Professional Documents
Culture Documents
[1 1]
4,243,444
Alley et al.
[45]
Jan. 6, 1981
[54]
[75]
Inventors:
[73] Assignee:
3,103,458
3,138,499
9/1963
6/1964
3,228,338
1/1966
McEwan et a1. .
149/98
3,228,815
1/1966
Henry et al. . . . . . .
. . . . .. 149/98
3,379,010
4/1968
[57]
ABSTRACT
[5
approximately
149/18; 149/20
Of Search ...................... ..
[56]
98, 18,
References Cited
3,032,972
5/1962
3,088,858
5/1963
H130" F
i
inA1
izi'w'o
BRUATENHI/SGO)
I
456%8510
PRESSURE(PSI x lo'3)
4,243,444
PROPELLANTS
IV herein below.
Existing
similiar
modi iers
t e
type
isc ose
EMBODIMENT
.
and storage to create serious problems. The monobasic 10 they are S?dh.a5t:f if approxm?ltely O'h5 to.6'per_
give betaqesorcylic acid as a product The acid Subse_ 15 these modi?ers is that they are very stable chemically,
is an object of this invention to provide ballisticmodi?- 20 l o e ase pro?le ants ma 6 y t e sodlggnt or so.v?nt'
ers that are stable and do not cause adverse side effects
this invention
25 compounds of salicylic and beta-resorcylic acids. They
A further object of this invention is to provide ballisgenefany react Wlth each other durmg propellant Pro
tic modi?ers that can be used in solvent, solventless and
zlgzfnlclzvig2221:3221tigeggtgllgiigf?geggg2233:;
duce mesa and/or plateau urning rate characteristics 35 problem of the DRAGON 51de thruster propellant.
SUMMARY OF THE INVENTION
The modi?ers described in this invention disclosure
This invention relates to chelate type ballistic'modi?ers for double base propellants and the processes of
ers are synthesized by either reacting metal ions with 4'0 .ers W111 producg ploljenanl mesa and/qr plateau bum
chelating agents in a reaction liquid or by reacting chemg. rate fcshoaorgctgrllstg?o wllh low 77K m the pressure
lating agents that already contain metal with each other
reglon o
to
ps1
100 c. The temperature at which the reaction takes 45 _A list of the most important ballistic modi?ers is
place is chosen according to the speed of reaction degwell m Table I ll'elow' Table I also Shows the correct
sired. Reaction is faster at the higher temperature. The
{dam/8 molar ratlos of reactants to use for the prepara
nitrocellulose, nitroglycerine, Di-n-propyl adipate, 2- 5O dwlded mm two types ln the ?rst type the modl?er
nitrodiphenylamine, candelilla wax and other desired
ingredients as appropriate_
TABLE I
REACTANTS AND THEIR RELATIVE PROPORTIONS FOR THE PREPARATION OF NEW BALLISTIC MODlFlERS
Metal Ions,
Chelating Agents, Gram - Moles
Grams ions
2,4-Dihydroxy2~Hydroxy~
2,5-Dihydroxy~ O-Acetamido- 4-Acetamido- SalicylBenzoic
Compound
Cu+ T Pb+ T
benzoic Acid
Benzoic Acid
benzoic Acid
benzoic Acid Salicylic Acid
amide
Acid
1
2
l
l
l
l
2
2
4,243,444
TABLE I-continued
REACTANTS AND THEIR RELATIVE PROPORTIONS FOR THE PREPARATION OF NEW BALLISTIC MODIFIERS
Metal Ions,
Chclating Agents, Gram - Moles
Grams - ions
2,4Dihydroxy
2Hydroxy
2,5-Dihydroxy~ O-Acetamido- 4-Acetamido- SalicylBenzoic
Compound
Cu+ + Pb++
benzoic Acid
Bcnzoic Acid
benzoic Acid
benzoic Acid Salicylic Acid
amide
Acid
3
4
5
6
1
1
l
1
1
1
1
1
s
9
10
11
12
13
14
1
1
1
1
1
l
1
1
1
1
1
1
1
1
2
2
1
1
1
1
1
1
1
1
1
1
TABLE H
CHEMlCAL STRUCTURES OF SELECTED
BALUSTIC MODIFIERS
g
HO
\I
O/C\O
||
OH
C\O/ Pb
HO
O /H
30
COMPOUND _ 1
ll
0/ C
/Cu\
h)
(I)
OH
c\ /pb
I!
0/
COMPOUND ' 7
l?
/C
HO\(|)
cu
0/
O
HO
bismuth.
(l:\ / Pb
I
C_CHJ
N /H
i)
(phenolic),
C'CI-I3
COMPOUND - 4
55
II
/C
O?
o
O/C"\O
|
OH
C \O/ Pb
[Q
N /H
\l|: CH
-
COMPOUND - 8
alkyl radicals).
All of the compounds in Table I are largely insoluble
in water and most organic liquids. They are highly
4,243,444
SYNTHESIS
(1)
ballistic modi?er
M] + M2 + Chelating Agent #1 +
(2)
I
ballistic modi?er .
Heat
chelating Agent # 2
Reactions are carried out in a vessel at atmospheric 40 are more dif?cult to prepare reproducibly and in high
tants in distilled or deionized water at elevated tempera
45
4,243,444
7
TABLE III-continued
5.
20
starting materials:
25
EXAMPLE 1
EXAMPLE 2
Compound - l.
EXAMPLE 3
The procedure of Example 1 was repeated in this
Example except that a 5% excess of 2,4-dihydroxyben
5.02g
65.. C
912s
2.l(2,4-dihydroxybenzoic acid) H2O=>Compound - l.
PbO
17.30g
8.82g
+ CuCO3 . Cu(OH)2 +
23.88g
45.6g
was then ?ltered using a Buchner funnel and a What 60
2(2,4-dihydroxybenzoic acid) 65128 Compound - l.
man #42 ?lter paper. The residue (Compound-l) was
washed with three 100 ml portions of distilled water at
65 C. and dried to constant weight in an oven at 160 F.
The steps of the procedure were the same as for Exam
The dried modi?er was lightly ground with a mortar
ple 1 except that the reaction was carried out in an 800
and pestle to break up agglomerates and produce a ?ne 65 ml beaker, and 600 ml of distilled water was used. The
light green powder. The yield was 98.6%, and subse
initial pH of the reaction mixture at room temperature
quent chemical analysis of the modi?er showed that its
was 3.60, and at the completion of the reaction was 5.60.
4,243,444
10
-continued
2.19g
8.24g
Compound 7.
.EXAMPLE 5
EXAMPLE 8
EXAMPLE 6
This experiment was a repeat of Example 5 except
3.33g
that a 5% by weight excess of the 2-hydroxybenzoic
PbO
acid was used. This has the advantage of increasing the
rate of reaction, and providing greater assurance that
the copper and lead salts will completely react. Care 40
must be exercised, however, to wash the excess acid
from the desired product. The reaction was:
1.70g
2.30g
2.67g
9.27g
Compound - 8.
4.73g
65.. C
8-62g
2.1(Z-hydroxybenzoic acid) Ti?compound - 2.
1.5 hours. The slurry was ?ltered and the residue (Com
8 was 94.7%.
EXAMPLE 9
EXAMPLE 7
60
3.00g
7.00g
65,, C
Monobasic cupric salicylate + lead beta-resorcylate
5.74g
65
1.81g
245g
4,243,444
11
12
TABLE IV
NOMINAL COMPOSITIONS OF HEN-l2 TYPE DOUBLE BASE PROPELLANTS CONTAINING
COMPOUNDS ~ 1 AND - 7
Ingredients
Composition - A
Composition - B
Composition - C
Composition - D
Composition - E
Composition - F
Nitrocellulose
49.0 i 1.5
49.0 i 1.5
49.0 i l.5
49.0 i 1.5
49.0 t 1.5
49.0 i 1.5
Nitroglycerine
Di-n-propyl adipate
40.6
3.3
40.6
3.3
40.6
3.3
40.6
3.3
40.6
3.3
40.6
3.3
Z-nitrodiphenylamine
Candelilla wax
*Compound - l
2.0 i 0.5
0.1
4.0
2.0 i 0.5
0.1
4.5
2.0 i 0.5
0.1
2.0 i: 0.5
0.1
4.0
2.0 i 0.5
0.1
5.0
2.0 i 0.5
0.1
4.0
1.0
(12.6 N)
*Compound - 7
5.0
steps of this synthesis were the same as those of Example 1. The initial pH of the reaction mixture at room
temperature (25 C.) was 4.50. After 20 minutes of mix
ing, the pH dropped to 4.00 at which time heat was
applied. The pH leveled off at 3.25 after 40 minutes at
which time the temperature of the reaction medium had
equilibrated at 70 C., and the reaction was complete.
The yield of Compound-l was 68.6% and its purity was 25
We claim:
45
13
4,243,444
14
Z-hydroxybenzoic acid.
1% by weight.
20
25
30
35
45
55
60
65
It