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Патент USA US2404688

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Patented July 23,1946
1 2,404,688
2,404,688 7 ,7
Herman A. Bruson and George ‘B. Butler, Phila
delphia, Pa., assignors to Rohm & Haas Com
' pany, Philadelphia, Pa., a corporation of Dela
3,1; ‘
No Drawing. Application January 21, 1944,
‘Serial No. 513,197
4 Claims.
This invention relates to explosive or readily
combustible plastics and deals more particularly
zene, toluene,-or xyleneyor ethers, such as iso
propyl ether, butyl ether, or the like, or mixtures
of such solvents.
with plastic polymers of Intro-compounds having
the formula:
(01. 200-’l8) 7 1 w
The esteri?cations involved may be performed
Within the range of 50° C. to 150°C; although ,
both somewhat lower and higher‘ temperatures
may be used, depending upon reactants, solvents,
wherein R is a nitro- or polynitro-hydrocarbon
radical from a monohydric nitroalcohol contain
ing at least one nitro group for each four carbon
atoms present therein and R’ is the hydrocarbon
There may be used in the .reaction mixture
polymerization inhibitors, such as hydroquinone,
pyrogallol, B-naphthol, etc.
' _
The following examples illustrate this inven
residue of a pry-unsaturated primary aliphatic al
The above nitro esters polymerize upon ex
] ~
Example 1
posure to heat, light, air, and/or catalysts such 15 A‘ mixture of 78 grams (0.5 mol) of’maleici acid
as benzoyl peroxide to form transparent plastics
mono-allyl ester, 60 grams (0.5 mol) of 2-nitro—‘ '
varying from hard, glassy masses to tough, some
l-butanol, .150‘ cc. of dry benzene, and 0.5 cciof
what elastic, rubbery materials.
concentrated sulfuric acid was boiled under a
These new plastics burn in the air with great
re?ux condenser attached to a water separator
vigor and possess explosive properties. They are 20 for five hours, until‘ no more water collected in
useful for the preparation of explosives, rockets,
the trap. After the mixture had been cooled, ?ve
fuses, ?ares, and the like, as combustible binders
grams of powdered anhydrous sodium'carbonate
or plasticizers for gun-cotton, TNT, picric acid,
was added and the mixture stirred for one hour
and other explosive compositions.
at room temperature. The mixture was ?ltered
As a monohydric nitroalcohol, there may be
and the clear ?ltrate evaporated to'dryness in
used 2-nitroethanol-1, 2-nitro-propanol-1, 2-nitro
vacuo. \The residual oil was then distilled in‘
butanol-l, 2-nitro-2-methyl propanol-l, l-di
vacuo. The allyl Z-nitrobutyl maleate
nitrophenyl-2-nitro-2-methyl propanol-l, l-tri
nitrophenyl-2-nitro-2~methy1 propanol-l, 2,4,6
trinitrophenylethanol, and other monohydric
alcohols in which there is present at least one
nitro group for each four or fewer carbon atoms.
As a lay-unsaturated primary aliphatic alcohol,
there may be used allyl, methallyl, propenyl, or
crotyl alcohol, or methyl-vinyl carbinol, or the
distilled over at‘ 156°‘-163° C./2-3 mm. as a pale
yellow oil. It serves as a colloiding agent for gun
cotton and can also be polymerized to a trans
parent‘plastic on heating with 1-2% of benzoyl
peroxide at 95°-1_00° C.
Example 2
The dibasic carboxylic nucleus may be obtained
from maleic or fumaric acids or their acyl halides
A mixture consisting of '72 grams of maleic acid
or from maleic anhydride.
mono-allyl ester, 56 grams of 2-nitro-2-methyl
The new esters of this invention are readily ob
propanol, 150 cc. of benzene, and 0.5 cc. of con
tainable in several ways. For example, maleic an
centrated sulfuric acid was re?uxed for ?ve hours
hydride can be ?rst esteri?ed with a nitroalcohol
with’ water removal and worked up as described
corresponding to group R and the resulting half
in Example 1. The allyl 2-nitro-2-methyl propyl
ester subsequently esteri?ed with the unsaturated
alcohol, R'OH, or the reverse procedure may be 45
According to another procedure, the acid chlo
ride of the half ester of one alcohol is condensed
with the other alcohol.
Although the esters may be prepared in the ab 50 was obtained as a colorless oil which boiled at
sence of solvents other than the reactants them
162°-163° C./2 mm. It polymerizes to a trans
selves, it is preferred that a solvent be used.
parent, plastic, readily combustible mass when
Suitable for this purpose are chlorinated sol
heated with 1-2% by weight of benzoyl peroxide
vents, such as carbon tetrachloride or ethylene
at 100° C. It may also be copolymerized. with an
dichloride; hydrocarbons, such as naphtha, ben 55 equal weight of di-(-2-nitro-2-methyl propyl)
Example 6
maleate in the presence of 2% by weight of ben
zoyl peroxide to a combustible polymer.
Example 3
To a solution of 2,4,6-trinitrophenylethanol in
v'70 cc. of hot dry benzene, there was gradually
added 7.5 grams of the acid chloride of fumaric
A mixture consisting of 78 grams of maleic acid
acid mono-allyl ester,
mono-allyl- ester, .53 grams of 1-nitro.-'-propano1‘-2,
150 cc. of benzene, and one gram of concentrated
sulfuric acid was boiled under re?ux for eight:
dissolved in 20 cc. of dry benzene. The mixture
was boiled for several hours, cooled, and the
product washed with water, dilute sodium car
hours while the water formed was continually re
moved by a water separator. After the mixture‘
was cooled, the product was Washed thoroughly
bonate solution, and ?nally with water, then
with water and the solvent distilled ‘off. The re
sidual oil was distilled in vacuo to yield allyl l
evaporated to dryness in vacuo. The residual oil
was puri?ed by-several washings with hot alco
nitro-isopropyl maleate
hol and ?nally'dried in vacuo at 90° C.
trinitrophenylethyl allyl fumarate
CH5-—CH—O-—C 0-oH=oH—oo0-0H-.-—oH=oH¢
as a pale yellow oil which boiled at 160° C./2 mm.
When heated at 100° C. with 1—2% by weight "of
benzoyl peroxide, it polymerized to a dark 20
brown, thermoplastic, readily combustible resin.
which was obtained polymerized when heated
with benzoyl peroxide (1%) at 100° C. to; a soft,
Example 4
By using 0.5 mol of maleic acid mono-methallyl
pliable, non-tacky resin.
The corresponding maleate is obtained by heat
ester in place of the maleic acid mono-allyl ester 25
in Example 2, the corresponding methallyl 2-ni
ing one molecular equivalent each of maleic an
hydride and 2,436-trinitrophenylethanol at 80° C.
tro-Z-methyl propyl maleate
in benzene solution for several hours, then add
ing an excess of allyl alcohol, a small amount
30 (1 cc.) of concentrated sulfuric acid, and re?ux
ing until no more water is evolved, then cooling,
Washing, and evaporating off the solvent. and
excess allyl alcohol. It is a brown oil whichalso
158°-159° C./1—2 mm. when heated with 2% by
polymerizes as above to an explosive plastic.
weight of benzoyl peroxide at 95°-100° C., it
We claim:
polymerized to a clear, yellowish, combustible 35
1. A readily combustible plastic polymer of an
ester having the formula
Example 5
isv obtained as a colorless oil which boils at
A mixture of 0.5 mol each of 2-nitro-2-methyl
propanol and maleic acid monopropargyl ester in
wherein R is a, nitro hydrocarbon radical having
150 cc. of benzene was boiled in, the presence of 40 one to ten carbon atoms» and containing at least
One nitro group i'or each‘four carbon atoms pres
0.5 cc. of concentrated sulfuric acid for ?ve to
ent in said hydrocarbon‘ radical, only one'nitro
six hours under a re?ux condenser attached to
group being present on any single carbon atom
a Water trap. After it Was washed and dried, the
thereof, and R’ is the hydrocarbon residue'of‘ a
product was distilled in vacuo to yield 2-nitro-2
45 monohydric ray-unsaturated primary aliphatic al
methyl propyl propargyl maleate
cohol of not over four carbon atoms.
2. A resinous polymer-of 2‘,4-,6'-trinitrophenyl
ethyl allyl maleate.
3. A resinous‘polymer or 2-nitro"-2'-meth-yl pro
as a colorless oil which boiled at l45°-155° C./2-3 50 pyl allyl maleate.
A sample of the oil was mixed with 2% by
weight of benzoyl. peroxide and polymerized at
100° C. to a thick syrup. This syrup was coated
onto a sheet of steel and heated at 100° C. until 55
a clear, hard, polymer ?lm was formed.
4. A resinous polymer of 1-nitro-isopropyl- allyl
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