CS233262B1 - Modified nitrosamines or mixtures thereof - Google Patents

Abstract

In the case of nitrosamines or mixtures based on them, especially blowing agents with a nitrosamine active component, the addition of triaryl phosphates or mixed triaryl phosphates significantly increases the thermal stability of the resulting mixture. The additives mentioned simultaneously suppress the dustiness of the mixture, act as phlegmatizing agents, plasticizers and flame retardants. Thus modified nitrosamines or their mixtures with other components are used primarily as blowing agents for plastics or rubber products; by using them in the above sense, a flame retardant is simultaneously introduced into the expanded material.

Description

(54) Modified nitrosamines or mixtures thereof

For nitrosamines or mixtures thereof, especially blowing agents with a nitrosamine active ingredient, the addition of triaryl phosphates or mixed triaryl phosphates significantly increases the thermal stability of the resulting mixture. At the same time, these additives suppress the dustiness of the mixture, acting as phlegmatizing agents, plasticizers and flame retardants. The modified nitrosamines or mixtures thereof with other components find use primarily as blowing agents for plastics or rubber products; by using this means, a flame retardant is simultaneously introduced into the expanded mass.

the

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The invention relates to the modification of nitrosamines or mixtures thereof based on triaryl phosphates or mixed triaryl phosphates.

Nitrosamines, as thermodynamically unstable substances, tend to undergo explosive transformations uncontrolled ·

For technically attractive nitrosamine-based products, this undesirable property is suppressed by phlegmatization or dilution with inert additives. · Phlegmatization of nitrosamines, which could be exploited as cast-explosive explosives, is problematic at all.

According to the invention, the modification of the properties of the nitrosamines, in particular the increase in their thermal stability, is achieved by the addition of triarylphosphates or mixed triarylphosphates to nitrosamine or a mixture thereof based on 0.1 to 60% by weight, preferably 3.9 to 50% by weight. to the weight of nitrosamine ·

By triaryl phosphates is meant the compounds of the general formula ZR-O- (R) = P, where R- is phenyl, chlorosp. polychlorophenyl, bromo- or polybromophenyl, methylrespdimethylphenyl, isopropyl- and polypropylphenyl; diisopropylphenyl, isobutyl- or diisobutylphenyl, biphenylyl, alkylchlor2

233 262 reap · alkylbromophenyl a-pod, This group of phosphates is characterized by a content of 5 to 10% by weight of phosphorus ·

By mixed triaryl phosphates is meant substances of the general formula

bo can possibly. R 6, R 6, wherein any of these groups may be chemically defined as any of the R groups of triaryl phosphates (see above). Mixed triaryl phosphates are characterized by a content of 4 to 9% by weight · phosphorus ·

In particular, the advantage of the present invention is a significant increase in the thermal stability of nitrosamines or mixtures based on them by a technically and economically readily available additive; this higher effect is of great importance for the safety of work in the storage, transport and handling of nitrosamine-based products. In the case of the blowing agents with the nitrosamine active ingredient, there is also a suppression of their dustiness and a decrease in the flammability of the expanded organic material / the phosphates applied are flame retardants of polymers /

In the case of cast explosives based on nitrosamines, there is a further increase in the flowability in the molten state and suppression of the brittleness of the solidified melt, since the triaryl phosphates and mixed / analogues thereof generally act as plasticizers.

Modifications according to the invention of nitrosamines or mixtures based on their triaryl phosphates or mixed triaryl phosphates have not been previously described in the literature; is documented by the following examples, but which in no way exclude the possible · variability of the modification process *

Example 1

Tricresyl phosphate with an o-isomer content of 8.4% by weight of phosphorus is available.

Mixed triaryl phosphate with a predominantly tris / isopropylphenyl / phosphate content, but also containing triphenylphosphate, bis / isopropylphenyl / phenylphosphate,

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-3-isopropylphenyl diphenylphosphate and triphenylphosphate derivatives having one or two isopropyl groups on any of the phenylft; this mixed triaryl phosphate, produced in the Czechoslovakia by the company name Retar 131 «, is characterized by a content of 7.48% by weight. phosphorus ·

Recrystallized N-methyl-N-nitrosourea (MNU) from aqueous methanol serves as starting nitrosamine for the preparation of mixtures of:

Mixture A: half paste with 10.1 wt. trikresylfosfátuj

Mixture B: Semi-Powder containing 3.9% Retar 131;

For the initial MNU, as well as mixtures A and B, thermal stability is specified by a non-isothermal differential thermal analysis (DTA) operating at a linear temperature rise rate of 5 ° / min, a measuring range of 1 mV per scale and sample weights 80- 90 mg. The results are presented in the following table. The exotherm break indicates the temperature at which a rapid increase in rate of decomposition occurs, resulting in sample explosion.

Sample Beginning exotherms from ° C / Zlom exotherms / ° c / MNU 86.6 103.5 Mixture A 96.3 110.4 Mixture B 103.9 117.7

Example 2

Arylphosphates as in Example 1 and technical 1,5-methoo-3,7-dinitroso-1,3,5,7-tetraazacyclooctane (DNPT) are available. Mixtures of 20% by weight are prepared from these raw materials. arylphosphates. In the same manner as in Example 1, i.e. by DTA, the thermal stability presented in the following tabular overview is specified for the starting DNPT · and the corresponding mixtures:

233 262 «· ψ« ·

Sample Beginning exotherms / ° C / First peak exotherms / ° c / default DNPT 136.4 160.5 with tricresyl phosphate 145.9 disappeared with phosphate Retar 131 148.0 disappeared

Example 3

The arylphosphates as in Example 1 and the technical 1,3,5-trinitroso-1,3,5-triazacyclohexane (NITROSOGEN) with which they were in the II. World War II made attempts to apply it as a cast explosive. Mixtures of the following raw materials are prepared:

Mixture A: half paste containing 10.4% by weight of tricresyl phosphate;

Mixture B: semi-loose with a 6.3% by weight Retar 131 content

In the same way as in Example 1, stability is specified by DTA, tabulated in the following:

Sample -Fomek thaw / ° c / pTk— thaw / ° C / řočáTéE- exotherms / ° c / NITROSOGEN 92.2 99.7 136.5 Mixture A 89.6 96.2 143.8 Mixture B 89.2 97.5 139.3

The arylphosphate-containing melt of NITROSOGEN is clearly less brittle after solidification than the melt of the starting substance; stiffened Mix-A visually resembles ceresin »

- 5 at 233 262 Example 4

From the technical 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacyclooctane, the mixed Retary 131 triaryl phosphate of Example 1, and other additives (see below), the blowing agents are prepared having a composition (w / w). %/and

Mixture A: 60% 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacyclooctane, 20% water-insoluble urea-formaldehyde condensate with a molar ratio of urea to formaldehyde and 1: 0.9 and 20% Retar 131.

Mixture B: 40% 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacyclooctane, 40% precipitated calcium carbonate and 20% Retar 131.

Mixture C: 80% 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacyclooctane, 10% precipitated calcium carbonate and 10% Retar 131.

All these mixtures are free-flowing and semi-flowing and do not change their consistency even after 180 days of storage at 20-23 ° C. For the starting nitrosamine and mixtures A and B, thermal stability was specified by DTA as in Example 1, only with a measuring range of 2 mV

Sample Beginning exotherms / ° c / ~ PrvnípTk- exotherms / »0 / 1,5-Methano-3,7-dinitroso-1,3,5,7-tetraazacyclooctane 136.4 160.5 Mixture A 151.2 disappeared Mixture B 147.8 disappeared

Eats A, B and C were monitored for their effect on the vulcanization system of the rubber compound. As a standard, commercial blowing agent of the company name Chempor PC-55 (65% by weight) was applied. % By weight of 1,5-methano-3,7-ainitroso-1,3,5,7-tetraazacyclooctane; urea complex with methylolurea respectively. % methylenebismurea and 14.5 wt. water. Vulcanization characteristics * »6 233 262 rubber mixtures were determined on a Qottfert elastograph at 155 ° C - results are presented in the table:

Sample / Nm / “Max / Nm / Si / min / ^ / 5min / - / kN / Chempor PC-65 0.18 0.72 3.0 1.68 Mixture A 0.16 0.60 4.8 1.35 Mixture B 0.16 0.60 3.7 1.38 Mixture C 0.16 0.60 3.9 1.44

where yo minimum torque is maximum torque t _bl is processing safety

F ^ is the pressure of the gas released in the 5 minute test

The growth properties of blowing rubber compounds Mixtures A and C are the same as those of Chempor PC-65. Mixing into the rubber blowing agent mixture The mixture of A, B and C was better than the commercial PC-65.

LEZU

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Claims (1)

SUBJECT MATTERS Modified nitrosamines or mixtures based thereon, characterized in that they contain 0.1 to 60% by weight, preferably 3.9 to 50% by weight, of triaryl phosphates or mixed triaryl phosphates, calculated on the weight of nitrosamine mixed with triaryl phosphate or mixed triaryl phosphate wherein the triaryl phosphates or mixed triaryl phosphates contain 4 to 10 wt% phosphorus, preferably they contain 7.48 to 8.4 wt% phosphorus. phosphorus.