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Патент USA US3093697

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United States Patent 0
Patented June 11, 1963
1
2
3,093,687
ORGANOBORON COPOLYMERS
Sheldon L. Clark, Eggertsville, June T. Duke, Tonawanda,
and Trescott B. Larchar and William K. Taft, Lewiston,
N.Y., assignors to Olin Mathieson Chemical Corpora
The liquid products prepared according to the method
of this invention can be cured to form solid products.
‘In accordance with the present invention, it was discov
ered that compounds of the above class can be copolymer
ized with conjugated diole?n hydrocarbons, such as 1,3
tion
butadiene and isoprene, to produce organoboron copoly
No Drawing. Filed Sept. 4, 1959, Ser. No. 838,356
9 Claims. (Cl. 260-6065)
mers. The organoboron copolymers are formed by a con
ventional emulsion polymerization process. In such a
process, the organoboron compound of the above class and
This invention relates to organoboron copolymers and 10 the conjugated diole?n hydrocarbon are charged to a re
to a method for their preparation. The organoboron
actor containing water, a soap and a catalyst such as azo
copolymers are prepared by the copolymerization of con
bis(isobutyronitrile) or potassium persulfate. A modi?er,
jugated diole?n hydrocarbons and compounds of the class
such as nedodecyl mercaptan or tertiary dodecyl meroap
RR'B10H8(CR”CR”’) wherein R and R’ are each selected
tan, whose function in emulsion polymerization system is
from the class consisting of hydrogen and an alkyl radical 15 to control the average molecular weight, is usually includ
containing from one to ?ve carbon atoms, wherein R"
ed. The polymerization system is then rapidly brought to a
and R’" are each selected from the class consisting of
suitable reaction temperature, generally between 30° and
hydrogen, an allryl radical and a monoalkenyl hydrocar
80° C. when using potassium persulfate as a catalyst and
bon radical, at least one of R" and R'” being a mono
45° to 80° C. when using azo isobutyric dinitrile as a
alkenyl hydrocarbon radical, the total number of carbon 20 catalyst, and the system is agitate ‘ for from about 12 to
atoms in R” and R'” taken together not exceeding eight.
72 hours. After the polymerization has proceeded to the
Further, this invention relates to solid propellant com
desired degree of conversion and has been shoitstopped
positions containing said organoboron copolymers and
if desired, the unreacted diole?n is vented off and the con
to a method for their preparation.
tents of the reactor are allowed to cool to room tempera
Compounds of the above class can be prepared by the 25 ture. Any unreacted ortganoborane monomer which set
tles out at this point is removed, and the latex is coagu
lated, usually with a dilute mineral acid such as hydro
atoms in each alkyl group with an acetylenic hydrocarbon
chloric acid. The copolymer which is thus precipitated is
reaction of decaborane or an alkylated decaborane hav
ing one to two alkyl groups containing 1 to 5 carbon
containing at least one ole?nic bond and from :four to ten
washed in water with methanol to remove ‘any emulsi
carbon atoms in the presence of a wide variety of ethers, 30 ?er and organoborane monomer still remaining, and the
nitriles, amines or sul?des.
The preparation of these
compounds is described in application Senial No. 813,032,
?led May 13, 1959, of Ager, Heying and Mangold. For
example, B10H10(CHCC(=CH2)CH3) can be prepared
washed elastomer is then dried.
The ratio of monomers can vary widely, generally
being ‘from 10 to 99 and preferably from 60 to 95 parts of
borane monomer of the above class per 100 total parts of
by reacting for about 12 hours ‘at 125° C. a mixture of 35 monomer, the remainder being conjugated diole?n hydro~
carbon. The amount of catalyst employed can also be
decaborane, isopropenylacetylene, and tetrahydrofuran in
varied considerably, although amounts in excess of 0.1
an autoclave.
part of azo isobutyric dinitrile or 0.03 part of potassium
The preparation of decaborane is known in the art.
Lower alkyl decaboranes, such as monomethyldecaborane, 40 persulfate per 100 parts of monomer usually are employed,
depending on the rate of polymerization desired. The
dimethyldecaborane, monoethyldecaborane, diethyldeca
amounts of emulsi?er and water employed are preferably
borane, monopropyldecaborane and the like, can be pre
between 3 and 10 parts and 180 and 300 parts respec
pared, for example, according to the method described
tively per 100 total parts of monomer.
in application Serial No. 497,407, ?led March 28, 1955,
The formation of the organoboron copolymers is more
now US. Patent No. 2,999,117, by Elmar R. Altwicker, 45
particularly
described in the following examples. In the
Alfred B. Garrett, Samuel W. Harris and Earl A.
examples, the formula parts are parts by weight. The
Weilmuenster.
emulsi?er, dimethyl benzyl C16 alkylammonium chloride
The solid products prepared in accordance with the
(Ammonyx T), as received and used is a 25 weight per
method of this invention, when incorporated with suitable
oxidizers such as ammonium perchlorate, potassium per 50 cent aqueous solution. All B10H10(CHCC(=CH2)CH3)
samples were distilled before use in polymerizations ex
chlorate, sodium perchlorate, ammonium nitrate and the
cept that used in Example XIII.
like, yield solid propellants suitable for rocket power
plants and other jet propelled devices. Such propellants
burn with high ?ame speeds, have high heats of combus
tion and are of the high speci?c impulse type. The solid
products of this invention, when incorporated with oxi
dizers, are capable of being formed into a wide variety
of grains, tablets and shapes, ‘all With desirable mechani
cal and chemical properties. Propellants produced by the 60
methods described in this application burn uniformly with
out disintegration when ignited by conventional means,
such as a pyrotechnic type igniter, and are mechanically
strong enough to withsand ordinary handling.
EXAMPLE 1
Material
B10H10(CHOC(=CH2) CH3) _______ __
Butadieno ________________________ __
Sulhle (tertiary dodecyl mercaptan)
Formula
parts
_
80
_
20
Grams used
5. 6
1. 4
__-
0. 5
0. 0368
Sodium fatty acid soap ______________________ ._
4. 3
0. 301
X28305 ______________________________________ -_
Water _______________________________________ __
0.23
180
0. 016
12. 60
3,093,687
3
4
Soap, water and potassium persulfate were mixed to
gether and put into an 8 oz. bottle, along with the
B1nI-I10(CHCC(=CH2)CH3) monomer. The Sulfole then
was added, and ?nally, the butadiene was added, using
diene. The bottle was opened and some solid material
(granular) found to be present was ?ltered out. The
solid material was washed with water and methanol. The
methanol dissolved the unreacted
an excess to ?ush the bottle. The bottle then was tightly
capped, placed in a protective cage and put in a water
bath at 48° C.
The bottle was rotated end over end in
and a small amount of elastic solid material remained.
the water bath for a reaction time of 24 hours. One-half
This latter was washed thoroughly with methanol and
ml. of a 5 percent aqueous solution of hydroquinone was
injected into the bottle as a shortstop. Excess pressure 10 then dried in a vacuum oven at room temperature. The
latex remaining after removal of the solid material was
was vented from the bottle with a hypodermic needle and
coagulated with dilute hydrochloric acid. An additional
the bottle was left sealed overnight. A good emulsion
quantity of elastic solid was obtained. This was thor
was evident in the bottle. Subsequent examination of the
oughly washed in water, then in methanol, and ‘dried in a
bottle containing the polymerization products indicated a
layering in the emulsion. The bottle was opened and the 15 vacuum oven at room temperature. The elastic product
which was obtained from the solid material weighed 0.14
contents transferred to a 400 ml. beaker. Additional
g. The elastic product which was obtained from the latex
water was added and a solid granular material formed a
weighed 1.15 g. and was found by duplicate chemical anal
layer at the top of the liquid. This was removed, placed
yses to contain 32.6, 32.6 percent boron. The methanol
in a medium grade sintered glass ?lter and washed sev
eral times with tap water. This solid material resembled 20 soluble material was found to weigh 1.56 g. The 32.6 per
cent boron found in the elastic material from the latex
the original B1oH10(CHCC(=CI-I2) CH3) monomer. The
corresponds to 57 percent of B10H10(CHCC(=CH2)CH3)
solid material was placed in a 100 ml. round bottom ?ask
in the product.
and a vacuum was applied for three hours to remove the
water.
The solid material,
EXAMPLE III
apparently unreacted
B1OHIO(CHCC(=CH2)CH3), which was recovered from 25
the polymerization reaction weighed 3.7 g. and had a
melting point of 44° C.
The liquid remaining after the removal of the solid
material was a creamy latex. Dilute hydrochloric acid
was added slowly while stirring with a glass rod. An
elastomeric solid precipitated leaving a clear serum. The
elastomer was washed several times in cold water, then
Material
Formula
parts
B10H1o(CHCC(=CH2) CH3) ................. ..-
Butadiene
30 Ammonyx
T (dimethyl benzyl C10 alkyl
ammonium chloride)
__
-____
Water
____
80
5. 20
20
1. 30
17. 92
Sulfole
AIBN (azo isobutyric dinitrile)- _
Grams used
0. 5
0. 525
166. 56
1. 2O
0. 032
0. 0339
10. 8
several times in warm water and placed in a vacuum desic
cator. The elastomeric material was removed from the 35
desiccator and was a doughy mass, obviously containing
The AIBN was weighed into an 8 oz. bottle. The
a quantity of unreacted B10H10(CHCC(=CH2)CH3) as
Ammonyx T soap, water, B10H10(CHCC(=CH2)CH3)
evidenced by crystalline portions. This doughy mass was
monomer, and Sulfole were added in that order. The
worked with a stirring rod under several portions of meth~
bottle was cooled and then the butadiene was added. The
‘anol, and then redried in the vacuum desiccator. The dry 40 bottle was placed in the polymerization bath as in Exam
product was a soft elastic material, very nearly liquid.
ple I. After about 40 hours, the bath temperature Was
The elastic material recovered weighed 1.5 g. and was
found to be 58° C., and readjusted to 50° C. The bottle
was removed from the bath after a total of 47 hours re
shown by duplicate chemical analyses to contain 24.0,
action time, and then cooled to room temperature. A
23.8 percent ‘boron.
45 100 ml. ?ask with a stopcock was weighed at atmos
pheric pressure, then evacuated and weighed again. The
EXAMPLE II
Material
Formula.
parts
B1oH10(CHCC(=CHz) CH3) _________________ -_
80
Bntarlirmo
20
Sulfole ______________________________________ _.
Sodium fatty acid soap ______________________ __
KgSgOn
Water
0. 5
Grams used
?ask and a length of rubber tubing with a hypodermic
syringe was cooled in a Dry Ice bath. The syringe was
50 inserted in the rubber gasket in the bottle and the stop
cock of the ?ask opened. The butadiene was removed
5. 20
1.30
0. 0325
4. 3
0. 2795
0. 23
180
0. 0149
11.700
and found to weigh 0.2712 g., corresponding to a 79.2
percent conversion of butadiene. The bottle was opened,
and some solid material (granular) which was present
55 was ?ltered out, and then washed with water and meth
anol. The methanol dissolved any unreacted
Soap, water and potassium persulfate were weighed into
an 8 oz. bottle. The BIOH1O(CHCC(=CHZ)CH3) mono
from the solid material and a small amount of solid
mer was added, followed by the Sulfole. The bottle was 60 elastic material remained. This was washed thoroughly
cooled and the butadiene was added with an excess to
with methanol and then dried in a vacuum oven at room
purge the bottle. The bottle was placed in the bath at
temperature. The latex remaining after removal of the
48° C. After approximately 40 hours, the 'bath tempera
solid material was coagulated with dilute hydrochloric
ture was found to ‘be 58° C. and was readjusted to 50° C.
acid. An additional small quantity of elastic solid was
After a total of 47 hours of reaction time, the bottle was 65 obtained. This was thoroughly washed in water, then
removed from the bath and cooled to room temperature.
methanol, and then dried in a vacuum oven at room tem
A 100 ml. ?ask with stopcock was weighed at atmospheric
perature. An attempt was made to collect all the meth
pressure, then evacuated and weighed again. The ?ask
anol soluble material (presumably excess
and a length of rubber tubing with a hypodermic syringe
70
was cooled in a Dry Ice bath. The syringe was inserted
in the rubber gasket in the bottle and the stopcock of the
?ask was opened to remove and weigh the unreacted buta
diene. A total of 0.2675 g. of unreacted 'butadiene was
to determine the recovery, and this was found to weigh
4.4 g. The elastic product from the solid material
recovered, indicating a 79.2 percent conversion of buta 75 weighed 1.05 g. and was found by chemical analysis to
/
3,093,687
contain 30.8, 30.4 percent boron. The elastic product
room temperature. All methanol rinsings (which should
from the latex was found to weigh 1.4 g. and was found
have contained any unreacted
by duplicate chemical analyses to contain 31.6, 31.3 per
cent boron.
EXAMPLE IV
. were saved in the beaker. Dilute hydrochloric acid was
added to the latex until a clear serum was obtained. A
Material
B1oH1o(CHCC(=CHz)CH3) _________________ ._
Butadienp
Formula
parts
90
10
0. 5
4. 3
0. 23
180
Grams used
large lump of white elastic material coagulated. This
was washed in water several times, then left ‘in methanol
5. 853
0. 65
0. 0348
0. 2810
0. 0154
11. 7786
10 overnight.
The white elastic material coagulated from
the latex Was washed several times in methanol. The
material was tough and elastic, with good recovery. A
?ame test showed it to burn evenly at a rather slow rate
with a green and yellow ?ame. The product was put
15 in a petri dish and placed in the vacuum oven at room
temperature overnight. The dried material coagulated
The soap, water and potassium persulfate were weighed
from the latex weighed 5.25 g. and was found by dupli
monomer
into ‘an 8 was
OZ. bottle.
added, the
TheSulfole was added, the bottle
cate chemical analyses to contain 17.2, 14.5 percent
Was cooled, and butadiene was added in excess to purge. 20 boron. The solid material not in emulsion, which weighed
The bottle was placed in the bath at 51° C. and allowed
1.44 g., was found by duplicate chemical analyses to con
to react for 48 hours. The bottle was vented and opened.
tain 28.9, 27.4 percent boron. The methanol soluble ma
The latex was a jelly-like semi-solid. Some solid mate
terial was found to weigh 1.50 g.
rial was present. The entire contents of the bottle were
washed into a beaker, and were then ?ltered through a 25
EXAMPLE VI
coarse sintered glass frit. The ?ltered latex was trans
ferred to a beaker. The solid material left on the ?lter
Material
appeared to be a mixture of rubber and
B1uH10(CHCC(=CI-Iz) CH3) ................. .Bntadimw
____
Ammonyx T ________________________________ __
Sulfa __
This solid material was then rinsed with methanol and
a small quantity of a solid elastic was left. The meth
anol rinsings were transferred to a beaker. Dilute hydro~
chloric acid was added to the ?ltered. latex and a large
AIBN.-.
Water___
Formula Grams used
parts
90
4. 50
0. 50
10
17. 92
O. 5
0.896
U. 025
O. 525
166. 56
0. 026
8. 328
quantity of white elastic material coagulated. The serum
The charge was prepared in an 8 oz. bottle and polym
erized at 50° C. for 48 hours. The latex was coagulated
to soak overnight. The solid material recovered from
the latex was given several additional rinsings in water 40 as in the previous examples with hydrochloric acid. A
solid material, separate from the coagulum, contained a
and then methanol. It was placed with the solid elastic
in the vacuum desiccator. The elastic from the latex
sticky elastic and B10H10(CHCC(=CH2)CH3). This
was washed with water and methanol in a dish. The
weighed 4.31 g. While the elastic from the solid material
elastic coagulated from the latex (coagulum) was thor
not in the emulsion weighed 0.8 g.
45 oughly Washed with water and methanol, and placed in
EXAMPLE V
a beaker. Both samples were dried in a vacuum oven at
room temperature. The solid material was found to
was discarded and the material was covered with water
Material
B10H10(CIICC(=CH2) CH3) _________________ __
Bntnrlipnp
Am monyx T """"""""" "
Formula
parts
90
92
0: s
0. 525
166. 56
weigh 0.3414 g. The elastic material coagulated from
Grams used
the latex was found to weigh 0.8226 g., and was found by
50 duplicate chemical analyses to contain 33.6, 34.0 percent
5. 8479
boron.
$3389
EXAMPLE VII
010343
O. 0349
10.8092
The AIBN was weighed into a bottle, followed by the
soap, water, B10H10(CHCC(=CH2)CH3) and then the
55
Material
Butadione
Formula
parts
_
5.0
Grams used
0.25
B1oH1o(CHCC(=CHz) CH3) _________________ __
95.0
4. 75
Ammonyx T.
17. 92
0. 896
__
--.__
5. 0
0. 24
Sulfole. The bottle was cooled and butadiene was added 60 SuliO
0. 525
U. 0204
in excess to purge. The bottle was placed in the bath
166. 56
8. 328
at 51° C. for a reaction time of 48 hours. Excess buta
diene was vented, and the bottle was opened. The latex
was transferred to a beaker and the bottle was rinsed with
The materials were charged in a 2 oz. square bottle
water which was added to the latex. A quantity of soft, 65 with a metal cap containing self-sealing vgaskets. The
sticky, rubbery material (yellow) was left in the bottle
bottle was placed in the bath at 50° C. After about 17
where it had adhered to the glass. This was scraped out,
hours, the bath temperature was at 56° C. The bottle
placed in a small beaker and found to weigh 1.44 g. The
was left in the bath for a total of 48 hours, at approxi
solid was washed in water, then methanol. Not all of
mately
50° C. The latex was coagulated with dilute
the sticky solid could be removed by spatula, so a small 70 hydrochloric acid. A soft, semi-liquid product was ob
quantity of benzene was added, the material was dis
tained which was dried at room temperature in a vacuum
solved and added to the beaker. When the benzene had
‘desiccator. The dried product weighed 0.5974 g. and was
evaporated, the elastic material was washed with water
found by chemical analysis to contain 28.9 percent boron.
and methanol and then placed in a Vacuum desiccator at 75
Examples VI-II through XI shown in Table I were per
3,093,687
1
8
formed in a manner similar to that employed in Exam
The charge was prepared in an 8 oz. bottle, and polym
ple X.
erized at 50° C. for 48 hours.
The bottle was then
opened, after venting off the very little excess butadiene.
No solid material was apparent in the latex. The latex
EXAMPLE X
was diluted with water and transferred to a beaker.
Material
Formula
parts
Butadiene ___________________________________ __
B1oH1o(CHCC(=CHg) CH3) . . _ _ _
Ammonyx ’I‘_
Sulfole._ _
AIBN___
_ _ . . _ _ _ _ . _.
__
5. 0
90. 0
45.0
_________________________________ __
Water
of the bottle. This was scraped out and added to a tared
10.0
17 . 92
0.5
1.00
166. 56
A
small quantity of rubbery material adhered to the sides
Grams used
8. 96
0.25
dish. The latex was coagulated with dilute hydrochloric
acid and a quantity of sticky elastomeric material coagu
10 lated.
This was transferred to the tared dish, washed
several times with water and then with methanol. The
0.5
serum and all rinsings were kept in a tared beaker. The
elastic product was placed in a vacuum desiccator. The
83. 28
product, when dried, was a sticky, highly elastic, semi
15 tluid polymer weighing 1.7031 g. It was found by dupli
cate chemical analyses to contain 27.8, 26.2 percent
The materials were charged to an 8 oz. bottle which
was placed in the bath at 60° C. for 48 hours. The soft
boron.
elastic product obtained weighed 12.5149 g., which cor
responded to a 25 percent conversion, and was found by
duplicate chemical analyses to contain 35.0, 34.9 percent 20
boron.
EXAMPLE XIX
Material
EXAMPLE XII
25
Material
Formula
parts
Butadiem
BmHm(CHCC (=CH2) CH3) _________________ -_
Ammonyx T
40
15.6
60
23. 4
17. 92
Sulfole _________________________ __
AIBN
Water
Grams used
6.99
0. 5
0. 195
1. 5
166. 56
0.585
65.0
Formula
parts
Butadiene
BwHm(CHOGH=CH2) _____________________ -_
Grams used
5.0
0. 25
95. 0
4. 75
17. 92
5. 0
0. 52'
166. 56
Water
0. 896
0. 24
0. 0264
8. 328
30
The materials were charged in a 2 oz. square bottle
with a metal cap containing self-sealing gaskets.
The
bottle was placed in the bath at 50° C. After about 17
hours, the bath temperature was at 56° C. The bottle
The charge was placed in an 8 oz. bottle with a mono
mer charge ratio approximately equal to the combining
ratio as determined from previous runs. The bottle was
was left in the bath for a total of 48 hours, at approxi—
maintained in the bath for a total of 481/2 hours, at a
mately 50° C. The latex was coagulated with dilute
temperature of 62° to 64° C. An excellent emulsion was 40 hydrochloric acid. Layers of what appeared to be liquid
obtained, and yellowish solid material was present around
the bottle. The latex was coagulated with hydrochloric
acid, and a large quantity of rubbery product was ob
tained. The yellowish material in the bottle was sticky
and elastic; it- was removed separately and washed in the 45
methanol. The bulk of the product from the latex was
product formed at the top. The liquid was scooped into
a beaker and dried at room temperature in a vacuum
desiccator. The product was found to weigh 0.8858 g.
and contained 25.4 percent boron.
washed in methanol. Both portions then were dried in a
vacuum. The bulk of the product, which was tough and
sticky, weighed 32.6228 g., and was found to contain
31.7, 31.1 percent boron.
EXAMPLE XX
The sticky material, not in 50
Material
the emulsion, weighed 3.57 g., and was found to contain
25.1, 25.2 percent boron. The conversion of monomers
was approximately 80 percent as calculated from the
Formula
parts
10. 0
90. O
yield.
Examples XIII through XVII were performed in the
same manner as Example XII, except that in Example
Grams used
55
Sulfole ________________ __
_
Sodium fatty acid soap ______________________ __
gSgOn
Water
XIII, undistilled B1OHm(CHCC(=CI-I2)CH3) containing
0. 5
0. 50
4. 5O
0.025
4. 3
0. 2158
0.23
180
0.011
9. 0187
approximately one percent decaborane as a major im
purity was used as a starting material. Conversion
dropped to 30 percent and the polymer was not in an 60
emulsion at the end of the reaction period. Although the
The materials were charged in a 2 oz. square bottle
boron content was 24.2 percent, the polymer was a viscous
liquid.
Bw M
The
bottle was placed in the bath at 50° C. After about 17
65 hours, the bath temperature was at 56° C. The bottle
EXAMPLE XVIII
was left in the bath for a total of 48 hours, at approxi
mately 50° C. The latex was coagulated with dilute
Material
Formula Gramsused
parts
hydrochloric acid. A creamy, soft mass was formed,
Bntndiene
H
with a metal cap containing self-sealing gaskets.
CHCCH=CH
70
lgg
2)
_____________________ _.
9.
.
17.92
0.866
0.5
0.525
166.56
0.025
0.026
8.328
which was transferred to a beaker and dried at room
temperature in a vacuum desiccator. The dried product
was found to weigh 1.3364 g. and was found by chemical
analysis to contain 27.5 percent boron.
Example XXI shown in Table I was performed in a
75 manner similar to that employed in Example XIX.
3,093,687
Table I
‘Ex .mple
I
II
r11
III
BmH1eO(H) C( 0-0133) ............................ -.
B1oH1o_O(H) G(OH_CH2)
80
80
Butadlene __________________________________________ -_
20
20
4. 3
4. 3
0. 23
0. 23
0.5
0.5
180
180
0. 525
0.5
166. 6
50
50
IV
V
VII
80
90
90
90
20
10
10
10
17. 92
17. 92
VIII
95
IX
:X
90
90
10
10
90
10
17. 92
17. 92
17. 92
0. 525
0.5
166. 6
0. 525
0. 5
166. 6
166. 56
..
Ammonyx T
17. 92 _______ __
NaFa soap
X23205 ________________________________________ -_
AIBN_-_ ..
Sulfole- _
Water
Temperature,° G ___________________________________ ._
50
Time, hours
_______ __
24
47
47
21
20
38
Boron content, percent ______________ __
24
32. c
31. 0
Borans monomer in polymer, percent ______________ -_
42
57
54. 5
Properties
(2)
Example _ _ _ .
XI
‘iH’
B1UH100(H)C(G—GH3) ______________________________ -_
BwHw_C(H) O(OH=OH2)
Butadiene
Ammonyx '1‘ ________________________________________ __
(2)
XII
-
0. 23
0. 5
180
0. 525
0.5
166. 6
0. 525
0. 5
166. 6
50
50
(2)
50
50
48
48
48
23
12
22
7. 7
28.1
33.8
28.9
34. 7
13. 5
49
59
51.
61. 9 _______________ -'__
(a)
XIII
XIV
(3)
XV
(9
XVII
60
60
60
60
60
60
4O
40
40
40
17. 92
17.92
17. 92 ______ ._
NaFa soap-
(4)
XVI
4
60
1. 00
0. 5
48
10
17.92
0. 525
5. 0
166. 6
22
48
_______ __
90
17. 92
17. 92
4. 3 _
__-.
Conversion, percent 1- _ _. _
VI
60
(2)
XIX
90‘
40
10*
17. 92
17. 92
95
5
XX
XXI
so
90
10
10
17.92
4. 3
0. 23
0. 23
AIBN
1. 50
1. 50
1. 50
1. 50
1. 50
0. 525
0.525 ______ __
Snlfnlo
Water
0.5
166. 56
0.5
166. 56
1.0
166. 56
1.0
166. 56
0.5
166. 56
0.5
180
1.0
166. 56
0.51
166. 6
5.0
166. 6
0. 5
180
0.5
180
60
52-60
60
60
60
60
60
56‘
50
50
60
58
48
48
Temperature, ° C ___________________________________ __
Tune, hours
1.50 ______ -_
g
(2)
17. 92 ______ __
4. 3
zSzOg“
48
25
35. a {
(a)
XVIII
60
48
....... -.
48. 5
48. 5
58
58
58
Conversion, pereentl ________________________________ __
22
80
30. 2
72. 8
70. 4
Boron content, percent ______________________________ --
g
l } 24. 2
28.5
29. 4
(2)
(2)
63. 6 ...... ._
Borane monomer in polymer, percent
Properties.
1 Based on total monomers.
4 Soft, semi-liquid elastonier.
(5)
2 Soft elastic solid.
5 Liquid elastomer.
(a)
(0
(a)
(2)
0. 525
48‘
48
48
35
18
27
18
27‘
25. 4
27. 5
28.3
43. 5t
39. 0
42. 3
(4)
(5)
(2)
43. 5
(2)
3 Firm elastic solid.
6 Tough elastic solid.
The true copolymeric nature of the product of this
2 ml. of methanol were added, (but no precipitation oc-‘
invention was established by exhaustive extraction of the
curred. Upon the addition of 8 m1. of methanol, a small
product, and by fractional molecular weight precipitation.
fraction precipitated.
This was transferred to a beaker
In the exhaustive extraction, a sample of the copolymer
and found to weigh 0.2764 g., corresponding to 13.27
obtained in Example X weighing 3.0792 g. was placed in 40 percent of the sample. An additional 10 ml. of methanol
a Soxhlet extractor having a water condenser. 250 ml.
were added in increments, resulting in poor separation of
of methanol was placed in the ?ask, and heat suiiicient tor
a fraction. When obtained, this was transferred to a
a gentle boil was supplied. The sample was continuous
‘beaker and found to weigh 0.2933 g. corresponding to
ly extracted for 6 days, with samples weighing 0.6524 g.,
14.08 percent of the copolymer sample. Chemical anal
0.3731 g., 0.5626 g., being taken on the ?rst, second and
ysis showed the ?rst fraction to contain 27.0, 27.7 percent
45
third days respectively. On the sixth day, the extraction
horon, the second fraction to contain 28.6 percent boron,
was stopped and the remainder ‘of the sample was placed
and the third fraction to contain 25.4 percent horon. The
in a vacuum desiccator. Duplicate chemical analyses of
close agreement between the boron contents of these vary
the extracted samples showed 31.1, 31.4 percent "boron
ing molecular weight ranges and that of the extracted
on the ?rst day, 29.1, 26.3 percent horon on the second
polymer is additional evidence for the existence of a true
50
day, 26.8, 26.0 percent boron on the third day and 25.89
copolymer.
percent boron ‘after extraction for 6 days.
The ‘average molecular weight of a sample of the solid
These analyses establish that the
BwI-I10(CHCC(=CH2)CH3) hutadiene copolymer as
B‘10Hm(CI-ICC( : CH2) CH3) /butadiene
prepared in Example XV has been measured by means of
product is a true copo-lymer containing approximately 26 55 light-scattering apparatus and found to he 270,000.
The boron~containing solid material produced by prac
percent boron. The higher boron content of the initial
ticing the method of this invention can be employed as
product (35 percent) can be attributed to the presence of
an ingredient of solid propellant compositions in accord
some trapped B10H10(CHCC(=CH2)CH3) which the
ance with general procedures which are Well-understood
methanol extraction removed. The physical character
istics of the copolymer were essentially unchanged after 60 in the art, inasmuch as the solids produced by practicing
the present process are readily oxidized using conventional
this extraction, again attesting to the true nature of the
solid oxidizers, such as ammonium perchlorate, potassium
product.
perchlorate, sodium perchlorate, ammonium nitrate and
the like. In formulating a solid propellant composition
vadded to the point of incipient precipitation, and any 65 employing one of the present boron-containing materials,
generally from \10t-o 35 parts by weight of boron-contain
insoluble material was allowed to settle slowly and was
ing material and from 65 to 90 parts vby weight of oxidizer,
removed. This was repeated two more times on the ?l
such as ammonium perchlorate are present in the ?nal
trate. The three precipitates represent di?erent molec
propellant composition. In the propellant, the oxidizer
‘ular weight ranges. in this procedure, a 2.0824 g. sample
In the fractional molecular weight precipitation, the
initial polymer was dissolved in benzene, methanol was
of the copolymer obtained in Example X was dissolved 70 and the product of the present process are formulated in
intimate admixture with each other, as by ?nely sub
in 100 ml. of henzene. 20‘ ml. of methanol were added,
dividing each of the materials separately and thereafter
but no precipitation occurred. An additional 18 m1. of
intimately admixing them. The purpose in doing this, as
methanol were added, and a fraction settled out. This
the art is aware, is to provide proper burning character
was transferred to a beaker and found to weigh 0.0416 g.
corresponding to 2 percent of the sample. An additional 75 istics in the ?nal propellant. In addition to the oxidizer
3,093,687
12
The weighed amount of copolymer and
and the oxidizable material, the ?nal propellant can also
contain a ‘binder such as an arti?cial resin generally of the
urea-formaldehyde or phenol-formaldehyde type, the func
B10H10'(CHCC( =CH2) CH3)
tion of the resin being to give the propellant added me
tchanical strength and at the same time improve its burn- 5 were heated at 60° C. to melt the
ing characteristics. Thus, in manufacturing a suitable
propellant proper proportions of ?nely divided oxidizer
B10H10'(CHCC(=CH2)CH3)
and ?nely divided boron-containing material can be ad-
_
mixed with a high solids content solution of partially
(meltlng Point ‘03- 45° C-) ‘and decrease the Viscosity of
condensed urea-formaldehyde or phenol-formaldehyde 10 the copolymer. The ammonium perchlorate, which was
resgnrthebpropomohs heme such that the amount of the
stored under vacuum at 115° c. at all times, and the
resin is 3’ out 5 F0. ‘10 Percant by Weight’ 'b_aS_ed upon Fhe
carbon black were weighed out and placed in an 80 1111.
Weight of the oxidizer and the boron-containing material.
capacity covered Bmbender Plasto
The ingredients are thoroughly mixed and following this
hi h
‘
.
_ ‘
o ‘
h (- t Hal
grap
“1 er
.- .
_m1Xe1" )
the mixture is molded into the desired shape, as by ex- 15 w o_ was mamFamed at 45 C- Thess were med: for
trusion. Thereafter, the binder can ‘be cured by resort15 mmfltes To ‘bung them to ‘the temperature of ‘the mlxe'r
For further in-
The mixer was turned on and O? by remote Control The
formation concerning the formulation of solid propellant
ing to heating at moderate temperatures.
copolymer, B10H10(CHCC(=CH2)CH3) and weighed
WIHPOSIUOIIS, Tefefence 15 made ‘[0 U-S- Patent No- 2r
amounts of the dry curing ingredients were added to the
K622i,” _t° Bgrrllen et a1‘ and U5‘ Patent No' 2’646’596 20 ammonium perchlorate-carbon black mixture. The cover
0
Omas e
-
. _
.
was put on and the mixer started.
After 1.5 hours of
Propellant compositions can also be prepared uslng as
an oxidizable material a boron-containing rfuel such as
. p.
h
.
d
Imxmg’ t' e mlxer was stoppe ’ the cover was ‘removed
B10H10(CHCC(=CH2)CH3) .01- ,a conventional fuel to_
and the propellant removed. . The propellant was spread
gether with ‘an ‘oxidizer and employing one or more of 25 011 a Piece ‘of aluminum £011 and Placed in a Vacuum
the products of this invention as a hinder or duel-binder.
chamber, where it was degased for 301 minutes at ambient
The followmg examples illustrate Solid propellant c9m-
temperature. The uncured propellant was then placed in
Posmons wmmmg, ‘the Kmpo‘lymers of 'thfimventlon-
a stainless steel mold with an aluminum foil lined cavity
propellant formulailons Wm: prepared contammg :Lhe co'
which was 2 in. x 5 in. thick. The cover plate of the
polymer as the solid fuel component and containing the 30 mold was m on and ‘the mold was‘ laced in a Carve 10
copolymer as a fuel-binder together with another solid
'
fueL
EXAMPLE XXII
Th
, ,
P
,
‘
P
‘
1'
ton laboratory hydraulic press. By remote control, pres
sure was applied to the press (5000 psi.) and the heat
_
f
_
was turned on.
The propellant was cured for 7.4 hours
e composition of the propellant mix was as ollows. 35 at 95° C" after which the heat was turned OE ‘and the
pressure was released. When cool, the mold was removed
Ingredient
{Am°‘mt'g‘,
L1 um b t d, I
n?gwwfrlcacieihnnom) ..... ..
12
from the press and the cured slab was removed from
the mold.
Ditferent shape molds were used, depending on the
Fuel-binder.
?g?ggggfgegj?gglg?a};
éinvbgxi?uk- ----------- -_
Fallen“
ggfé'izen
40 required tests. The above cure was obtained in slab form
(113 gctll?lgmtgogggigrator
sgi‘furiluffnzi ________________ __
0:2
oiiilnéitgent.
Captax (mercaptobcnzothiazole) ..
Methyéi’l‘lliggs (tetramethylthiu-
0.1
0.1
Primary accelerator.
Primary accelerator.
M
0.1
s
“1111
h
SE1
9-
.
2
h l i-
f?iohhrli?gcgmc (“met y d
for cutting into strands to Ibe used to determine the rate
'
l
of burning.
t
45
mommy me em or
.
Results from this determination are shown
in Table II
E
I ’
xamp es XXI
H
an
_
d
XXI
V
f
were per orme
.
d _
_
in a sim
.
.
ilar manner, except that m Example XXIII, the ingred1ents
were mixed by hand.
Table II
‘Fxa‘mnla
XXIII
Ingredients, grams:
Gopolymer
BmH1o(CHCC(=CHz)GHQ/butadienc
of Example.
XXII
XXIV
1.0/XII ...................... .- 12/XII ...................... _- 12/XII, XIII 1.
Carbon blank
0.01...
0.1.-
0.2.
Ammoniumperchlorate _____________________________ ..
3.0...
75
75.
B10Hm(CHCC(=CHz)CH3)--_
None
sultuiMethymm‘
12
3.8%..
0:011;
12.
8%
0:1:
011::
.01
0.1.-
0.1.
.
0.03 _________________________ --
0.03.
45
45.
Percent boron in binder and fuel (calculated)
35...
Mix time, hr
Hand mixed ................ -- 3.0 (slow speed) _____________ -- 1.5 (fast speed).
Processing:
Mix temperature ° 0....
Prccure time, hr. .
Ambient
4%
1.0 2-_
Ambient
-
Precure temperature, ° C.-_
Cure time, 111'
24
Curetemperature,° C .............................. ..
90 . . . . . . .
Remarks
Short pot life but excellent
45,
1.0.2
Ambient.
48.
24
. . . . ..
‘H
_
90.
Rubbery,s11ght1y porous .... .. Rubbery, good cure.
cured specimen.
Hardness, Shore A
59-0‘?
Burning rate, in./sec.:
500 p e1
1,000 p.s.i-
1.44.
1,500 p.s.iPressure exponent (n).-..
1 1:1 mixture.
3 Under reduced pressure.
1.85.-
-_
.---
2.27-.
0.41.
70.
Auto ignition temp.,
340° 0.
13
8,093,687
14
We claim:
‘1. A method for the production of an onganoboron
oopolymer which comprims copolymerizing in an emul~
sion polymerization system containing water, an emulsi?er
and an emulsion polymerization catalyst a conjugated
diole?n hydrocarbon with a compound of the class
RR"B-mH8*(CR"CR"') wherein R and R’ are each select
ed t?rom the class consisting of hydrogen and an alkyl
6. The method of claim 1 in which the conjugated diole
?n hydrocarbon is butadiene and said compound is
B10H10(CHCCH=CH2).
7. An onganoboron copolymer of a conjugated diole
?n hydrocarbon with a compound of the class
wherein R and R’ are each selected from the class con
radical containing from one to ?ve carbon atoms, where
sisting of hydrogen and an alkyl radical containing from
in R" and R'” each are selected from the class consisting 10
one to live carbon atoms, wherein R" and R’" are each
of hydrogen, an alkyl radical and a monoalkenyl hydro
selected
from the class consisting of hydrogen, an alkyl
cambon radical, at least one of R" and R'" being a mono
radical and a monoalkenyl hydrocarbon radical, at least
alkenyl hydrocarbon radical, the total number of carbon
one of R" and R'” being a monoallcenyl hydrocarbon
atoms in R" and R'” taken together not exceeding eight.
2. The method of claim 1 in which the conjugated diole 15 radical, the total number of carbon atoms in R" and R'”
taken together not exceeding eight.
?n hydrocarbon is butadiene.
3. The method of claim 1 in which said compound is
8. An organoboron copolymer of butadiene with
BmHm(CHCO( =CHZ)CH3) .
B10H1d(OHCC(=CH2:)CH3)
4. The method of claim 1 in which said compound is
BmHm(CI-ICCH=CH2).
5. The method of claim =1 in which the conjugated diole
?n hydrocarbon is butadiene and said compound is
B10H10(CHCO(=CH2)CH3).
20
9. An organoboron copolymer of butad-iene with
B10H10(CHCCH=CH2)
No references cited.
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