DE1058895B - Means for smoldering chemical substances - Google Patents

Description

GERMAN

kl. 78 d

INTERNAT. KL. C 06 d

PATENT OFFICE

M36546IVa / 78d

REGISTRATION DATE: JANUARY 30, 1958

NOTICE THE REGISTRATION AND ISSUE OF THE EDITORIAL:

June 4, 1959

The known self-smoldering fumigants generally contain a flammable substance, such as wood flour, Milk sugar or the like, together with an oxygen-releasing substance, e.g. B. a nitrate, chromate, perchlorate or the like, and smolder, lit at one point, more or less quickly, with the smoke to be smoked Substance in the glow zone evaporates and then outside the glow zone again to a finely divided Smoke or mist condenses. Such fumigants have the disadvantage that they are heat-sensitive and heavy Vaporizable substances in the glow zone, which reaches several hundred degrees, are largely decomposed. Man therefore distributes sensitive substances with the help of special devices in the gas space, which is always one requires considerable expenditure on equipment, compressed gases or similar means.

The present invention is based on the object of developing a fumigant with which also thermally easily decomposable and / or difficult to evaporate substances are carbonized without significant losses can.

It was found that "fumigants containing 1,5-endomethylene - 3,7- dinitroso -1,3,5,7-tetraaza-cyclooctane of the formula

CH ₅ ,

CH ₂

I.
ON-N

CH ₈

N -
I.
CH ₂

NO

CH,

are suitable for distributing even decomposable substances in aerosol form in the gas space. It is about self-smoldering preparations, so that no apparatus or other devices are necessary.

IS-endomethylene-SV-dinitroso-IST-tetraaza-cyclooctane decomposes when it is ignited or acidified with evolution of heat and gas. The compound is not hygroscopic, easily accessible (see Mayer, Reports of the German Chemical Society, vol. 21, p. 2883 [2888]) and burns down after lighting with a bright flame. In admixture with non-flammable and / or extinguishing additives or flameless localized heating to at least 200 ° C (possibly in an acidic medium at temperatures below 200 ⁰ C) a flame either remains entirely of or can be easily blow out, and the decomposition reaction passes through the whole mass correspondingly slower. With EhS

octane can therefore be used to produce mixtures that, locally ignited or heated, progressively reacting, with briefly the temperature in the reaction zone Means for smoldering chemical substances

Applicant:

E. Merck Aktiengesellschaft, Darmstadt, Frankfurter Str. 50

Dr. Ernst Jacobi and Hans Bremer, Darmstadt, have been named as inventors

increased and a large volume of gas is ejected. ^{The temperature peak can be reduced to significantly below 200 °} C. by a sufficient proportion of non-combustible, inert accompanying substances; it is thus far below the red heat that is reached in the smoldering zone with the previously known incense. In addition to the low temperature, a substance to be discharged is also spared in that it is removed from the heated reaction zone as quickly as possible by the gas formed.

It was also found that the quality of the fumigants according to the invention and the process of Fumigation reaction through the addition of thermally decomposable nitrogen compounds such as ammonium salts and / or cyanamide and / or urea or its salts and / or compounds which form the group

contain as a structural element, such as melamine, guanidine or preferably dicyandiamide, is improved. These compounds increase the shelf life of the fumigants according to the invention. Since the substances also decompose thermally and thereby increase the p _n value in the reaction zone and release an additional volume of gas, the addition of the nitrogen compounds identified above can lead to the p _H -dependent decomposition reaction of IS-endomethylene-SJ-dinitroso-1, Control 3,5,7-tetraaza-cyclooctane and suppress a flame. Finally, the substances also reduce the formaldehyde odor that occurs during the decomposition of IS-endomethylene-SJ-dinitroso-IS1-tetraazacyclooctane.

3 4

It has also been found that a molten content of 72 parts of γ-hexachlorocyclohexane is found at one point

difficult or non-flammable halogen compounds, lit with a match. It responds without

which split off hydrogen halide above 100 ⁰ C, like a flame and encounters a dense y-hexachlorocyclo-

Tetrachlorocyclohexanone, hexachlorocyclohexane, polyhexane aerosol.

vinyl chloride, trachlorophthalic anhydride, magnesium 5 2. A powder containing 30 parts of 1,5-endomethylene-3,7-dibromide and the like, the p _K value in the reaction zone and nitroso-1SS ^ -tetraaza-cyclooctane, 20 Parts of dicyanim aerosol lowers and suppresses flames without damaging the diamide, 20 parts of α-hexachlorocyclohexane, 12 parts of silica-shelf life of the fumigants according to the invention, 10 parts of talc and 8 parts of aminoazobenzene-azoic acid. / Contains 5-naphthol (Sudan red) is at one point with

Of course, you can touch these incense in a smoldering piece of KNO ₃ -impregnated also the usual additives, such as fillers, salts, binding paper. It reacts flamelessly and emits medium, resins (the latter also used to regulate the exhaustion) from an intensely red-colored smoke.
smoldering speed), means for regulating the 3. A 5.2 g tablet, consisting of 1.7 g moisture content, such as water repellants (e.g. IS-endomethylene-S ^ -dinitroso-IS ^ -tetraaza-cyclo-silicones) and conditioning agents (e.g. B. Sorbitol), 15 octane, 1.0 g melamine, 1.0 g polyvinyl chloride, 0.5 g clay-free odorous substances, dyes, denaturants etc. earth gel, 0.1 g swelling clay, 0.4 g talc and 0.5 g g of N-methyl to be added. You can also add additional energy phenyl carbamic acid, which is placed in a dispenser with a corner, such as B. BaNO ₃ , lactose and the like., Add. aqueous slurry of 40 parts of dextrin, 7 parts

When smoking sensitive substances are borax, 15 parts cellulose powder, 1 part antimony pentadie Fillers are particularly important, as they are used to make the ao sulfide, 12 parts of potassium persulfate and 25 parts of potassium mixture stretch and so immersed the fumigation reaction bromate. This primer will slow down drying can. Depending on the thermal conductivity of the let. The fillers attached to this primer with the match one can see the zone from which the smoke-ignited tablet reacts from there without a flame The substances are driven out, widen or through and pushes a dense N-methyl-carbamic acid narrowing. 25 smoke containing phenyl ester.

In the case of the present fumigants, absorbent 4. A 4.1 g tablet, consisting of 0.80 g of capable fillers, has proven particularly advantageous, IS-endomethylene-S ^ -dinitroso-ISSJ-tetraaza-cyclowenn the substances to be fumigated are sensitive are. octane, 0.45 g dicyandiamide, 0.25 g polyvinyl chloride Melt silicic acid, 0.08 g of swelling clay, 0.17 g of talc, 0.65 g of the reaction zone, unless N-methyl-carbamic acid phenyl ester and 0.35 g of y-hexa are at all substances that are found in room chlorocyclohexane , reacts, at a corner with the painting temperature are liquid. These fillers include fine wood ignited and shortly afterwards blown out, flameless, partial types of silicic acid and other silicates and oxides, and emits a thick smoke, which contains the two, above all, those active substances mentioned under the term »light injuries .
Starch fillers "fall, furthermore alumina gel, finely divided 5. A powder consisting of 15 parts 1,5-endo-clays, kieselguhr, other metal oxides and also wood methylene-3,7-dinitroso-1,3,5,7-tetraaza -cyclooctane, 30 part flour, cellulose powder, carbon black, graphite, fine-powdered art len dicyandiamide, 30 parts of sulfur bloom and 25 parts of substances, such as polyvinyl alcohol and hardened amino-N-trichloromethylthiotetrahydrophthalimide, is, as described in the plastic, etc. 40 Example 2, ignited . It reacts flamelessly

The self-smoldering smokers according to the invention through, and from the smoke that does not produce sulfur dioxide

means can be used in any form, lasts and is well tolerated by plants, proves itself

z. B. as powder, granules, tablets, sticks or even from a large dilution, a coating that

Carrier applied layers etc. The fumigation prevents germination of fungal spores,

can easily be used with a match flame, a heating 45 6. A powder consisting of 30 parts of 1,5-endo-

wire, a heating plate, a fuse or with fuse methylene-S ^ -dinitroso-IASJ-tetraaza-cyclooctane, 30 parts

introduce paper. It is always sufficient to add the incense to len dicyandiamide, 25 parts of Attaclay (highly absorbent

to ignite one place and react from there clay mineral) and 15 parts of N-diethyl-n-caprylic acid amide,

allow. is, as described in Examples 2 and 5, ignited. Of the

For the fumigants according to the invention there are 50 mists containing the active ingredient mentioned last

no equipment necessary, but you can z. B. one and drives away insects.

free-flowing fumigant continuously a heating 7. A powder with 30 parts of 1,5-endomethylene-3,7-di-

supply source. The aerosol can also be replaced by a nitroso-l.S.S ^ -tetraaza-cyclooctane, 20 parts of cyanogen

Gas stream, e.g. B. with a blower, into a desired diamide, 10 parts of aluminum hydroxide gel and 40 parts

Drive direction or the fumigation in a 55 2,2'-dioxy-3,5,6-3 ', 5', 6'-hexachlorodiphenylmethane

Perform chamber, which has a small opening, gives, according to Examples 2, 5 and 6, a

from which the aerosol in the desired direction from smoke, the last mentioned active ingredient

flows. It is also possible to get the aerosol particles through it.

an apparatus in addition a stronger electrostatic 8. A granulate, consisting of 9 parts 1,5-endo-

To give charge. 60 methylene - 3,7 - dinitroso - 1,3,5,7 - tetraaza - cyclooctane,

For the fumigants according to the invention there are 55 parts of guanidine nitrate, 2 parts of rosin, 9 parts rich fields of application, e.g. B. pest wood flour, 3 parts kaolin, 2 parts swelling clay, 2 parts control, in plant protection, in disinfection, in talc and 18 parts ^ / - hexachlorocyclohexane, reacts, the fireworks, for signaling purposes etc. You can light them with a match, flameless by and So use wherever solid or liquid substances 65 emit a smoke, the γ-hexachlorocyclohexane entin Air or in other gases are to be distributed. holds.

. 9. A powder consisting of 44 parts of 1,5-endomethy-

Examples len-SJ-dinitroso-LASJ-tetraaza-cyclooctane, 15 parts

1. A powder consisting of 28 parts of 1,5-endo-guanidine carbonate, 20 parts of magnesium bromide, 10 parts methylene-S ^ -dinitroso-l.S.S ^ -tetraaza-cyclooctane and 70 alumina gel, 20 parts of y-hexachlorocyclohexane and 6 parts

len methylcarbamic acid phenyl ester, corresponding to example 1.

Claims (4)

Patent claims: 1. Agent for smoldering chemical substances, characterized by a content of 1,5-endomethylene-S.T-dinitroso-l.S.S.T-tetraaza-cyclooctane. 2. Means according to claim 1, characterized by an addition of ammonium salts and / or Cy anamid and / or urea or its salts and / or compounds which form the group • N = c: reacts as a structural element, such as melamine, guanidine or preferably dicyandiamide. 3. Composition according to claim 1 and 2, characterized by an addition of one or more fusible, difficult or incombustible halogen compounds which ^{split off hydrogen halide above 100 0} C, such as. B. tetrachlorocyclohexanone, hexachlorocyclohexane, polyvinyl chloride, tetrachlorophthalic anhydride, magnesium bromide and the like. 4. Means according to claim 1 to 3, characterized by an addition of absorbent fillers, such as z. B. finely divided types of silica, silicates, alumina gel, finely divided clays, kieselguhr, metal oxides, Wood flour, cellulose powder, carbon black, graphite, fine-powdered plastics such as polyvinyl alcohol or cured aminoplasts.