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Патент USA US3033657

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_ , ited States Patent
1 CC
‘1
3,033,644
Patented May 8, 1962.
2 V
3,033,644
a few minutes, 0.567 gram of calcium was added. The
mixture was allowed to warm to about ~33°~ C. and was’
CALCIUM nEcAnoRANn ADDUCTS AND
METHOD FOR 'I‘HEIR PREPARATION
stirred while re?uxing. The reactants dissolved in ap<
proximately 25 minutes. ‘Then the ammonia wasallowed
John W. Ager, Jr., Buffalo, ‘N.Y., assignor ‘to Olin
Mathieson Chemical Corporation, a corporation of Vir
ginia
5 to evaporate. Vacuum was applied to the system at room
temperature. A gray solid remained in the ?ask. This
No Drawing. Filed Sept. 30. 1958, Ser. No. 764,452
2 Claims. (CI. 23-14)
solid was subjected to an absolute pressure of '1 mm. Hg
for four and one-quarter hours. The ?ask was heated to
110° C. and maintained at this temperature at an absolute
.This invention relates'to the preparation of the new 10 pressure of 1 mm. mercury for one additional hour.
. adduct, calcium decaborane ammonia, CaBwH14-6NH3.
In an inert atmosphere, the solids were washed three
More in particular, this invention relates to the prepara
tion of calcium decaborane ammonia adducts by the direct
reaction of calcium and decaborane while they are dis
solved inliquid ammonia. The reaction is generally con
times, using about 20 ml. portions of normal pentane, to
remove the unreacted decaborane. The solids then were
transferred to a ?lter and extracted four times with a
' 15
ducted at a temperature of from -60° C. to +40° C., ele- '
.vated pressures being used when needed to keep the am
monia‘ in liquid phase. vThe adducts are gray solids and
are soluble in tetrahydrofuran.
The calcium decaborane adducts prepared by the
method of this invention‘can be incorporated with suit
able oxidizers such as ammonium perchlorate, potassium
perchlorate, sodium perchlorate, lithium perchlorate, alu
’ minum perchlorate, amonium nitrate, etc., to yield a solid
total of 50ml. of tetrahydrofuran. A partial solution of
the solids occurred in the tetrahydrofuran. A clear ?l
trate was separated. The remaining material was a dark
metallicsolid and a gray oily material which subsequently
appeared to decompose with a small amount of gas evolu
tion.
'
The ?ltrate was evaporated at room temperature at an
absolute pressure of 1 to 10 mm. of mercury. A light
, yellow solid, frothy and waxy remained. This material
weighed 0.828 gram, approximately a 26 percent yield.
propellant suitable for rocket power plants and other jet 25 An elemental analysis showed that it contained 35.7 per
propelled devices. Such propellants burn with high ?ame
cent boron.
speeds, have high heats of combustion and are of the high
The boron-containing solid material produced by prac
speci?c impulse type. These calcium decaborane adducts
ticing the method of this invention can be employed as
when incorporated with oxidizers are capable of being
an ingredient of solid propellant compositions in accord
formed into a wide variety of grains, tablets and shapes, 30 ance with general procedures which are well understood
all with desirable mechanical and chemical properties.
in the art, inasmuch as the solids produced by practicing
Propellants produced by the methods described in this
the present process are readily oxidized using conventional
application burn uniformly without disintegration when
solid oxidizers, such as ammonium perchlorate, potassium
ignited by conventionalrmeans', such as a pyrotechnic type
perchlorate, sodium perchlorate, ammonium nitrate and
igniter, and are mechanically strong enough to withstand 35 the like. In formulating a solid propellant composition
ordinary handling.
Example I
In this example, 24.0 grams of decaborane dissolved in
‘ a small amount of pcntane were placed in a 250 ml. three
neck ?ask. The ?ask was, connected to a fraction cutter
employing the calcium decaborane products, generally
from 10 to 35 parts by weight of boron-containing mate
rial?and from 65 to 90 parts by weight of oxidizer, such
40 as ammonium perchlorate, are present in the ?nal pro
pellant composition. In the propellant, the oxidizer and
the product of the present process are formulated in inti
of 100 ml. capacity and a “Dry Ice” cold ?nger condenser.
The apparatus was swept with nitrogen. 50 ml. of am
mate admixture with each other, as by ?nely subdividing
.m-onia ‘gas were condensed in the graduated tube of the
each of the materials separately and thereafter intimately
fraction cutter. Then the liquid ammonia was transferred 45 admixing them. The purpose in doing this, as the art is
aware, is to provide proper burning characteristics in the
to the reaction ?ask which was cooled with “Dry Ice.”
?nal propellant. In addition to the oxidizer and the oxi
1.31 grams of calcium were added and as the calcium dis
solved, a blue color formed but quickly faded. A small
dizable material, the ?nal propellant can also contain a
additional amount of calcium (0.05 gram) was then added
binder such as an arti?cial resin, generally of the urea
and the solution remained blue. A coating of calcium 50 formaldehyde or phenol-formaldehyde type, or an arti
oxide on the metal probably made the additional calcium
?cial rubber like substance, the function of the binder
being to give the propellant mechanical strength and at
necessary. The ammonia and pentane were evaporated
and the gray solid obtained was washed with ether and
the same time improve its burning characteristics. Thus,
' submitted for boron and calcium analysis, both of which
in manufacturing a suitable propellant proper proportions
were lower than required for (B10H14)2Ca. The solid was 55 of ?nely divided oxidizer and ?nely divided calcium deca
insoluble in acetone and alcohol and soluble in water.
borane product can be admixed with a suitable binder,
No decaborane odor was noticed.
the proportions being such that the amount of the binder
The vsolid was ground in a mortar in an inert atmos~
is about 5 to 10 percent by weight, based upd'n the weight
of theoxidizer and the calcium decaborane product. The
additional ether. Elemental analysis showed that it con 60 ingredients are thoroughly mixed and following this the,
tained 38.5, 38.5 percent boron and 17.26, 17.24 percent
mixture is molded into the desired shape, as by extrusion.
calcium. An infrared analysis showed that it did not ap
Thereafter, the binder can be cured by resorting to heating ‘Y
pear to contain any B—H_-—B bonds. The elemental‘
at moderate temperatures. For further information con
analysis obtained corresponds to a material having the‘
phe‘re, then re?uxed with ether, ?ltered and washed with
formula B1oI-I14Ca-6NH3.
'
Example II
cerning the formulation of solid propellant compositions,
reference is made to U.S. Patent No. 2,622,277 to Bonnell
et. al. and ‘U.S. Patent No. 2,646,596 to Thomas et al.
I claim:
1. A method for the preparation of a calcium decabo
Decaborane, 2.600 grams,~was placed- in a 300 ml.
three-neck flask equipped with a condenser. The system
was evacuated, then purged with nitrogen. The reactor 70 rane ammonia adduct which comprises reacting calcium
was cooled and 50 ml. of ammonia gas was condensed
into the ?ask in order to dissolve the decaborane. After
metal and decaborane at a temperature of from —-60° to
+40° C. while the reactants are dissolved in liquid am
3,0333%
0
_
a
and evaporating the tetrahydrofuran extract to provide the
calcium decaborane ammonia adduct.
monia‘ and thereafter recovering the adduct- from‘ the re
action mixture.
2. A method for the preparation of a calcium decabo
rane ammonia adduct whichcomprises reacting calcium
metal and'decaborane ata temperature'of from ~69° to
+40°' C. while‘ the-reactantstarery dissolved in:1iquicl'am—
mania-,evaparating the‘ ammonia to provide av solidlresi=
due, extracting the solid residue with tetrahydro?lran',
5
References Cited in the ?le of this patent
Stock: “Hydrides of Boron and Silicon,” page 127
(1935 ) , Cornell University Press»
Stock at 211.: “Z; Anorg: Allgem. Chem-,7’ vol. 228, pages
178-192, (1936‘);
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