United States Patent (19) [11] 3,798,090

Alabashi (45) Mar. 19, 1974

54 PROCESS FOR PRODUCING 3, 141,294 7/1964 Lawrence et al..................... 149/19

CROSS-LINKED PROPELLANTS 3,215,573 1 1/1965 Winkler............................ 149/19 X
3.245,849 4/1966 Klager et al.......................... 149/19
75) Inventor: John C. Alabashi, Morristown, N.J. 3,260,631 7/1966 Witz et al......................... 49/19 X
3,296,043
(73) Assignee: Hercules Incorporated, Wilmington, 36, i?E.
1967 Fluke et al............................ 149/19
Estam 3.
Del. 3,351,506 1 1/1967 Grigon et al...................... 49/38 X
22 Filed: Dec. 4, 1968
(21) Appl. No.: 781,284 Primary Examiner-Benjamin R. Padgett
Attorney, Agent, or Firn-Michael B. Keehan
Related U.S. Application Data
63 Continuation-in-part of Ser. No. 605,142, Dec. 22,
1966. (57) ABSTRACT
52 U.S. Cl 149/19.4, 149/8, 149/38 Chemically modified double base propellant formula
a a a ww a a l 4939 49/44 i 49/19s tions containing a phenol-blocked diisocyanate as
51) Int. Cl co6d 5f06 cross-liking agent are cross-linked by unblocking the
is 8 Fields. 497,9,8,83992. diisocyanate during propellant cure. A typical formu
149/44 lation contains nitrocellulose, nitroglycerin, ammo
nium perchlorate or cyclotrimethylene trinitramine,
56) References Cited
aluminum and a prepolymer of polyglycoladipate and
2,4-tolvlene diisocyanate
UNITED STATES PATENTS ,4-toly ocyanate.
3,132,976 5/1964 Klager et al.......................... 149/19 10 Claims, No Drawings
 3,798,090
2
PROCESS FOR PRODUCING CROSS-LINKED be soluble in the plasticizer, stable at mixing condi
PROPELLANTS tions, and unstable under curing conditions. Preferably,
the blocked diisocyanate is relatively stable up to about
This application is a continuation-in-part of my co 40°C. and unstable at about 60°C. so that unblocking
pending application Ser. No. 605,142 filed Dec. 22, 5 will take place at a reasonable rate. Suitable diisocya
1966. nates which can be blocked to meet the above criteria
The present invention relates to cross-linkable, nitro include the alkane diisocyanates such as ethylene diiso
cellulose propellant formulations and to a process for cyanate, trimethylene diisocyanate, hexamethylene di
producing cross-linked propellants therefrom. isocyanate and decamethylene diisocyanate; the alkane
It is known that the mechanical properties of double 10 diosocyanates such as 1-propylene-1,2-diisocyanate
base propellants can be improved by using prepolymers and 1-butylene-1,3-diisocyanate; the alkylidene diiso
of polyglycoladipate and tolylene diisocyanate as cross cyanates such as ethylidene diioscyanate and propyli
linking agents for the nitrocellulose. However, unless dene-1,1-diisocyanate; the aromatic diisocyanates such
all of the ingredients are carefully dried and the mois as m-phenylene diisocyanate, p-phenylene diisocya
ture content maintained throughout at less than 0.10 5 nate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocya
percent, propellants with inferior mechanical proper nate, 4,4'-diphenylmethane diisocyanate, naphthalene
ties or porosity result. Furthermore, since cornmercial 1,5-diisocyanate, m-xylylene diisocyanate, 3,3'-
ingredients usually contain about 0.15 percent water dimethoxy-4,4'-biphenylene diisocyanate, and 3,3'-
and even in a “dry system' the moisture content is dimethyl-4,4'-biphenylene diisocyanate; prepolymers
about 0.05 percent, the maintenance of anhydrous con 20 of polyalkylene ether glycols with aromatic or aliphatic
ditions creates additional problems and adds apprecia diisocyanates such as the prepolymer of polyethylene
bly to the cost of the operation. ether glycol, polypropylene ether glycol or polytetra
Now, in accordance with the present invention, it has methylene ether glycol with 2,4-tolylene diisocyanate;
been found that essentially void-free propellants having the prepolymers of hydroxy-terminated polyesters with
the improved properties obtained by the prior process 25 aromatic or aliphatic diisocyanates such as the prepoly
can be produced without the disadvantage of having to mers of polyesters obtained from the reaction of poly
employ anhydrous conditions provided that a blocked ethylene glycol, polypropylene glycol, polybutylene
diisocyanate which unblocks during curing is used as glycol or polyhexamethylene glycol with succinic acid,
the cross-linking agent. adipic acid, sebacic acid, oxadibutyric acid or sulfodi
More particularly, the present invention relates to a 30 propionic acid with 2,4-tolylene diisocyanate, the pre
propellant formulation consisting essentially of nitro polymers of hydroxy-terminated polycaprolactones
cellulose binder, plasticizer, solid oxidizer, metal fuel, and aromatic or aliphatic diisocyanates; the nitrazapen
and a plasticizer-soluble diisocyanate blocked with tadiisocyanates such as 4-nitrazapentadiisocyanate;
phenolic end groupings, and to a process for producing 35
and the like. Such blocked diisocyanates can be readily
an essentially void-free propellant therefrom by mixing produced by methods known to the art, as, for exam
nitrocellulose binder, solid oxidizer, and metal fuel in ple, by reacting the phenol and diisocyanate under ni
the plasticizer containing in solution a diisocyanate trogen at above room temperature, and, if desired in
blocked with phenolic end groupings at ambient tem the presence of a diluent and/or a catalyst.
perature and then curing the mixture under conditions 40
The following examples illustrate but do not limit the
which effect unblocking of the diisocyanate and cross invention. In these examples all parts and percentages
linking of the nitrocellulose. are by weight unless otherwise indicated.
By the term “blocked' diisocyanate as used in the EXAMPLES - O
present invention is meant a diisocyanate which has
been reacted with the active hydrogen of a phenolic 45
Various propellant compositions were prepared
compound, i.e., the isocyanato group -NCO is no using blocked or nonblocked prepolymer of poly
longer terminal. By "unblocked' is meant that the glycoladipate and tolylenediisocyanate (PGA-TDI) in
isocyanato group has been regenerated and become systems containing 0.05 or 0.10 percent water (all in
available for reaction. gredients were carefully dried), 0.15 percent water (in
The blocked nature of the diisocyanate is important 50
gredients used "as received'), or 0.2 percent water
to the invention. As stated, it must be blocked with (additional water introduced through wet ammonium
phenolic groupings. Phenols which are suitable as perchlorate). The nonblocked prepolymer was com
blocking agents are negatively substituted phenols, i.e., mercial prepolymer having a molecular weight of 1,250
phenols substituted with such negative groups as nitro, and containing 5.7 percent isocyanate groups. The
nitroso, cyano, bromo, chloro, iodo, chloromethyl, di 55
blocked prepolymer was prepared by agitating an
chloromethyl, trichloromethyl, ester, keto, and like equivalent weight of m-nitrophenol with an equivalent
groups. Typical of such phenols are o-, m- or p weight of the commercial prepolymer of polyglycoladi
nitrophenol, o-, m- or p-chlorophenol, o-, m- or p pate and tolylenediisocyanate at 80°C. under nitrogen
bromophenol, 2, 4 or 3,4-dinitrophenol, 2,4 or 3,4- for 4 hours, transferring the reaction mixture to storage
dichlorophenol, 2,4 or 3,4-dibromophenol, 4-chloro-2- 60 containers and maintaining at 80°C. without agitation
methylphenol, 4-chloro-3-methylphenol, 3 for 6 days at which time any residual isocyanate was re
cyanophenol, 4-cyanophenol, p-hydroxybutyrylphenol, moved by adding a stoichiometric amount of ethylene
4-hydroxy-3-methyl-acetylphenol, 4-nitro-3- glycol and stirring for 20 hours at 80°C. The propellant
trifluoromethylphenol, 3-iodophenol, 4-iodophenol, compositions were prepared as follows: The prepoly
p-nitrosophenol, p-chloromethylphenol, p 65 mer of polyglycoladipate and diisocyanate (PGA-TDI)
dichloromethylphenol, p-trichloromethylphenol, or the blocked prepolymer thereof (B-PGA-TDI) was
3-hydroxyethylbenzoate, 4-hydroxyethylbenzoate, and dissolved in dry nitroglycerin plasticizer (NG) contain
the like. Additionally, the blocked diisocyanate must ing 0.67 percent stabilizer 2-nitrodiphenylamine
 3,798,090
3 4.
(NDPA) and 0.45 percent of dibutyl tin diacetate cata be tolerated without porosity. The significance of appli
lyst, and the resultant solution evacuated for 20 min cant's findings can be better appreciated by a compari
utes to remove air. The solution was then transferred Son of the amount of water and isocyanate present in
to a mixer into which plastisol nitrocellulose (NC) of the system on an equivalency basis. At the 0.2 percent
2.6 percent nitrogen and 2.3 percent of a stabilizer 5 water level there is a two-fold mole equivalent excess
comprising l percent resorcinol, 1% MnO, and 0.3 of water present per equivalent of isocyanate whereas
percent 2-nitrodiphenylamine, based on the weight of in the "dry' system there is a two-fold excess of isocya
propellant, were added and mixed for about 3 minutes nate to water. Thus the margin of safety with respect to
after which time the ammonium perchlorate (AP) or porosity of grain can be considerably increased through
cyclotrimethylene trinitramine (HMX) oxidizer was O the use of the blocked diisocyanates of the invention.
added and mixing continued for 10 minutes. Into this
mixture was then mixed for 5 minutes the aluminum The amount of blocked diisocyanate necessary to ef
metal (Al) to give a slurry and the resultant slurry was fect cross-linking of the propellant formulation will de
mixed for an additional 15 minutes under vacuum. The pend upon the particular formulation and the cross
slurry was then cast into an appropriate mold, deaer 15 linking agent employed. Generally speaking, amounts
ated for 1.5 hours at 1 mm. Hg and cured for 6 days at of 6 to 9 percent will be sufficient to yield good me
38°C. and 4 days at 60°C. (Exs. 2, 4, and 7) for 4 (Exs. chanical properties while maintaining the impulse level
1, 3, 5, and 6) 5 (Ex. 10) or 7 (Ex. 9) days at 60°C. or of the propellant at a maximum. Cross-linking, as state
for 4 days at 42°C. and 18 days at 60°C. (Ex. 8). The d, is effected by curing the propellant formulation
composition of the propellants of these examples and under conditions which unblock the diisocyanate. Pref
data on the properties of the propellants are tabulated erably, curing is carried out at elevated temperature,
below. as, for example, 38 to 60°C. for 4 to 18 or more days.
PROPELLANT COMPOSITION (Parts by weight) PROPERTIES

Oxidizer Tensile Elongation Modulus

Strength X 10-2
Ex. NC NG PGA-TDI B-PGA-TDI AP HMX Al Catalyst HO(%) (p.s. i.) (%) (p.s. i.)
No. Porosity
40 22 65 ww. 45.0 w 9.0 m O. No 165 95 922
2 40 250 -- 8.5 450 90 0.2 O. N 23 76 938
3 4.0 27.2 6.5 45) - 9. ().2 Yes; Not Porous Porous
obtained
4. 40 250 m 85 45.0 9.0 O.2 0.2 No 168 67 1050
5 6.O 272 65 450 13.0 m 0.05 N 53 55 314
6 6.O 27.2 65 w 450 3O O. 5 Yes Not Porous Porous
obtained
7 6.O 250 am 8.5 450 3.0 0.2 0.5 No 55 59 360
8 6.O. 23.2 55 --- --- 47.0 18.0 O.OS No 46 94. 833
9 3.3 26.9 6.8 w 46.5 6.2 O.15 Yes Not porous Porous
obtained
O 6.O. 233 w 7.8 w 45.4 17.0 O.2 O. 5 No 70 39 77

The above data show that the mechanical properties of When necessary, acid catalysts may also be employed
propellants prepared with blocked prepolymers are to facilitate unblocking. Suitable acid catalysts which
better than those with nonblocked prepolymer when do not affect propellant stability include the organo tin
equal amounts of water are present in the system (com- compounds such as dibutyltindiacetate, dibutyltin
parison of Examples 1 and 2), that essentially the same 45 dilaurate, and the like.
properties can be obtained with 'wet' ingredients Ingredients other than those named above and which
using blocked prepolymer as with 'dry' materials using do not interfere with the cross-linking action or do not
nonblocked prepolymer (Examples 1 v. 4 and 5 v. 7) adversely affect stability of the propellant can also be
and that more water can be tolerated in the system if present in the formulation. For example, the solid oxi
a blocked prepolymer is used (Examples 3 v. 4; 6 v. 7; 50 dizer can be an inorganic or organic oxidizing agent.
and 9 v. O). Thus instead of ammonium perchlorate, other inor
In addition to the procedural and economic advan- ganic oxidizing salts such as the ammonium, alkali
tages of being able to use commercially available ingre- metal or alkaline earth metal nitrates can be used alone
dients without predrying, the use of the blocked diiso- or in mixtures with other inorganic oxidizing salts such
cyanates of the invention offers the safety feature of de- as the chromates, dichromates, permanganates, chlo
sensitizing the plasticizer. rates and perchlorates of the alkali or alkaline earth
As the examples show, by the process of the present metals or ammonia. Likewise, instead of cyclotrimethy
invention it is possible to produce void-free cross- lene trinitramine other organic oxidizers such as cy
linked propellants in the presence of small amounts of clotetramethylene tetranitramine, pentaerythritol tet
water. The maximum amount of water which can be ranitrate, dipentaerythritol hexanitrate, ethylene dini
tolerated in the system without introducing porosity de- tramine, 2,4,2', 4'-tetranitro-oxanilide, 2,4,6,2', 4',
pends primarily upon the amount of nitrocellulose em- 6'-hexanitro-oxanilide, mannitol hexanitrate, ni
ployed. For example, at low nitrocellulose levels (6 troguanidine, lead 2,4-dinitroresorcinate, lead 4,6-
percent or below), void-free cross-linked propellants 65 dinitroresorcinol, trinitrotoluene, and the like can be
can be produced with as much as 0.15 percent water in used alone or in mixtures with each other or with one
the overall system whereas at higher nitrocellulose lev or more of the above inorganic oxidizing salts. Instead
els ( 14 percent), as much as 0.2 percent or more can of nitroglycerin the plasticizer can also be other nitrate
 3,798,090
5 6
esters such as trimethylolethane trinitrate, diethylene 2. The process of claim 1 wherein the plasticizer is a
glycol dinitrate, triethyleneglycol dinitrate, 1,2,4- nitrate ester.
butanetriol trinitrate, bis(dinitropropyl) acetal, bis(- 3. The process of claim 2 wherein the curing is ef.
dinitropropyl) formal, glycerol monolacetate trinitrate, fected in the presence of an unblocking catalyst.
glycol dinitrate, nitroisobutylglycerol trinitrate, and the 5 4. The process of claim 3 wherein the nitrate ester is
like, and other plasticizers such as triacetin, the phos nitroglycerin and the diisocyanate is a prepolymer of
phates such as tributylphosphate, the phthalates, di polyglycoladipate and 2,4-tolylenediisocyanate having
fluoroamino compounds, and the like can also be pres the isocyanate end groups blocked with m-nitrophenol.
ent to improve the compatability or solubility of the
blocked diisocyanate. In addition to aluminum, other O 5. A propellant formulation consisting essentially of
metal fuels such as aluminum hydride, beryllium, beryl nitrocellulose binder, plasticizer, solid oxidizer, metal
lium hydride, zirconium and the like can be used, and fuel, and a plasticizer-soluble, blocked diisocyanate
the propellant can contain other well known agents prepared by reacting a diisocyanate with a negatively
such as processing aids, wetting agents, and the like. substitued phenol.
The formulations of the present invention are suit 15 6. The formulation of claim 5 wherein the plasticizer
able for solution, or slurry or casting powder processes, is a nitrate ester.
and many modifications and variations of the invention 7. The formulation of claim 6 wherein the nitrate
will be obvious to those skilled in the art in light of the ester is nitroglycerin and the blocked diisocyanate is
above teachings. the reaction product of a prepolymer of polyglycoladi
What I claim and desire to protect by Letters Patent pate and 2,4-tolylenediisocyanate with m-nitrophenol.
S:
1. A process for producing a solid propellant com 8. The formulation of claim 7 wherein the oxidizer is
prising mixing at ambient temperature nitrocellulose cyclotrimethylene trinitramine and the metal fuel is
binder, solid oxidizer, and metal fuel with a plasticizer aluminum.
containing in solution a blocked diisocyanate prepared 25 9. The formulation of claim 7 wherein the oxidizer is
by reacting a diisocyanate with a negatively substituted ammonium perchlorate and the metal fuel is aluminum.
phenol and then curing the mixture at 38 to 60°C.
whereby unblocking of the diisocyanate and cross 10. The formulation of claim 9 also containing dibu
linking of the nitrocellulose occurs. tyltindiacetate catalyst.
30 sk xk :k :k :k

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60

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