elastomers by exposing test pieces in air
at 423 K and 473 K. The ingredients of test pieces are a
- mixture of prepolymer - IPDI-BD, 1 : 3 : 2 by mole. The
HTPB, Poly-BD, supplied by Atochem-Idemitsu Petro-
1 1 I
chemical Co. is equivalent to HTPB, R-45 HT, produced
by Elf-Atochem, France. The difference of HHTPI from
HTPB elastomer subjected to an accelerated thermal attack
appeared in the color aspect. The addition of oxygen atoms
and/or hydroxyl groups to the double bond of HTPB made
Figure 1. Viscosity of HHTPI, HHTPB and HTPB prepolymer. the test piece brownish and caused numerous cracks to in-
troduce a poor elongation in the material test.
nn Table 3 is an evaluation result on the deterioration prop-
Sample : TH-21/IPDI/Short Chain Diol=1/3/2(mole) erty for three polymers having the saturated hydrocarbons
Diols : BD 1,4-butanediol
MPD 3-methvl-l,5-~entadiol as the main chain. The test pieces were soaked in distilled
15 - ND 1,9-noianedioi
EHD 2-ethyl-1,3-hexanediol
hot water at 373 K. In this case, methylene bis(4-phenyl
,-. Tensile Rate : 500mm/min, 298K diisocyanate) is used as a common currant for three differ-
a
.5, ent polyols; polybutyl adipate (M, = 2000), polytetra-
b 10- methylene glycol (M, = 1000). The ingredient ratio of the
Lo
2 test piece is prepolymer-MDI-BD, 1 :3 :2 by mole and the
3 mixing and curing are done at 393 K by one shot method.
The dumbbell configuration and test procedure are pro-
duced and performed according to the Japan Industrial Spe-
cification K6301-1962 for rubbers. On soaking these dumb-
500
Strain, E (%)
bells in hot water the PTG and HHTPI elastomer would
induce an increase in elongation without a remarkable de-
Figure 2. Stress-strain curves of some HHTPI elastomers (num- crease in the tensile strength. The PBA lost rapidly the me-
bers in parenthesis indicate shore hardness). chanical integrity to come back to the liquid state 168 h
after. As for HTPB the attack of hot water at the first stage
is directed to the OH addition to the double bond, keeping
pace with the cleavage of the urethane bond. If the main

Heating Rate : lO%/min Table 3. Deterioration of Saturated Hydrocarbon Polymers in Hot

80 - Water
-5 Sample Compositions
2 60- Polyol TH- 1 PBA PTG
U Isocyanate MDI MDI MDI
HHTPI(TH-21)/IPDI = l / l ( m o l e )
0 Short Chain Diol 1,4-BD 1,4-BD 1,4-BD
4 40 - HTPB(P-41)/IPDI=l/l(mole)
VI
K
0 ob Eb ob Eb ob Eb
Blank 100 100 100 100 100 100
20 -
4 days 100 113 65 130 74 122
8 days 90 111 16 110 68 126
I I I 12 days 93 118 unmeasurable 66 126
Temperature, T (‘C) ob; Ratio to the tensile strength of virgin samples to that of pro-
cessed samples at break point.
Figure 3. Thermogravimetry curves of an HHTPI and HTPB poly- &b; Ratio to the elongation of virgin samples to that of processed
mer. samples at break point.
Propellants, Explosives, Pyrotechnics 21, 43-50 (1996) Hydrogenated Hydroxy-Terminated Polyisoprene as a Fuel Binder 47

Table 4. Aging Property of HHTPI and HTPB gives HHTPI a high thermal stability and long shelf life.
~~-
However, high viscosity of HHTPI prepolymer, exceeds by
Process- Sample
ing Time HHTPI HTPB * eight times the value of HHTPI having a similar M, of
[hl Mechanical Properties around 3000. Fortunately, the appropriate compositions that
ob Emax El00 OP Emax EIOO generate the maximum specific impulse, shift 1-2 wt%
[MPal [%I [MPal [MPal [%I [MPa] fuel rich side by weight from that of HTPB-based propel-
0 2.1 580 0.19 5.0 250 1.8 lants. The addition of plasticizer or viscosity depressant is,
100 1.9 610 0.22 2.2 30 1.6 however, required to accomplish the direct casting opera-
300 1.8 610 0.21 1.9 0 0 tion of TH-21 based propellant dough.
500 1.7 550 0.23 1.8 0 0 We obtained a dough castable smoothly at 308 K by
~~-

* No anti-aging agent included.

chain is the saturated hydrocarbon the action of hot water
is primarily directed to the cleavage of the urethane bonds
rather than against the fission of prepolymer chains.
Thus, the saturated hydrocarbon chains implied a strong
resistance against the hot water attack so that the deteriora-
tion of HHTPI elastomer is delayed. However, the liberated
prepolymer migrates in the matrix and takes a behavior like
a plasticizer. Therefore, on soaking the test pieces in hot
water the elongation of any polyurethane elastomer in-
creases to some extent once. Although in case of HTPB
elastomer the OH or 0 addition to the double bond at
373 K is limited on the surface, it should be noted the pre-
polymer with only 1% loss of double bonds due to oxida-
tion brings a vital effect on the mechanical property of the
tailored elastomer(6).The addition of oxygen to the double
bonds with a HTPB prepolymer that not included anti-
aging agent and was stored more than ten years, would
form a hard skin on the liquid surface and make the grain
brittle remarkably.
An accelerated aging test, cyclic exposure in water and
on hot panel witnessed to cause a rapid deterioration for
HTPB because the loss of double bonds and cleavage of
urethane bonds go on simultaneously. Saturated polymers,
HHTPI and HHTPB revealed and excellent anti-aging prop-
erty. This test was carried out by means of a xenon weather-
ometer (Shimazu VW-6OV3, lamp output 4.5-6.5 kW); the
test conditions were decided as the black panel temperature
335 K, the rain period 18 min for one cycle 102 min, 15%,
and hot air exposure period 84min for 102min, 85% for
the samples prepared from the same currant and short chain
diol with the test pieces for the previous hot water dete-
rioration test. Table4 compares the aging property of
HHTPI with that of HTPB. No significant deterioration of
HTPB elastomer is seen within the first 100 h but after
300 h both the elongation and tensile strength become
nearly zero. Superiority of HHTPI and HHTPB in terms of
the aging characteristics derives itself from the toughness
of the main chain against the chemical attacks.
5. Modification of HHTPI Prepolymer for the Applica-
tion to Fuel Binders
The predicted advantage of HHTPI is a possibility to
become a fuel binder with which solid propellant can gen-
erate a ballistic performance not inferior to HTPB-based
propellant. Besides, the main chain saturated with hydrogen
adding 10-23 phr of conventional plasticizers such as dioc-
tyl adipate (DOA), dibutylphthalate (DBP), di- (2-ethylhex-
y1)azelate (DOZ), isodecyl pelargonate (IDP) and non-func-
tional saturated liquid olefin polymers to the HHTPI
prepolymers. After many diisocyanates have been checked,
isophorone diisocyanate was nominated most favorable.
But, at present, commercially available HHTPB prepolymer
of OH functionality 2.6 and M, 2700, indicated too fast
curing rate to produce large propellant grains over 500 kg.
For this purpose, it is required to add a curing rate retarder
such as tetracycline(7).Another prepolymer EP-25 reduced
to OH functionality down to 2.2 as indicated in Table 1,
guarantees a pot life or zero flow time enough to take a
long time casting operation.
6. Combustion Property of HHTPI-Based Propellants
and Firing Results
We produced tentatively a series of HHTPI-based propel-
lants aiming the final application to a sounding rocket. The
compositions and mechanical properties are shown in Ta-
ble 5. Herein, it must be stressed that without bonding
agent HHTPI grain manifests a very poor mechanical prop-
erty to reject the practical use. The inclusion of a proper
bonding agent to realize a mechanical property level in-
sures a stable motor combustion. Methylamino- bis (methyl-
2-aziridinyl-1) phosphoric oxide [MEBAPO] is one of the
good bonding agents.
The results of linear burning rate measurements for the
strands are shown in Fig. 4. The pressure exponent is 0.46,
0.47 and 0.5 for A, B and C composition, respectively.
This values are 5-8% higher than the pressure exponent of
HTPB-based propellants, but acceptable enough for inside-
burning motors. The level of the linear burning rate is
nearly equal to that of HTPB-based propellants at the op-
eration pressures of conventional motors for the same pro-
pellant compositions. As the best performance composition
of HHTPI-based propellants shifts to fuel-rich side, the
composition A and B that is expected to issue the maxi-
mum performance have the burning rates a few percent
lower than would have a composition of 12 wt% HTPB,
70 wt% AP and 18 wt% Al.
As for the mechanical properties the propellant grains A
and B in Table 5 could pass our specification. A rp 70 mm
heavy wall motor loaded with the HHTP-based propellants
3.2 kg were static-fired. An example of pressure- and
thrust-time histories are shown in Fig. 5. Through the firing
tests, we noticed the startability of the motors loaded with
48 A. Twama, K. Hasue, T. Takahashi, K. Matsui, and K. Ishiura Propellants, Explosives, Pyrotechnics 21, 43-50 (1 996)

____. ~~ ~

Compositions Mechanical Properties

AP HHTPI A1 MEBAPO Max. Tensile Elongation Young's
Tensile Strength at Break Modulus
Strength at Break Point E
omax Point Eh
oh
[wt%] [wt%l [wt%] [phrl [MPaI ["/.I ["/.I [MPal

A* 68 14 18 0 0.58 0.39 4.8 8.3

A 68 14 18 3.5 1.57 1.50 21.3 11.7
B 69 13 18 3.5 1.62 1.58 18.2 13.4
C 70 12 18 3.5 2.4 1 2.30 16.9 17.6

HHTPI-based propellants is considerably poor. If the igni- polymer are rich in reactivity, so no ignition problem has
tion material amount is short, the conventional igniter B/ been noted except very low temperature conditions in
KNO3 granules and pellets, independently of the fuel-bin- HTPB propellants.
der content of HHTPI 11.5-14.0 wt%, might take around We already observed that the highly aluminum oxide
one second from the ignition to the build-up of chamber filled HHTPI approached a self-extinguishing feature and
pressure as seen in Fig. 5 if any measure is not made other- the ignitability of HHTPI-based propellants is poor at
wise. A considerable increase in the amount of B/KNO3 around 0.1 MPa nitrogen through the static firing test and
igniter might make the pressure build-up time shorten with- the burning rate measurement. In a nitrogen flow at the
out and allowable delay. The allyl carbon atoms in HTPB pressure less than 0.2 MPa, it is difficult to maintain self-
sustaining combustion after the ignition with a Joule-heated
nickel/chrome alloy wire, and a spontaneous burning inter-
ruption was often observed. It has been proved also in mo-
tor firings that the flame spreading along the surface is ex-
tremely slow even though the igniter's burning products
run over the grain channel. Krupp ignition test was made
to know the ignitability when the bulk heating is imposed
on the sample at given temperatures. Figure 6 indicates the
ignition delay of HHTPI-based propellant is approximately
twice longer compared to that of HTPB-based propellants.
To observe the burning-interrupted surface we identified the
IHHTPI~ AP 1 AL IMEBAPO* presence of a thin liquid layer that is mostly liquid prepoly-
-1 14 I68 I 1 8 I 3.5 mer coming back from the polymer.
-.+.- The reactions HHTPI rendered as a fuel-binder, present a
different aspect from HTPB in the preignition process. Be-
fore the decomposition of main chain and the subsequent
ignition occur, the following reactions are presumed
(s. next page).
On heating or irradiating the polybutadiene elastomer
strongly, the hydrogen atoms with methylene group adja-
cent to the double bond unit are easily withdrawn from the
main chain, and radicals having an allyl structure are

12r

Figure 5. Pressure- and thrust-time history showing the de-

layed pressure build-up of 3.2 kg HHTPI-based propellant
Time, t (s) grain (HHTPI 12 wt%, AP 70 wt%, cp 5 Frn Al 18 wt%).
Propellants, Explosives, Pyrotechnics 21, 43-50 (1996) Hydrogenated Hydroxy-Terminated Polyisoprene as a Fuel Binder 49

HHTPI

yH3 H 7%
-(CH,-CH-CH,-CHJ,-O-C-N-R --heat, hv - (CH,-CH-CH,-CH,),- + - 0 - C - N - R
II
0 0

HTPB

-(cH,- CH = CH - CH,), - GT -(CH - CH =CH -cH,)- = (CH= CH - CH - CH,)-

1%
- (CH- CH = CH -CH2)-
I
0
I
0

ethane bond and the surface is covered with a liquid layer

of HHTPI prepolymer. This liquid layer impedes the quick
A :HHTPI 12wt%
A :HTPB 12wt% A
A flame propagation along the initial propellant surface and
At : I 8 w t % A becomes the cause of a long delay till the build-up of the
I
AP : Balance chamber pressure from the action of igniter.
This disadvantage imposed upon us to take some mea-
sures in order to get quick pressure build-up. We have tried
the installation of a nozzle closure to be removed upon the
pressure rise beyond 2 MPa with a thin wall cp 100mm
motor (Fig. 7). This motor was prepared as an upper stage
motor that we have developed for the two-stage rocket for
1.2 1.3 1.4 1.5 1.6 1.7
sounding a middle stratum 30- 100 km altitude. Figure 8 is
Reciprocal of Ambient Temperature , x 10’ (K”) a pressure- and thrust-time history ‘example. The delay
from the igniter initiation to the build-up of thrust is within
Figure 6. Krupp ignition test result showing a poor ignitability of an allowable period 150 ms.
HHTPI propellant.

formed(@. These free hydrogens and ally1 radicals react
with the ambient oxidizing gases rapidly and make a trig-
ger to ignition. Accordingly, there is no serious ignition
delay problem with HTPB-based propellants. On the other
hand, such a fully saturated hydrocarbon chain as HHTPI
is chemically tough, hydrogens are not liberated from main
chain at a very short stage while the propellant receives
much enery from igniter. Rather a large part of the energy
issued from igniter is consumed for the cleavage of ur-
7. Conclusions
(1) Hydrogenated hydroxy-terminated polyisoprene is a
promising fuel binder for producing thermally stable, high
anti-aging and anti-humidity composite solid propellants,
and it provides a smokeless insulator/liner. The viscosity of
the prepolymer that has 2500-3800 of number-averaged
mean molecular weight, and 2.2-2.6 of OH functionality,
is not so high for us to undergo hardships to perform the
direct casting operation of the highly filled propellant
dough. For this purpose, the use of some plasticizers such
as dioctyl adipate, isodecyl pelargonate, non-functional hy-
drogenated polymers, etc. is indispensable and these may

+ l o 0 Motor
Ignitor Grain
/

1 1 2 0 4 -
Figure 7. A cp 100 mm motor
1394 nominated as the second stage of
(unit : mm) meteorological sounding rocket.
50 A. Iwama, K. Hasue, T. Takahashi, K. Matsui, and K. Ishiura Propellants, Explosives, Pyrotechnics 21, 43-50 (1 996)

1000 the powerful igniter can overcome this disadvantage in

14- 900- practical motor applications. However, further investiga-
12- 800-
tions are required on the ignition and combustion character-
m istics.
A
a 700 -
z
Y 10-"M
5 600-
a"
8- 500- 8. References
2 -
Y)

2 6 - f2 400- (1) H. Staudinger, Helv. Chim. Acta 5, 785-806 (1922).

a (2) R. hmmerer and P. A. Burkard, Ber: 55, 3458 (1922).
L
300 -
d (3) R. M. Thomas, I. E. Lightbown, W. J. Sparks, P. K. Frolich,
E
K
. 4- 200- and E. V. Murphree, Znd. Eng. Chem. 32, 1283-1288 (1940).
0
2- 100- (4) R. V. Jones, C. W. Moberly, and W. B. Reynolds, Ind. Eng.
Chena. 45, 1117-1122 (1953).
0-
(5) S. Gordon and B. J. McBride, NASA SP-273 ( 1 97 1 ).
0- d

I I I I I I
(6) H. Tokui and A. Iwama, J. Jupan Ind. Expl. Soc. 52, 2,

play a role to improve the mechanical property at low tem-

peratures.
(2) The ballistic performance of HHTPI-based propel-
lants is not inferior to that of HTPB-based propellants.
(3) The high thermal stability of the native polymer
leads to a little poor ignitability of tailored grains. An
ignition operation at pressurized conditions, or the use of (Received June 7, 1994; Ms 19/94)