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Патент USA US2407131

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Patented Sept. 3, 1946
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e
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2,407,131
UNITED STATES PATENT OFFICE
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'
‘2,407,131
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'
PLASTICS
. Herman A. Bruson and George B.~.Butler,».\Phila->'
delphia, Pa., assignors to Rohm & Haas Com
pany, Philadelphia, Pa., a. corporation o£ Dela
ware
.
' No Drawing. Application January 21, 1944,
.
Serial No. 519,193
9- Claims.
(01. zen-set"
4
1
‘
2
This invention) relates to explosive or readily
26 grams (0.10‘ mol) of 2,4,6-trinitrophenyleth
combustible». plastics» and deals more particularly
anolI added irrso‘li‘d“ form. Stirring was-‘continued,
with trinitrophenylethyl esterst of. acrylic or of-
and the reaction mixture heated gradually to
methacrylic acid- and polymers. thereof.
re?ux and re?uxed for one-half hour. After the
, I
It is already known that traces of polynitro- 5? mixture had been‘ cooled, the solution was washed
aromatic compounds, such as trinitrobenzene or
thoroughly‘ with 10%‘ NazCO'a‘ and water, and the
trinitrotoluene, will, inhibit or entirely suppress
benzene was removed under vacuum on a steam
the polymerization of“ acrylic or methacrylic
bath. The residue was a resinous material, but,
esters, for example, methyl acrylate or methyl
after: washing with. dilute potassium hydroxide
methacrylate. _It' was surprising to discover, 10'? solution, it became a crystalline" solid.“ Itrwas‘
therefore, that’the trirritro'phenyletl’iyl- esters of
recrystallized from methanol and melts, when
acrylic or methacrylic acid polymerize readily to
pure, at 70° C. On heating at 100° C. with 1-5%
hard, tough plastics when these esters are heated
of benzoyl peroxide, it polymerized to a hard,
with organic polymerization catalysts such as
brown resin which melts at 8‘0°‘-90‘°' C‘.
peroxides, for‘ example, benzoyl peroxide.
The 15'
‘
"
nitroplastics thus‘ obtained are useful for the
Example 2
preparation: of military explosives.
2;4,6-txinitrophenylethyl>
In carrying out thisrinvention, it has been found
methccrylate.-—(A)>
To 10.4 grams (0.04 mol) of‘ 2,4;6-trinitrophenyh
advantageous to prepare the monomeric esters
ethanol was added 9.2 grams (0.06 mol) of meth
by esterifying 2,4,6-t1‘initr0Dh6nylethanol with 20 acrylic anhydride, and. the reaction mixture was
the acid chloride or anhydride of acrylic or meth-
heated for one hour in an oil bath at l10°‘-120° C.
acrylic acid respectively The 2,4,6-trinitrophenylethanol used is obtained by condensing
After the mixture had been cooled, the resinous
product was washed with .1 N sodium hydroxide
TNT (trinitrotoluene) with formaldehyde. The
solution to remove the excess anhydride and the
monomeric esters obtained are crystalline solids 25 acid formed in the reaction. After a thorough
having the general formula:
1'1 (I?
washing with cold water, the product became
N0,
solid.
I
pure ester melts at 94° C.
CHFC__C_O_CH,OH,
_NO,
.
.
The
Analysis: Found: C=44.3%; H=3.60%; N=
30 13.05%.
Calculated for C12H11O8N3:
NO,
.
It was recrystallized from ethanol.
.
3,39%;
?lglfgggfa?dagei?ler °f the gmup c‘ms‘stmg "f
C=44.3.%; H=
N=12.9%.
On heating the ester at 1102120" 0. with 2-5%
The polymerization of these esters can be car- M gifsgegzgilsi?emmde’ 1t polymenzes w a’ brown’
ried out at a temperature at which they are ?uid, "0
i. e., at or somewhat above their melting points,
'
‘
. .
(B) 5'2 grams (9021mm) of z’é?lgnng’ro'
preferably at 95°—120° C., or in solution, as, for
example, in acetone at the boiling point thereof.
The peroxides which can be used include benzoyl,
la’uroyl or other organic peroxide The polymer_ to
phenylethant’l was dlsso Ved.m 50 Sc‘ of W en
Zene by heatmg’ and .a solptlqn of '1 grams (0'02
mol) of methacrylyl “910MB m 20 0020f dry pen
zene was added dropwise to the re?uxing 80111131011.‘
ization can also be carried out in aqueous suspen-
R'ta?uxmg was con?rmed’ for 13w‘; h?urs' After?he
sion 01, emulsion’ in which case ammonium per_
mixture had been cooled, the so ut1on was was ed
sulfate
can be used as polymerization catalyst.
The following examples illustrate this inven-
w'llth
iqueous Sada‘ sglutlora ang Witter am?) the
so Ven remove un er re use p esstlre n 8'
tion:
1
Example 1
_
2,4,6-trinitrophenylethyl acrylate.—To a vigorously stirred suspension of 21 grams (0.1 mol)
_
4a steam bath. The product was recrystallized from
ethanol and it melts at 94° C. It polymerizes in
the same way as the product prepared by the
anhydride method described above.
These resins‘ burn with considerable vigor.
of phosphorus pentachloride in 50 cc. of dry ben- 50 When a ?ame is applied, they become ?uid be
zene was added 14.5 grams (0.2‘ mol) of acrylic
fore igniting, but, after ignition, they burn con
acid from a dropping funnel While the temperatinuously, leaving only a small carbonaceous res
ture was kept vbelow 10° C. The reaction mixture
idue. They are soluble in ketones' but are in
was then heated in a Water bath at 30°'-35° C. for
soluble in alcohols, hydrocarbons, and chlorinated
one-half hour. It was then cooled to 20° C. and 55 solvents. They are partcularly valuable as bind
2,407,131
3
4
ers for other explosives in the manufacture of
5. A polymer of an ester having in its mono
meric form the formula:
fuses, rockets, incendiary bombs, and related
military‘ explosives.
N01
We claim:
1. As a new compound, a substance having in
its monomeric form the formula:
.
N02
R O
6. A polymer of an ester having in its mono
10 meric form the formula:
N0;
N02
|
CH:
wherein R is a member of the group consisting
of hydrogen and methyl.
.
V
2. As a new compound, a substance having in
15
its monomeric form the formula:
N0:
7. As a new compound, the ester:
N0:
CH:=CH—OO 0-CH1CH
1?“
N01
N02
> 3. As a new compound, a substance having in
20
N03
wherein R. is a member of the group consisting
its monomeric form the formula:
of hydrogen and methyl.
8. As a new compound, the ester:
25
4. A polymer of an ester having in its mono
meric form the formula:
30
NO:
N02
9. As a new compound, the ester:
N02
0
N02
.
OH:
I t
I
011,:(1-00 o CHaCH
No,
35
N02
wherein R is a member of the group consisting of
hydrogen and methyl.
HERMAN A. BRUSON.
GEORGE E. BUTLER.
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