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Propellants, Explosives, Pyrotechnics 21, 43-50 (1 996) 43

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 Polyisoprhe hydrogin6 B terminaison OH c o m e liant com-
Brennstofminder fur Komposit-Festtreibstdfe bustible pour des propergols solides composites
Versuche zur Synthese von hydriertem Polyisopren mit endst&- Des essais ont Ctt rtalists en vue de synthttiser du polysioprhe
digen OH-Gruppen (HHTPI) zur Anwendung als Binder fur Kom- hydrogtnt B terminaison OH (HHTPI) utilist en tant que Iiant pour
posit-Festtreibstoffe wurden durchgefihrt. Ein HHTPI-Prapolymer des propergols solides composites. Un prtpolym&re HHTPI a t t t
wurde hergestellt durch Hydrierung von Polyisopren mit endstiindi- synthktist par hydrogtnation de polyisoprhe 8 terminaison
gen OH-Gruppen (HTPI) in Gegenwart von Nickel- und Zirco- OH (HTPI) en prtsence de catalyseurs nickel et zirconium sur de
nium-Katalysatoren an Kieselgur mit Wasserstoff bei einem Druck la diatomite dans de l’hydrogtne B 2,O MPa, ? i K-453 K pen-
443
von 2.0 MPa, bei 443 K-453 K warend 24 Stunden. Ein Prapoly- dant 24 heures. Un prtpolym2re posstdant un poids moltculaire
mer mit einem mittleren Molekulargewicht von 2500-3800 er- moyen de 2500-3800 a donnt le niveau de viscosit6 ntcessaire
brachte den f i r den Einsatz als Binder erforderlichen Viskositlits- pour I’utilisation en tant que liant, B partir duquel les propergols
bereich, so daB damit die Festtreibstoffe wahrscheinlich direkt im solides peuvent &trevraisemblablement fabriquts par un processus
GieRprozeB hergestellt werden konnen. Die thennische Stabilitat de coulte directe. La stabilitt thennique et le vieillissement des
und Alterung der HHTPI-Elastomeren gegenuber Umgebungsein- tlastomtres HHTPI contre les agressions exttrieures sont suptr-
fliissen ist der von HTPB-Treibstoffen uberlegen. Einige Weichma- ieurs B ceux des propergols HTPB. Certains plastifiants et agents
cher und Haftvermittler konnen brauchbare mechanische Ei- adhksifs peuvent donner des proprittts mtcaniques utiles aux prop-
genschaften hervorbringen bei Treibsatzen, die hauptsachlich aus ergols composts essentiellement de HHTPI, perchlorate d‘ammo-
HHTPI, Ammoniumperchlorat und Aluminiumpulver bestehen. Die nium et poudre d’aluminium. La vitesse de combustion lintaire de
lineare Abbrandgeschwindigkeit von HHTPI-haltigen Treibstoffen propergols ? base
i de HHTPI se situe au m2me niveau que celle
hat dieselbe GroBe wie bei den HTPB-haltigen. Jedoch verschiebt des propergols 8 base de HTPB. Toutefois, h puissance maximale,
sich die Zusammensetzung der HHTPI-Treibstoffe bei maximaler la composition des propergols HHTPI est d6caEe de 1-2% en
Leistung um 1-2 Gew.% auf die Brennstoffseite im Vergleich zu poids du cStt combustible par rapport 8 la teneur en combustible
dem entsprechenden Brennstoffgehalt bei HTPBl APl A1 mit correspondante de 12% en poids pour HTPBIAPIAl. Les proper-
12 Gew.%. Die HHTPI-Treibstoffe zeigten anliche lineare Ab- gols HHTPI ont donne des vitesses de combustion linkaires sembl-
brandgeschwindigkeiten wie die HTPB-Treibstoffe trotz der ver- ables 8 celles des propergols HTPB en dtpit de leur amorqabilitt
gleichsweise geringen Zundf&igkeit. Dennoch wurden statische proportionnellement plus faible. Toutefois, des tests statiques ont
Tests bei Forschungsraketen mit einem Durchmesser von 100 mm Ct6 rtalists avec succi.s sous pression sur des fusees-sondes de
erfolgreich unter Druck durchgefuhrt. Die ballistischen Leistungen diamktre 100 mm. Les performances balistiques ne sont pas inf6r-
sind nicht niedriger als bei den HTPB-Treibstoffen. ieures B celles des propergols HTPB.

Summary can bring about the acceptable mechanical properties to the propel-
lant grains mainly composed of HHTPI, ammonium perchlorate
The synthesis and application of hydrogenated hydroxy-termi- and aluminium powder. The linear burning rates of HHTPI-based
nated polyisoprene (HHTPI) to a fuel binder of composite solid propellants are at the same level with that of HTPB-based propel-
propellants were attempted. An HHTPI prepolymer was synthe- lants. However, the composition that gives the maximum perfor-
sized through the hydrogenation for the hydroxy-terminated poly- mance with HHTPI-based propellants, shifts to 1-2 wt% fuel-rich
isoprene (HTPI)in the presence of nickel and zirconium catalysts side from the most adequate fuel content 12 wt% in HTPBIAPIAl.
over kieselguhr in 2.0 MPa hydrogen and at 443 K-453 K for The HHPTI propellants indicated the similar burning rate as
24h. A prepolymer of a number-averaged molecular weight HTPB-based propellants in the linear burning rates in spite of the
2500-3800, provided a viscosity level required for the use of a comparatively poor ignitability. Nevertheless, the static tests of
fuel binder from which solid propellant can be possibly made by 100 mm dia. sounding rocket motors are successfully performed
means of direct casting method. Thermal stability and aging char- by an ignition operation at the pressurized condition. The ballistic
acteristics of HHTPI elastomer against environmental attacks are performances are not inferior to those of the HTPB-based propel-
superior to those of HTPB. Some plasticizers and bonding agents lants.

0 VCH Verlagsgesellschaft, 0-6945 1 Weinheim, 1996 0721-3115/96/01/02-043$10.00+.25/0


44 A. Iwama, K. Hasue, T. Takahashi, K. Matsui, and K. Ishiura Propellants, Explosives, Pyrotechnics 21, 43-50 (1996)

1. Introduction polymerization of isoprene monoiners was conducted : hy-


drogen peroxide, 1.2 g-12 g for isoprene monomer, 100 g,
Full saturation of the double bonds in the diene polymer and isopropyl alcohol being used as reaction initiator and
type fuel binders would lengthen the service life, and im- solvent, respectively. The reaction temperature of 400 K
prove the thermal and aging stability. It may increase in the and reaction time of 6 h yielded a polymer of the number-
ballistic performance and lower the vulnerability in the ap- averaged molecular weight, M,, 3800, hydroxyl group con-
plication to solid propellants and plastic bonded explosives. tent of 0.73meq/g and hydroxyl number of 2.19. The
Staudinger(') and Pummerer(2)early in 1922 tried a hydro- mean molecular weight was varied by adjusting the initia-
genation for natural rubber of which ingredient is mostly tor fraction for monomer and reaction temperature. The vi-
cis-polyisoprene. Thomas(3)pointed out that chemical unsa- nyl-microstructure content less than 7.2% in the product
turation, in spite of its importance from a stand point of can insure such a liquid property as HTBP prepolymer.
permitting the vulcanization to take place, induces a great The hydrogenating operation of HTPI under 2.0 MPa and
weakness of the natural rubber concerning the aging pro- 443 K-453 K for 24 h in tetrahydrofuran solvent has satu-
blem. Long time exposure of unsaturated fuel binder in air rated up to 98% in the presence of nickel-over-kieselguhr
would cause the addition of oxygen atoms or hydroxyl catalyst and zirconium co-catalyst.
groups to the double bonds; this would bring about the de- Varying the synthesis condition, we can provide the fob
terioration in mechanical properties and court the combus- lowing prepolymers available for propellant and explosive
tion instability on making the motor firing. The inclusion of binders,
any anti-aging agent in such a propellant as practiced for CH3
butadiene polymer -based propellants are indispensable. I
Joned4) first reported that, when non-functional polybuta- OH-(CH2-CH-CH2-CH2),-OH n = 28-54.
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- 3. Characteristics and Modification of HHTPI
lymers convert to the thermoplastics having a strong oil- Elastomer for the Application to Liner/Insulation
resistance and high tensile strength with their glass transi-
Table 1 shows the fundamental properties of HTPI and
tion point maintained at low values. Nearly 100% hydroge-
HHTPI prepolymers that are suitable for propellant applica-
nation for the polybutadiene including high fractions of
tions at present. Herein, TH-1 and TH-21 are Kurary Com-
trans- and cis-microstructures would form the polybuta-
pany's products, and recently, Atochem-Idemitsu Petro-
diene inelastic even at room temperature. Jones also studied
chem Company, Japan participated in the production of
the hydrogenation of non-functional polybutadiene and de-
HHTPI, EP-25 that has a longer curing time with a combi-
scribed the synthetic process and the results of the analysis
nation of isophorone diisocyanate.
and mechanical property measurements of hydrogenated
The HTPI and HHTPI (TH-21) prepolymer indicate the
polybutadiene. His study avoided a complete hydrogenation
viscosities higher by 6 and 16 times, respectively, than that
because the product would become a waxy state. At pre-
of HTPB prepolymers for the similar mean molecular
sent fully hydrogenated products of 1,4-polybutadiene
weight. However, the propellant dough whose fuel binder
(HTPB) are provided by Mitsubishi Chemical Industries
is either HTPI or HHTPI (TH-21) prepolymer, has not dis-
Co. in Japan.
turbed the mixing and casting operation even in case of
Nisso Chemical Industries Co. is providing almost com-
high solid filler 86-88.5 wt%. It is because a better dough
pletely hydrogenated hydroxy-terminated polybutadiene
fluidity is obtained owing to the more uniform distribution
(HHTPB) with vinyl microstructure. This prepolymer is a
of atomized solid fillers and the addition of conventional or
highly viscous fluid as it indicates a viscosity of 55 P a . s
particular plasticizers. Further, at elevated temperatures,
at 318 K. This value is near the critical viscosity to make
340 K-350 K, we noted the viscocity of TH-21 lowers
the direct casting of propellant dough possible barely.
down to the similar value to that of HTPB as shown in
Thus, vinyl group pendant from every monomer retains a
Fig. 1. The HHTPI prepolymer which we aim to use for
better fluidity and lowers the glass transition temperature,
extrudable propellants, expresses favorable viscosity also
and results in a better processability of the dough made
for the application to plastic bonded explosives.
from 1,ZHHTPB. Linear polymers of fully saturated hy-
Remarkable characteristic of HHTPI consists in a high
drocarbons have a higher glass transition temperature, and
H/C atom number ratio 2.0 whereas H/C of HTPB is 1.5.
the addition of a side arm plays a role to lower the glass
The high hydrogen content contributes to an increase of the
transition temperature. Therefore, we expected that the in-
specific impulse effectively without an elevation of com-
troduction of hydrogen atoms to the double bonds in hy-
bustion temperatures. As shown in Table 2, the perform-
droxy-terminated polyisoprene (HTPI) should not make
ance calculation according to NASA standard computer
viscosity increase till the directs casting becomes difficult.
program(5)demonstrates that the suitable HHTPI fuel-bin-
der content is 13-14 wt% for AP-based propellants with
2. Production of HTPI and HHTPI Prepolymers fixed aluminum content 18-20 wt%. These composition
shifts apparently to fuel rich side compared to the HTPB
Hydroxy-terminated polyisoprene (HTPI) was synthe- propellant for which the most suitable fuel-binder content
sized through a similar procedure to that of HTPB: radical 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 polybutylene adipate (M,, = 500) gives a good mechanical
practice. property but generates smoke slightly. Conventional plasti-
For surveying the appropriate compositions for linerlin- cizers such as dioctyl adipate, dioctyl phthalate, polybu-
sulation applications, aluminum oxide filled and unfilled tene, non-functional HHTPI prepolymer can improve the
HHTPI elastomers were tentatively produced and tested. At elasticity at low temperatures. A composition of the
first, since OH functionality of 2.6 in TH-21 is too many HHTPI-based elastomer has such a good bonding strength
to apply to the linerhsulation, the four different diols are as its peeling test for the sheet sample bonded to a stain-
blended in the HHTPI prepolymer: 1,4-butanediol (BD), less steel plate indicated 1000-1500 g/in at 300 K and
3-methyl-l,5-pentanediol (MPD), 1,9-nonanediol (ND), 300mm/min of peeling rate. As many kinds of hydrocar-
and 2-ethyl-1,3-hexanediol (EHD). Figure 2 shows the bons, ethers, esters, and ketones dissolve HHTPI elasto-
stress-strain curves of the dumbbells made from the mix- mers, it is not difficult work to remove the liner/insulator
tures of prepolymer(TH-21)-isophorone diisocyanate-diol, from motor case.
1 :3 :2 by mole ratio. The mixing operation was conducted An emphasized merit of HHTPI polymer is the possibi-
by one shot method in vacuum condition less than 1 Tom lity that it can provide a binder for smokeless liner/insula-
and the curing for one hour at 393 K. As a diol for smoke- tor. Figure 3 is thennogravimetry curve to show the prop-
less liner or insulation EHD can be recommended, and 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.


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

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