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Патент USA US3028282

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United States Patent 0
1
3,028,272
Patented Apr. 3, 1962
1
3,028,272
SELF-IGNITING ROCKET PROPELLANTS CON
TAINING ORGANIC SILANES
Pliny 0. Tawney, Passaic, N.J., assignor to United States
Rubber Company, New York, N.Y., a corporation of
2
former are preferred.
Of this class, the allylic-type
silanes, i.e., those containing the group
I
I
l
I
—C=C-—(|)-Sll—
New Jersey
No Drawing. Filed Nov. 17, 1948, Ser. No. 60,618
are preferred on the basis of cost, availability and per
tion machinery and more particularly relates to the use
of certain chemical igniters for fuels which are based
-(R-—CH=CR’—-CH2—),,Si(R*).,_n where n is an integer
having a value of 3 or 4, R and R’ are each one of the
on a mixture of an organic material and an oxidizing
radicals, hydrogen and lower alkyl (e.g., methyl, ethyl)
formance, particularly those silanes containing three or
four of such allylic-type radicals e.g., allyl, Z-methylallyl,
7 Claims. (Cl. 149-36)
Z-ethylallyl and 3-methylallyl groups. This preferred
This invention concerns self-igniting fuels for combus 10 group of silanes can be represented by the type formula
agent. Such fuels, e.g., gasoline-nitric acid mixtures, have
and R* is one of the radicals, hydrogen and alkyl (e.g.,
been employed in a variety of combustion machines and 15 methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl,
particularly in the jet propulsion type of engines, e.g.,
hexyl, 2-ethylhexyl, heptyl, octyl, nonyl and decyl). R*
is usually hydrogen or lower alkyl particularly methyl.
rockets. However, in such applications, these fuels re
quire ignition either by an electrical or mechanical device
Exemplary of such compounds are diallyl silane, tetra
or by chemical means.
This invention also relates to a new method of causing 20
spontaneous ignition and to a new method of spontane
(Z-methallyl) silane, triallyl silane, tetraallyl silane, di
allyl dimethyl silane, di(2-methylaliyl) dimethyl silane,
allyl trimethyl silane and diallyl ethyl propyl silane. Tetra
allyl silane and triallyl silane are especially preferred.
ously igniting hydrocarbon fuels, particularly in rocket
propulsion.
These allylic-type silanes can be prepared by methods
It has now been found that unsaturated organic silanes
well-known to those skilled in the art, e.g., by the reac
undergo spontaneous ignition when admixed with inor 25 tion of an allylic magnesium halide with a silicon halide.
ganic oxidizing agents, particularly those derived from
The corresponding vinyl and isopropenyl silanes, e.g.,
nitrogen oxides, and it has been further discovered that
divinyl silane, trivinyl silane and trivinylethyl silane are
likewise operable but suffer the disadvantage of higher
such unsaturated silanes are particularly and unexpected
ly efficacious as igniters for fuels based on mixtures of
preparative costs.
combustible organic materials and such inorganic oxidiz
class other unsaturated silanes include bis (trimethylsilyl)
In addition to the above preferred
ing agents. This discovery is particularly surprising in
acetylene.
view of the behavior of the corresponding saturated or
ganic silanes lwhich are relatively ineffective as igniters.
The above unsaturated silanes can be employed as
igniters for a wide variety of combustible organic ma
terials and inorganic oxidizing agents. Suitable combus
Indeed even many of the unsaturated silanes containing
atoms other than carbon, hydrogen and silicon, and par 35 tible organic materials include those well-known to the
art of jet-propulsion fuels such as hydrocarbons (e.g.,
ticularly oxygen, nitrogen and sulfur are markedly in
ferior or completely useless for this purpose.
propane, butane, butene, pentane, pentene-l, isopentane,
In practice, the blend of the combustible organic ma
cyclopentane, methylcyclopentane, hexane, isohexane, cy
terial and the unsaturated silane (preferably from 0.1 to 40 clohexane, heptane, octane, isooctane, mixtures thereof
50% by Weight based on the organic fuel) is admixed in
such as gasoline and kerosene, benzene, toluene and xyl
the combustion chamber of the engine with an appro—
ene), alcohols (e.g., methanol, ethanol, propanol, iso
priate oxidizing agent and ignition occurs instantaneously
thereby initiating combustion of the fuel. Usually at
propanol, ethylene glycol, butanol and butanediol), ethers
‘(e.g., dimethyl ether and dimethyl acetal), aldehydes
‘(e.g., acetaldehyde, butyraldehyde and glyoxal), ketones
(e.g., acetone, methyl ethyl ketone and butyl methyl ke
least 5% of the unsaturated silane based on the hydro 45
carbon is employed. The amount employed should be
tone and acetophenone), amines (e.g., methyl amine, di
suf?cient to e?ect ignition. The amount required for
ignition will depend upon the particular unsaturated silane
methyl amine, trimethyl amine, methyl ethyl amine,
ethanol amine, aniline, N-methylaniline and p-phenylene
used and can be readily determined by those skilled in
the art in the light of this speci?cation.
50 diamine), hydrazines' (e.g., hydrazine, methyl ‘hydrazine,
Since the use of these novel igniters obviates the neces
sity for a mechanical or electrical ignition system, the
design and maintenance of the combustion machine is
dimethylhydrazine and phenylhydrazine). Among such
organic materials the liquid compounds and/or mixtures
correspondingly simpli?ed. Moreover it has been found
Among the inorganic oxidizing agents those derived
thereof are preferred.
that the use of these new chemical igniters introduce few 55 from nitrogen oxides e.g., concentrated nitric acid, fum
ing nitric acid, nitrogen tetraoxide and mixtures of fum
or no additional problems such as corrosion, in?am
mability, toxicity, premature decomposition, etc. and
hence propellant fuels based on these igniters can be em~
ployed in present installations and motors with little or no
ing nitric acid with sulfuric acid have proven satisfactory.
Some mixtures of the above fuels and oxidizing agents
are themselves capable of spontaneous ignition, but even
adaptation. Indeed the combustion reaction of my fuel 60 in such cases I have found that my unsaturated hydro
deposits a protective refractory coating of ?nely divided
carbon silanes decrease the ignition time and improve the
efficacy of such fuel mixtures, particularly with respect
silica on the walls of the combustion chamber, which
to the deposition of a protective silica deposit on the com
retards the development of “hot spots” and other high
bustion chamber as ‘described above.
temperature corrosion phenomena and thus prolongs the
operational life cycle of the engine. This is particularly 65 The following examples disclose the invention in more
detail.
important in the art of jet propulsion since it permits sus
EXAMPLE 1
tained and protracted operation of such engines e.g.,
rockets, with a minimum of maintenance, repair and re
The ignition ensuing from the reaction of the unsatu
placement.
rated silanes with various oxidizing agents derived from
The unsaturated silanes which are operable in this in 70 nitrogen oxides can be illustrated by adding 0.1 g. of the
vention include both alkenyl and alkynyl silanes and the
silane to 0.5 g. of the oxidizing agent. A number of
3,028,272
4
combustion chamber in conjunction with the combustible
organic fuel. The resulting mixture ignites spontaneous
these reactions are tabulated below (Table I) wherein
the abbreviation “Ig.” signi?es that ignition occurs while
“No Ig.” means that no ignition is detected at the above
ly as soon as the materials are mixed.
concentrations.
The term “inorganic oxidizing agent derived from an
Table I
5 oxide of nitrogen” as used herein denotes either the oxides
of nitrogen themselves, particularly nitrogen tetraoxide,
silane
Red
oxidizing Agent
and materials containing nitrogen tetraoxide especially
white
turning nitric oxide, as well as materials containing the
oxides of nitrogen in chemically combined form and ca
White
@1253’; f?lfriglf
(sp,g_; (sp.g.=
N20‘
filignga‘i 10 pable of releasing such oxides of nitrogen under the con
12%
ditions prevailing in the mixing chamber, for example,
1.59-1.00 1.40-1.50)
H2504
concentrated nitric acid_
As used herein the term “dispersion” is used to denote
the mixture of the unsaturated hydrocarbon silane and
_
------- -~ g:
(a) 121512111311 dimefliilsilzineII _ijI?lo %g... N I
in) rrliirrhtiiliiiirignsiiiie...__ rio Ig_._ N3 15m No I?“ No 1g
___.
_____ __
___
o
___
________ __
15 the combustible organic fuel whether such mixture be a
true solution or a_collo1_da1 d1spers1on.
-
(f) Tetrnethyl silane _______ __ N0 Ig___ No Ig___ N0 Ig-.- N0 Ig
‘
.
I
.
.
I clalm as my invention:
1. A self-igniting rfuel obtained by mixing an inorganic
.
Flam glfle‘t?gogli’ iiblse?gn
1“ 3.’
‘
.
y‘
.
.
.‘
. .
_
oxidizing ‘agent derived from an oxide of nitrogen and
aria/219g :3: 15338323 20 selected from the group consisting of concentrated nitric
.
gre
.
allyhc substituents 1s increased.
-
acid, fuming nitric acid, nitrogen tetraoxide and mixtures
Moreover it W111 be
of fuming nitric acid and Sulfuric ‘acid with a liquid hy
noted that, in contrast, the saturated alkyl silanes of
d
231522111?‘ d'lsplay no igmuon' amvl'ty under these same
weight of a poly-2-alkenyl silane of the type formula
I .
.
'
. .
. .
EXAMPLE 2
.
.
‘.
'
rocarbon having dispersed therein ‘from 0.1 to 50% by
25 (R-—CI-I=CR'—-CH2),,Si(R*)4_n where n is 3 or 4, R
and R’ are each one of the radicals, hydrogen, methyl
A number of the most active unsaturated silanes from
‘and ethyl 'and,R*,is one _of the TadiQaIS’ hydrogen’ and
Table I above are employed as igniters for typical hydro-
gszetro'aglgig 35113511122232“? Ptrizsslgflilh:1111:33:“ 6&0‘
°arb9n*’X1d‘Zmg.age“;t mlxmres by addfng 0'1 'g' "f a 30
Solution of the silane in four representative hydrocarbon
to
.
g. o
e oxi izing agent.
e res
as emlgoged
.
g.” meamng
_
d
_
d f
1 Y_
g _ 1
8 me
edge; .stsiagfsiznaizzip .21.";sagadtstaazaaai
ts, ta u ae
.
below (Table II) are indicated by the same abbreviations
tion “
2 A self-igniting fuel obtgariilned b mixin an nor a '
o _
new the
‘ or er ne lgmtlon at
at con-
.
.
.‘
.1
.
.
,
gilil’l?gungttrlfmc ‘fidcld’ EIU‘EEIK ten‘{10nd}? animlgdures
35 ........i.:.ti;t:.
centration” has been added. The concentrations of the
silane in the hydrocarbon fuel are expressed in weight
‘
anatomist:
_
'
_
-
‘
'
gglslign?lleliim fr%1Tt1h0'1 to 50% by Welght of a Poll"
y S1 am’ 0
percent.
8 type ormula
(R—CH=CR'—CH2)nSi(R*)4-n
Table II
Oxidizing Agent
Tetraallyl
Hydrocarbon silane, Cone.
Triallyl
Silane, Cone.
Diallyl
s_gnimetchyl
i
0,
one.
Ally]
sffrimeéhyi
1 ane,
one.
0350111100-- 1° 0 1g
15-0 B- Ig-----
50.0 No Ig.
Benzene_____
18-0 B- 79
50.0 No Ig.
Red fuming HNO° ---------- -- T01uene_____ s 5 lg
‘22.0 B. Ig ................... .. 50.0 No Ig.
Xylene ____ __
20.0 B. Ig--"-
aasolmenu 15
50.0 B. Ig."..- 50.0 No Ig...." 50.0 No Ig.
50.0 No Ig.
Benzene_____
25.0 B. Ig__.._. 50.0 No Ig.._-- 50.0 No Ig.
N10‘ ------------------------ -- To1uene_____
22.0 B. Ig.-..- 50.0 No Ig----- 50.0 No Ig.
Xylene ____ __
28.0 B. Ig--.._ 50.0 No Ig."-.. 50.0 No Ig.
Gasoline____
30.0 B. T!
Benmne_____ {35 0
30.0 B. Ig ................... -
White turning HNO; ........ _.
Tnlmmo
Xylene .... ..
350Ig
Gas01ine..-_ 350
White fuming HNO;,+12% Benzene..___{
H150‘
35.0 Ig ....... _
Toluene..--_
yo Ig_____
Xylene ---- -- {2518 10mm‘
The principles of my invention may be employed
where n is 3 or 4, R and R’ are each one of the radicals,
wherever it is desired to effect spontaneous ignition. My
hydrogen, methyl and ethyl and R* is one of the radi
invention is particularly applicable in the ?eld of jet pro- 70 cals, hydrogen and lower alkyl, said silane being present
pulsion. In the usual application of my invention to jet
in an amount e?ective to cause instantaneous ignition of
propulsion, I provide separate supplies of the oxidizing
the mixture.
agent derived from the nitrogen oxide on the one hand
3. A self-igniting fuel obtained by mixing an inorganic
and of the unsaturated hydrocarbon silane on the other
oxidizing agent derived from an oxide of nitrogen and
hand and meter these materials continuously into the 75 selected from the group consisting of concentrated nitric
3,028,272
5
6
acid, fuming nitric acid, nitrogen tetraoxide and mixtures
said liquid combustible organic material of a poly-2
alkenyl silane of the type formula
of fuming nitric acid and sulfuric acid with a liquid hy
drocarbon having dispersed therein from 0.1 to 50% by
weight of tetraallyl silane, said silane being present in an
where n is 3 or 4, R and R’ are each one of the radicals,
amount effective to cause instantaneous ignition of the
mixture.
4. A self-igniting fuel obtained by mixing an inorganic
hydrogen, methyl and ethyl, and R* is one of the radicals,
hydrogen and lower alkyl, said silane being present in an
oxidizing agent derived from an oxide of nitrogen and
selected from the group consisting of concentrated nitric
amount e?ective to cause instantaneous ignition of the
mixture.
acid, fuming nitric acid, nitrogen tetraoxide and mixtures 10
7. A propulsion fuel consisting of a liquid combustible
organic material selected from the group consisting of
of fuming nitric acid and sulfuric acid with a liquid by
drocarbon boiling in the range of 75-300” C. having
dispersed therein from 0.1 to 50% by weight of tetra—
allyl silane, said silane being present in an amount effec
tive to cause instantaneous ignition of the mixture.
hydrocarbons, alcohols, ethers, aldehydes, ketones,
amines, hydrazine, and substituted hydrazines and from
0.1 to 50% by weight based on said combustible organic
15 material of a poly-2-alkeny1 silane of the type formula
(R--CH=CR’—-CH2),,Si(R*)4_,u where n is 3 or 4, R
and R’ are each one of the radicals, hydrogen, methyl
and ethyl, and R* is one of the radicals, hydrogen and
acid, fuming nitric acid, nitrogen tetraoxide and mixtures 20 lower alkyl, said silane being present in an amount effec
tive to cause instantaneous ignition of said fuel when it
of fuming nitric acid and sulfuric acid with a liquid hy
5. A self-igniting fuel obtained by mixing an inorganic
oxidizing agent derived from an oxide of nitrogen and
selected from the group consisting of concentrated nitric
drocarbon boiling in the range of 75-300“ C. having dis
persed therein from 0.1 to 50% by weight of triallyl
silane, said silane being present in an amount effective
to cause instantaneous ignition of the mixture.
25
is admixed with an inorganic oxidizing agent selected
from the group consisting of concentrated nitric acid,
fuming nitric acid, nitrogen tetraoxide and mixtures of
fuming nitric acid and sulfuric acid.
6. A self-igniting fuel obtained by mixing an inorganic
References Cited in the ?le of this patent
oxidizing agent selected from the group consisting of con
UNITED STATES PATENTS
centrated nitric acid, fuming nitric acid, nitrogen tetra
oxide, and mixtures of fuming nitric acid and sulfuric
2,298,255
Hopkins ______________ __ Oct. ‘6, 1942
acid, a liquid combustible organic material selected from 30 2,356,476
Shappirio ____________ __ Aug. 22, 1944
the group consisting of hydrocarbons, alcohols, ethers,
2,388,161
Kropa _______________ __ Oct. 30, 1945
aldehydes, ketones, amines, hydrazine, and substituted
hydrazines, and from 0.1 to 50% by weight based on
2,474,183
King ________________ __ June 21, 1949
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