CS258208B1 - Modifiers of aliphatic nitroamines and/or azo-compounds - Google Patents

Abstract

The use methylated or 2-etylhe- hexanol esterified and / or transesterifi- forged side products oxidation cyclo hexane on the cyclohexanol and cyclohexane than modi fikátorov aliphatic nitrosamine, than They are 1 . 5-methano 3 7-dinitroso-l 3.5. 7-tetraazacyklo- octane and 1 . 3 . 5-l-trinitrózo . 3 5-triazacyklohe- XAN and / or aliphatic azo compounds, than They are azodicarbonamide and azobisisobutyronitrile diizobutyronitril . in quantity 2 until 20 weight parts nitróz- amine and / or azo compounds on the one weight part esterified and / or transesterifi- forged side products. Approach is a suitable najmS for modification features blowing agents with active ingredients nitrosamine and / or azodikarboxamidové type, and it than at country it production blowing agents, so at their use.

Description

I 258208

SUMMARY OF THE INVENTION The present invention relates to modifiers based on esterified and re-esterified by-products of cyclohexane to cyclohexanol and cyclohexanone for the modification of nitrosamine and / or aliphatic azo compounds.

Nitrosamines, as thermodynamically unstable substances, tend to uncontrollable explosions. In the case of technically attractive nitrosaraine-based products, these undesirable properties are suppressed by phlegmatization and / or control with inert additives. However, in the case of rubber blowing agents with nitrosamines as active components, traditional phlegmatizing agents such as water, mineral oils, or silicone oils may have an adverse effect on the quality of the product to be coated. At present, the most widely used blowing agents for the production of microporous articles made of artificial and rubber are mixtures based on azodicarboxamide, but mostly technical azodicarboxamide.

The less used azo group compound in the molecule for this purpose, in particular as a polymerization initiator, is azo-bis-diisobutyronitrile.

Even as 3, azodicarboxamide is also one of the thermodynamically unstable substances, it is practically non-flammable (self-extinguishing), but when it is incorporated into a bottled mixture, its explosions, caused inter alia by its impact on impact, are not rare. A very unpleasant property of azodicarboxamide is its dustiness, which can lead to bronchial asthma disease in people working with it (described in 18.5% of the monitored population - see A. R. Nutt:

Toxic Hazards of Rubber Chemicals; Elsevíer Appl. Sci. Publ., London, 1984). Powderazodicarboxamide also appears to be markedly susceptible to agglomeration.

In the application of azodicarboxamide-based blowing agents, especially in the rubber industry, or in ethylene-venylacetate copolymers, it is desirable to reduce the decomposition temperature of the azodicarboxamide, i.e., this. and to activate the compound. This is achieved by the addition of various activator to the bottled mixture and / or the azodicarboxamide itself, such as zinc, cadmium and other salts, hexamethylenetetramine, urea water-soluble powder derivatives, biuret, and, in essence, demanding chemical technology products for raw materials, energy and human labor. gii. In order to meet the requirements of special and new uses of aliphatic nitrosamine / or azocompounds, there is an increased activity in the field of modification of their properties, especially motivated by efforts to replace expensive, less available or environmentally friendly modifiers with technically and economically more affordable products of the chemical industry.

According to the invention, for the modification of the properties of aliphatic nitrosamines, such as 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacyclooctane, and / or azo compounds such as azodiocarboxamide and azo-bis-diisobutyronitrile, used by methanol or 2-ethylhexanol by esterified and / or re-esterified by-products of cyclohexane to cyclohexanol and cyclohexanone, in an amount of 2 to 20 wt. parts of nitrosamine and / or azo compound per one part of the by-products thus treated. The advantage of the present invention is in particular the availability of by-products of cyclohexanone cyclohexanol and cyclohexanone oxidation, which are a mixture of aliphatic diacids, monoacid esters of which are esterifiable and / or re-esterified to obtain modifiers of the present invention. By the process of the present invention, it is possible to utilize secondary raw materials resulting from the production of cyclohexanone by oxidation of cyclohexane, which is another advantage of the process. By suitable application of a suitable disintegrating agent in the sense of the present invention, the aliphatic nitrosamine and / or the azo compound can be activated or, conversely, stabilized, which is also a preferred feature of the present invention, especially in the case of blowing agents containing said compounds as active ingredients.

The modifiers of the present invention contain components, some of which are self-used as plasticizers, respectively. plasticizer plasticizers, the process of this invention in the case of blowing agents may contribute to obtaining refined products with favorable physical-mechanical properties at the potential savings of "noble" plasticizers, respectively. a softener, which is a further advantage of the present invention.

The use of esterified and / or re-esterified (transesterified) byproducts of cyclohexane to cyclohexanol and cyclohexanone oxidation as aliphatic nitrosamphine and / or azo compound modifiers has not been described in the literature; is documented by the following examples, which in no way exclude the variability of the process of the invention. EXAMPLE 1 There is a methyl ester fraction obtained by esterification and transesterification of the other products of cyclohexane to cyclohexanone oxidation with methanol under reaction conditions: temperature 210 ° C, pressure 4.5 MPa, for 1.5 to 3 hours, at a weight ratio of methanol to by-product equal to 2 , catalysing 0.7 wt. p-toluenesulfonic acid. This fraction is characterized by the following parameters: - saponification number ............................... 427.2 mg potassium hydroxide per g; - ester number ............................... 399.18 mg potassium hydroxide per g; 20 -3 - specific weight ....................... d ^ = 1,034.4 kg.m; refractive index ........................ n ^ O = 1.438 3; - viscosity at 20 ° C .................................. 5 192 mPa.s; - coloring according to Hanzen scale less than 1; - hydroxyl content ........................ 3.97% by weight; - water content ............................. 0.73% by weight;

Chromatographically determined (% by weight): 27.4% dimethyl adipate, 6.3% dimethylglutarate, 5.4% dimethyl succinate, 0.5% methylvalerate, 0.9% methylcaproate, 0.01% methylpropionate, 0.46% methanol and 10.0% 1,2-cyclohexanediol; the esters thus determined represent 67.25% by weight, all the esters in the fraction and similarly determined alcohols represent 79.91% by weight of all hydroxyl compounds in the fraction.

The methyl fraction begins to distil at temperatures above 100 ° C to 145 ° C. 50% by weight distilled to 214 ° C; % and 95% by weight of the fraction are distilled to 236 ° C. fractions. . Of this fraction and technical 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacycloctane (contains up to 5% by weight 1,3,5-trinitroso-1,3,5-triazacyclohexane), a semi-particulate mixture with a content of 10% by wt. of said fraction. As can be seen from the thermal stability (see Example 5), the methyl ester fraction activates DNPT. EXAMPLE 2 A slurry containing 8% by weight of said fraction is prepared from the methyl ester fraction of Example 1 and the technical azodicarboxamide. The dustiness and sintering of the mixture is suppressed by the opaque azodicarboxamide. As can be seen from the thermal stability (see Example 5), the thermal stability of the azodicarboxamide is increased by addition of the methyl ester fraction.

Example3

The methyl ester fraction of Example 1 is transesterified with 2-ethylhexanol at 170 ° C for 2-3 hours, the weight ratio of ethylhexanol to methyl ester fraction 2 to 2.5, catalysed with 0.5% by weight. titanium dioxide and catalysis of 1 wt. sodium hypophosphite monohydrate. The resulting 2-ethyl-hexyl ester fraction is characterized by parameters: 258208 4 - acid number ............... 2 mg of potassium hydroxide per g; - saponification number .............. 317.1 mg of potassium hydroxide per gram; ester number ............... 315.1 mg potassium hydroxide per gram; a free 2-ethylhexanol content of 0.2% by weight. From this fraction and the technical 1,5-methano-3,7-dinitroso-1,3,5,7-tetracycloctane from Example 2, a mixture containing 10 wt. of said fraction. As can be seen from the overview of thermal stability (see Example 5), the 2-ethylhexyl ester fraction increases the stability of DNPT. EXAMPLE 4 A powder mixture containing 7% by weight of the azodicarboxamide is prepared from the ethylhexyl ester fraction of Example 3 and the technical azodicarboxamide. of this fraction. The dustiness and sintering of the mixture is suppressed compared to the starting azodicarboxamide. As can be seen from the thermal stability (see Example 5), the addition of the 2-ethylhexyl ester fraction to the azodicarboxamide has no significant effect on the stability. Example 5

Using non-isothermal differential thermal analysis (DTA), operating at a linear temperature rise of 5 ° C / min, a measuring range of 1 mV on a scale scale, and about 50 mg of the sample, the methano-3,7-dinitroso-1,3,5,7-tetraazacyclooctane and azodicarboxamide, using the commercial product Chempor N 90 (technical DNPT containing 10% by weight of mineral oil) as a comparative standard for mixtures based on DNPT, established beginnings and other thermal decomposition characteristics.

The heat explosion method of H. Henkin and R. McGill (Ind. Eng. Chem. 1952, 44, No. 06, 1391-1395) for the mixtures of Examples 1 to 4 as well as for the initial 1,5-methane -3,7-dinitroso-1,3,5,7-tetraazacyclooctane and azodicarboxamide, using Chempor N 90, Specified Induction Periods for DNTP and NeedleBase Mixtures in the Temperature Range 190 to 210 ° C, for Azodicarboxamide and mixtures based on its base in the temperature range of 210 to 250 ° C. From the thus obtained induction periods, the activation energy of the explosion E and the extrapolated induction periods for 150 and 190 ° C are calculated, and the results of these thermoanalytical methods are presented in Table 1. Example 6 K the methyl ester fraction of Example 1 and the azo-bis-diisobutyronitrile are available, of which a mixture containing 5% by weight of the methyl ester fraction is prepared, which significantly increases the thermal explosion stability of said azo compound (Table 2). in Example 8) 5 258208

Table 1 is an overview of the results of the thermostable measurements of Example 5

Sample Odaie from DTA Thermal explosion method Exot origin <° C) ermic decomposition first pl (° C) explosion (° C) E (kj.mol-1) TaU150 <s) Tau190 (s) DNPT initial disc 139, 1 ± 0 , 4 169.7 ± 0.4 185.3 ± 1.0 58.94 213.8 50.3 according to Example 1 119.9 ± 0.8 172.8 ± 0.5 180.3 ± 0, 7 49.70 160.4 47.3 According to Example 3 134.2 ± 0.7 171.7 ± 0.3 180.2 ± 1, 5 63.71 277.3 58.0 Chempor N 90 119, 2 ± 3.1 169.2 ± 2.8 185, lil, 7 55.27 217.4 55.9 ADC initial 161.5 ± 1.2 193.0 ± 0.9 57.68 341.0 82.7 according to Example 2 172.5 ± 2.3 195.0 ± 0.6 65.50 607.0 121.0 according to Example 4 162.7 ± 0.9 - 193.2 ± 0, 0 53.85 321.0 85.6

Notes: DNPT = 1,5-metano-3,7-dinitroso-1,3,5,7-tetraazacyclooctane technical (containing up to 5% by weight 1,3,5-trinitroso-1,3,5-triazacyclohexane); ADC = azodicarboxamide; E = activation energy of the explosion;

Tau150 = extrapolated for induction periods at 150 ° C;

Averaged for DNTP, extrapolated for explosive-based mixtures at 190 ° C; EXAMPLE 7 A 2-ethylhexyl ester fraction from Example 3 and azo-bis-diisobutyronitrile are available, and a blend of 5% by weight of these materials is prepared. an ethylhexyl ester fraction which enhances the stability of said azo compound from the point of view of thermal explosion (see Table 2 of Example 8). Example 8

With the aid of DTA as in Example 5 and using the method of thermal explosion as in Example 5, the thermal stability of the compositions of Examples 6 and 7 as well as the starting azo-bis-diisobutyronitrile is specified; the results are presented in Table 2:

Claims (3)

OBJECT OF THE INVENTION Use of methyl alcohol or 2-ethylhexanol esterified and / or transesterified by-products of cyclohexane oxidation to cyclohexanol and cyclohexanone as modifiers of aliphatic nitrosamines, such as 1,5-methano-3,7-dihydro-1,3,5,7-tetraazacyclooctane and 3,5-trinitroso-1,3,5-triazacyclohexane and / or aliphatic azo compounds such as azodicarboxamide and azo-bis-diisobutyronitrile.