CS238441B1 - Rubber and plastic wrapping - Google Patents

Abstract

The invention relates to a rubber and plastic blowing agent based on cyclic nitrosamines, such as 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacyclooctane and/or 1,3,5-trinitroso-1,3,5-triazacyclohexane, or as mixtures based on them, which contain, per 1 wt. part of cyclic nitrasamine, 0.01 to 1 wt. part of halogenated tripropyl phosphate, characterized by a phosphorus content of 3.8 to 8 wt. %. The process according to the invention is useful in the production and/or application of rubber and plastic blowing agents with new utility properties.

Description

The invention relates to a rubber and plastic blowing agent based on cyclic nitrosamines modified with halogenated tripropyl phosphates.

Nitrosamines, as thermodynamically unstable substances, can undergo uncontrolled explosive transformations. In technically attractive products based on them, this undesirable property is suppressed by phlegmatization and/or dilution with inert additives. In the case of rubber blowing agents with nitrosamines as active ingredients, however, traditional phlegmatizing agents, such as water, mineral or silicone oils, can have an adverse effect on the quality of the lightened product. In order to meet the requirements of special and new applications of cyclic nitrosamines, especially in the field of production of lightened materials and/or products, there is an effort to modify the properties of the aforementioned nitrosamine compounds so that they meet the intensification and innovation measures in the national economy.

According to the present invention, the properties of cyclic nitrosamines and/or mixtures based on them, used as rubber or plastic anti-blowing agents, are modified by halogenated tripropyl phosphates, such as technical tris(dichloropropyl)-phosphate and technical tris(dibromopropyl)-phosphate in an amount of 0.01 to 1 part by weight of phosphate per 1 part by weight of cyclic nitrosamine. The applied tripropyl phosphate derivatives contain 3.8 to 8% by weight of phosphorus.

The advantage of this invention is the elimination of dustiness of cyclic nitrosamines and/or products based on them by a technically available additive, which in many cases significantly improves the thermostability characteristics of the above-mentioned nitroso compounds. In the case of blowing agents with an active component of the nitrosamine type with phlegmatization based on tripropyl phosphate derivatives, another advantage is the potential reduction of flammability and plasticization of the lightened material, since man-made phosphates are applied in technical practice as flame retardants and plasticizers of organic macromolecular materials.

The modification according to the present invention of cyclic nitrosamines and/or mixtures based on them with halogenated tripropyl phosphate derivatives has not been described in the literature so far; it is documented by the following examples, which, however, in no way exclude possible variability of the process according to the present invention.

Example

Technical 1,5-methano-3,7-dintroso-1,3,5,7-tetraazacyclooctane (codenamed DNPT) with a content below 2.5% by weight is available.

1,3,5-trinitroso-1,3,5-triazacyclohexane (code name NITROSOGEN). Furthermore, technical tris (2,3-dibromopropyl) phosphate (hereinafter referred to as DBPF) with a phosphorus content of 5.01% by weight, and technical tris (dichloropropyl) phosphate (hereinafter referred to as DCPF) with a phosphorus content of 7.79% by weight are available.

From the above raw materials, mixtures of semi-loose consistency are prepared, which does not change after storage for 30 days at a temperature of 20 to 24 °C. Using non-isothermal differential thermal analysis (DTA), working with a linear rate of temperature increase of 6 °C. min ^-1 , a measuring range of 0.5 mV per scale scale, a paper feed rate in the recorder of 20 mm. min ^-1 and weighings of 150 to 200 mg of sample, the thermostability of the prepared mixtures and the starting DNPT is specified both by the beginnings of exothermic decomposition and by the Pilojan decomposition energies (for the methodology of the given case, see S. Zeman: J. Thermal. Anal. 1979, 17, 19—29). The results are presented in Table No. 1, from which it is evident that tris(2,3-dibromopropyl)-phosphate in particular significantly suppresses the exothermicity of the initial stage of thermal decomposition of DNPT. Tris(dichloropropyl)phosphate slightly increases the onset of decomposition, and after its onset slightly accelerates the decomposition of DNPT, which may be advantageous in some applications of the corresponding blowing agents.

Table No. 1:

Additive content in DNPT Beginning Pilojan's activation phosphate mass parts exothermic energy per 1 wt. decomposition temperature (kj.: part of DNPT PC) range (°C)

without additives 0.000 113.3 114—130 83.62 DCPF 0.066 115.6 118—130 58.94 DBPF 0.020 113.2 114—128 130.01

Example 2

Technical 1,3,5-trinitroso-1,3,5-triazacyclohexane (NITROSOGEN) and tris(dichloropropyl)-phosphate (DCPF) from example 1 are available. In principle, the procedure is according to example 1:

— for the starting NISTROSOGEN, the onset of melting at 97.3 °C, its peak at 106.5 °C, the onset of the first peak of exothermic decomposition at 125.5 °C, its peak at 131.3 °C and the onset of the second pi- to exo-decomposition at 145.7 °C were found using DTA, with the Pilojan activation energy in the temperature range 126—131 °C equal to 326.30 kj . mol“ ¹ ;

— for a mixture containing 0.0699 parts by weight of DCPF per 1 part by weight of NITROSOGEN, the onset of melting was found using DTA at

96.1 °C, its double peak at temperatures of 104.9 and

100.8 °C, the beginning of the first exothermic decomposition peak at 125.0 °C, its peak at 132.0 °C and the beginning of the second exo-peak at 148.0 °C, with the Pilojan activation energy of decomposition in the temperature range 126—130 °C equal to 466.62 kj . mol“ ¹ .

Example 3

From DNPT and DBPF from Example 1, water-insoluble urea-formaldehyde condensate with a molar ratio of formaldehyde to urea of 0.9:1 and rubber kaolin, a mixture is prepared with the composition (%/wt.): 30 percent condensate, 30% DBPF and 10% kaolin. This mixture has a semi-freezing consistency and using DTA as in Example 1, the onset of exothermic decomposition is found at

114.9 °C.

Claims (3)

Example 2 Technical 1,3,5-trinitroso-1,3,5-triazacyclohexane (NITROSOGEN) atris (dichloropropyl) phosphate (DCPF) from Example 1 is available. 1: - at the starting NISTROSOGEN, the start of the melting point at 97.3 ° C, its peak at 106.5 ° C, the beginning of the first peak of exothermic decomposition at 125.5 ° C, its peak at 131.3 ° C and the origin a second peak of exo-decomposition at 145.7 ° C, with Pilojan inactivation energy in the temperature range 126-131 ° C equal to 326.30 kj. mol '1; - in a mixture containing 0.0699 wt. die-hunting DCPF per 1 wt. part of NITROSOGEN is the starting point of melting at 96.1 ° C, its peak at 104.9 and 100.8 ° C, the beginning of the first peak of the exothermic deposit at 125.0 ° C, its peak at 132.0 ° C and the second exo-peak at 148.0 ° C, with a decomposition digestion energy in the temperature range of 126-130 ° C equal to 466.62 ° C, temperature range 126-130 ° C equal to 466.62 kj. mol '1. EXAMPLE 3 From DNPT and DBPF of Example 1, a water-soluble urea-formaldehyde condensate having a molar ratio of urea formaldehyde of 0.9: 1 and a rubber kaolin, the prepared mixture of (% by weight): 30% of condensate, 30% of DBPF and 10% of kao -lin. This mixture is of semi-solid consistency, and with DTA as in Example 1, the most exotic heat is at 114.9 ° C. OBJECT 1. Rubber and plastics surfactant base of cyclic nitrosamines such as 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacyclo-octane, 1,3,5-trinitroso-1, 3,5 triazacyclohexane, or as mixtures thereof based on 1 wt. part of the cyclic nitrosamine contains 0.01 to 1 part by weight of halogenated tripropyl phosphate, the main component of which is tris (dichloropropyl) phosphate or tris i-dibromopropyl propyl phosphate, containing 3.8 to 8% by weight. phosphorus. Y N A L E z u 2. Rubber and plastics blowing agent according to claim 1, characterized in that it is 1 wt. parts of cyclic nitrosamine contain at least 0.02 wt. a diet of halogenatedhotropropyl phosphate. 3. Rubber and plastics blowing agents according to claim 1, characterized in that the halogenated tripropyl phosphate contains 5.01 to 7.79% by weight. phosphorus.