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Патент USA US3042588

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United States Patent
Patented July 3, 1962
I l
smoldering zone of the known smoke or mist generators.
In addition to the low temperature, the substance to be
released or volatized is further protected by moving it
very quickly away from the heated reaction zone in the
Ernst Jacobi and Hans Brenner, Darmstadt, Germany,
assignors to E. Merck Aktiengesellschaft, Darms‘tadt,
Germany, a German corporation
No Drawing. Filed Jan. 26, 1959, Ser. ‘No. 788,718
evolving gas.
generating preparations according to the invention, and
the progress of the fumigating reaction, is improved ‘by
Claims priority, application Germany Jan; 30, 1958
6 Claims. (Cl. 167—39)
The known self-smoldering preparations for fumigat
g It has been further found that the quality of the aerosol
the addition of thermally decomposable nitrogen com
10 pounds, such as ammonium salts and/or cyanamide
and/or urea or the salts thereof, and/or compounds
ing, fogging or generating smokes or mists contain gen
which contain, as a structural element, the group:
erally a combustible substance, such as, wood?our, lac
tose, etc., together with an oxygen-releasing agent, for
instance, a nitrate, chromate, perchlorate, etc. and the
substances to be fumigated, and when ignited at one point 15
C/ \
smolder throughout more or less rapidly, whereby the sub
\ /
stances to be dispersed are vaporized or volatized in. the
smoldering zone. Such customarily known preparanons
such as melamine, guanidine, or preferably dicyandi
have the disadvantage that the substances to be dispersed
which are heat sensitive or di?icult to volatize are mostly 20 amide. These compounds increase the storability of
the aerosol generating preparations in accordance with
decomposed in the smoldering zone which reaches a tem
this invention. Since these substances are furthermore
perature of several 1hundred degrees centigrade. In vlew
thermally decomposed, and while undergoing such de-i
of this situation, it is customary to distribute such sens1-'
composition, increase the pH factor in the reaction zone
tive substances in form of an aerosol by means of special
devices. This entails a substantial expenditure of appa
ratus, compressed gas, or similar means.
25 and also release an additional volume of gas, the pH
dependent decomposition reaction of the 1,5-endomethyl
It is the object of the present invention to provide an
aerosol generating preparation by means of which even
be regulated and the formation of a ?ame can be sup—
thermally easily decomposable, and/or ‘di?icult to vola
ene - 3,7 - dinitroso - 1,3,5,7 - tetraaza - cyclooctane can
Finally, these substances reduce the odor of
tize substances can be distributed in form of an aerosol 30 formaldehyde which occurs when 1,5-endomethylene
3,7-dinitroso-1,3,5,7-tetraaza-cyclooctane decomposes.
without substantial material losses. According to the in
vention, aerosols can be produced by a thermal decom
It was further found that a content of meltable, di?i
cultly combustible or non-combustible halogen com
position reaction of 1,5-eudomethylene-3,7-dinitroso
pounds which split off hydrogen halides above 100° C.,
which contain l,5-endomethylene-3,7edinitroso-1,3,5,7
ane, polyvinylchloride, tetrachlorophthalic acid anhydride,
magnesium bromide, etc., lowers the pH factor in the
It has been found that aerosol generating preparations 35 such' as tetrachlorocyclohexanone, hexac‘hlorocyclohex
tetraazacyclooctane of the formula:
reaction zone, and in the aerosol, and suppresses ?am
ing without causing a deterioration of the storage prop
40 erties of the aerosol generating preparations according to
the invention.
Obviously, it is possible to add to these aerosol
generating preparations the usual additives, such as ?llers,
salts, binding agents, resins (the latter also to regulate
are suitable‘to e?ectuate the distribution even of decom
posable substances in aerosol form Within the space to 45 the rate ‘of smoldering), means for regulating the mois
ture content, such as silicones or sorbitol, further scent
be fumigated. The preparations are of the self-smolder
ing agents, dyes, denaturants,’etc. One can also add fur
ing type so that no apparatus or other devices are re
ther energy sources, as for example, Ba(NO3)2, lactose,
1,5 - endomethylene - 3,7 - dinitroso - 1,3,5,7 - tetra
aza-cyclooctane decomposes when it is ignited or acidi?ed 50
‘When sensitive substances are to be dispensed in form
with evolution of heat and gas; The compound is not
of an aerosol, ?llersare particularly important since they '
hygroscopic, and is readily available (see Mayer, Berichte
der Deutschen Chemischen Gesellscha-ft, vol. 21, page
2888 (1888)). The compound is de?ned in this publica
allowa dilution of the mixture, thereby slowing the fumi
gation reaction. Depending upon the heat conductivity
composition reaction progresses correspondingly slower
zone, provided they are not substances which are already
liquid at room temperature. Fillers of this kind are
of the ?llers, the zone from which the substances to be
tion as dinitroso-pentamethylenetetramine, and burns with 55 dispersed are expelled can be broadened or narrowed.
. For theuse in the aerosol generating preparations of
a bright ?ame after ‘being ignited. When mixed with non
this invention absorptive ?llers have been found to be
combustible and/or ?ame-retarding additives, or when
particularly advantageous when the substances to be dis
locally heated to atleast 200° C. (in an acidic medium
persed in form of an ‘aerosol are sensitive. Such ?llers
also possibly at temperatures below 200° C.) without
absorb the readily melting among those substances so
use of a ?ame, a ?ame does not form at all, or if it
that they do not melt away in the vicinity of the reaction
?ames, the ?ame can be readily snuffed out; and the de
through the entire mass.
Hence, 1,5-endomethylene
3,7-dinitroso-1,3,5,7-tetraazacyclooctane permits the prep
powdered silicic acid types and other silicates and oxides,
aration of mixtures which, when locally ignited or heated, 6 particularly those which come under the heading “color
react progressively through the mass, whereby within
less reinforcing ?llers,” furthermore alumina gel, ?nely
discrete clays, diatomaceous earth, other metal oxides and
the reaction zone the temperature, is temporarily ele
also wood ?our, cellulose powder, carbon black, graphite,
vated and a large volume of gas is‘ evolved. The peak
?nely powderized synthetic plastics, such as, polyvinyl
temperature can be lowered to substantially below 200°
C. by including a suitable proportion'of known non-com 70 ‘alcohol and hardened aminoplasts, etc.
The' aerosol generating preparations according to the
bustible or inert ?llers. Hence, the temperature is far
below that of the red glow which isdbtained in the
invention can be applied in any desired form, for in
stance, as powder, granules, tablets, small sticks, or as
layers applied to a carrier, etc. The generation of the
a-Hexachlorocyclohexane ____________________ __ 0.95
Silicic acid
aerosol can be readily initiated by means of a match ?ame,
a hot wire, a heating plate, a fuse cord or paper fuse.
Swellable clay _____________________ __; _____ __ 0.80
It is su?icient to ignite the aerosol generating preparations
at one point. The reaction progresses from there through
N-methyl-carbamic acid-phenylester ___________ __ 0.65
out the mass.
___________________ __ 0.35
reacts throughout when ignited at one corner with a
The aerosol generating preparations according to the
invention do not require apparatus, but they may, for
match, and when the ?ame has been extinguished without
further formation of ?ame and expels a dense smoke
instance, be fed continuously to a source of heat if they 10 which contains the two last mentioned active ingredients.
are sufficiently loose. The aerosol may also be propelled
Example 5
A powder consisting of:
in a desired direction by means of a gas current, for in
stance, produced by a blower; or the production of the
aerosol can be effected in a combustion chamber which
has a small aperture from which the aerosol ?ows in the
desired direction. It is also possible to apply addition
ally a strong electrostatic charge to the aerosol particles
by means of suitable apparatus.
1,5 - endomethylene - 3,7 - dinitroso-1,3,5,7-tetraaza
cyclooctane ________________________________ _.
Dicyandiamide ______________________________ ___.
Flowers of sulfur _
____ _.
N-trichloromethylthiotetrahydrophthalimide _____ __
There are numerous ?elds of application for the aerosol
generating preparations according to the invention, as 20
for instance, those of pest control, plant protection, dis
is ignited as described in Example 2. It reacts through
infection, for ?reworks, for signalling purposes etc. The
out without forming ?ames. From the smoke which does
method can be used in any case where solid or liquid
substances are to be dispersed in air or in other gases.
not contain sulfur dioxide and which is Well tolerated
by plants, a deposit and/or coating is formed, and even
The following are examples in accordance with this 25 if the smoke is strongly diluted, this coating prevents
the germination of mold spores.
Example I
A powder constisting of 28 parts of 1,5-endomethylene
3,7-dinitroso-1,3,5,7-tetraaza-cyclooctane and 72 parts of
ry-hexachlorocyclohexane is ignited at one point with a 30
match. It reacts throughout without flame and expels a
dense 'y-hexachlorocyclohexane aerosol.
Example 2
A powder which contains:
aza-cyclooctane ___________________________ __ 30
35 N-diethyl-n-caprylic acid amide ________________ __ 15
is ignited as described in Examples 2 and 5. The mist
20 40
a-Hexachlorocyclohexane _____________________ __ 20
Attapulgus clay (a highly absorptive clay) _______ __ 25
1,5 - endomethylene - 3,7 - dinitroso-l,3,5,7-tetraaza
1,5 - endomethylene - 3,7 - dinitroso - 1,3,5,7 - tetra
Dicyandiamide _______ __, _____________________ __
Example 6
A powder consisting of:
contains the last mentioned active ingredient and repels
Example 7
A powder which contains:
Talc _______________________________________ __. 10
Aminoazobenzene-azo-?-naphthol (Sudan red) ____ 8
is touched at one point with a glowing or smoldering piece 45
1,5 - endomethylene - 3,7 - dinitroso - 1,3,5,7 - tetra
aza-cyclooctane ___________________________ __ 30
Dicyandiamide ______________________________ __ 20
of paper impregnated with KNO3. It reacts throughout
Aluminium hydroxide gel _____________________ __ 10
without ?ame and expels an intensely red-colored smoke. _ 2,2’ - dihydroxy - 3,5,6 -.3',5',6' - hexachlorodiphenyl
Example 3
methane _________________________________ ___ 40
in accordance with Examples 2, 5 and 6, a smoke
A tablet weighing 5.2 grams and‘ consisting of:
which contains the last mentioned active ingredient.
1,5 - endomethylene - 3,7 - dinitroso-1,3,5,7-tetraaza
Example 8
A granule consisting of:
cyclooctane ______________________________ ___. 1.7
Melamine __________________________________ _'_ 1.0
Polyvinylchloride ___________________________ __ 1.0
Alumina gel ________________________________ __ 0.5
Swellable clay ___
____ __
1,5 - endomethylene - 3,7 - dinitroso - 1,3,5,7 - tetra
aza-cyclooctane ___________________________ __
_ 0.1
Talc ______________________________________ __ 0.4
N-methyl-carbamic acid-phenylester ___________ ___ 0.5,
is dipped at one corner into an aqueous slurry of 40 parts 60
Wood flour
of dextrine, 7 parts of borax, 15 parts of cellulose powder,
1 part of antimony pentasul?de, 12 parts of potassium
persulfate and 25 parts of potassium bromate. This com
bustible composition is dried. A tablet ignited at its com
bustible portion-with a match reacts ?ameless through
out, starting from there, and expels a dense smoke con
Swell-able clay ______________________________ __
Talc _______________________________________ __
'y-Hex'achlorocyclohexane ______________________ ___ 18
reacts throughout without forming ?ames when ignited
with a match and expels a smoke which contains 'y-hexa
taining N-methylcarbamic acid phenylester.
' Example 4
A tablet weighing 4.1 grams and consisting. of:
Guanidine nitrate
____ __
Colophony _________________________________ __ 2
Example 9
A powder consisting of:
cyclooctane _____________________________ __ 0.80
1,5 - endomethylene - 3,7 - dinitroso - 1,3,5,7 - tetra
aza-cyclooc-tane ___________________________ __ 44
1,5 - endomethylene - 3,7 - dinitroso-1,3,5,7-tetraaza
Dicyandiamide ____________________________ __ 0.45
P'olyvinylchloride __________________________ __ 0.25
Guanidine carbonate _________________________ __ 15
Magnesium bromide _________________________ __ 20
of insecticides, fungicides, :bactericides, repellents, and
organic dyestuffs.
Alumina gel
___ 10
'y-Hexachlorocyclohexane _____________________ __ 20
Methylcarbamic acid-phenylester _______________ __
2. A composition in accordance with claim 1, wherein
the member is an insecticide.
3. A composition in accordance with claim 1, wherein
reacts according to Example 1.
The content of l,5-endomethylene-3,7-dinitroso-1,3,5,
7-tetraaza-cyclooctane in the aerosol generating prepara
tions according to the invention has been found to be
most advantageous within the range from 5 to 55%.
the member is a fungicide.
4. A composition in accordance with claim 1, wherein
the member is a bactericide.
5. A composition in accordance with claim 1, wherein
Fillers or diluents ‘are usually used up to a content of 10 the member is a repellent.
6. A composition in accordance with claim 1, wherein
' 30%, in some casesit may be increased to 50%.
the member is an organic dyestuff.
It will be understood that the foregoing description of
the invention and the examples set forth are merely illus
trative of the principles thereof.
Accordingly, the
appended claims are to be construed as de?ning the inven
tion Within the full spirit and scope thereof.
We claim:
1. A composition for use in the preparation of aerosols
consisting essentially of l,5~endomethylene-3,7-di-nitroso
1,3,5 ,7-tetraaza-cyclooctane in a concentration of approx
imately 5 to 55% and a member of the group consisting
References Cited in the ?le of this patent
Peer _________________ __ May 5, 1953
Wunderly ______., ______ __ Jan. 19, 1954
Wright et al __________ .... May 18, 1954
Courtier ______________ .. May 3, 1955
Walker et al _______ _..'_..__ July 10, 1956
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