CS235581B1 - A blowing agent based on a mixture of 1,5-5-ethano-3,7-din - Google Patents

Abstract

The invention relates to the production of a blowing agent based on a mixture of 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacyclooctane with azodicarbonamide, wherein the blowing agent may also contain modifying components. The weight ratio of the nitrosoamine component to azodicarbonamide ranges from 10:1 to 1:1 and the weight ratio of both active components to the other components of the blowing agent is greater than 0.5:1. The blowing agent is applicable for lightening products of rubber, but especially plastics technology.

Description

(54) Blowing agent based on a mixture of 1,5-5-hexane-3,7-dinitroso-1,3,5,7-tetraazacyclooctane with azodicarbonamide

The invention relates to the production of a blowing agent based on a mixture of 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacyclooctane with azodicarbonamide, wherein the blowing agent may also contain modifying components. The weight ratio of the nitrosoamine component to azodicarbonamide ranges from 10:1 to 1:1 and the weight ratio of both active components to the other components of the blowing agent is greater than 0.5:1. The blowing agent is applicable for lightening products of rubber, but especially plastics technology.

The invention relates to the production of a blowing agent based on a mixture of 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacyclooctane with azodicarbonamide.

The lightening of various rubber or plastic products is attractive not only from the point of view of saving often expensive macromolecular raw materials, but also from the point of view of obtaining better or new utility properties of rubber and plastic technology products.

The choice of a blowing agent (blowing agent) is determined primarily by the nature of the material to be lightened and the temperature regime of its processing and, last but not least, by the required utility properties of the final product. The wide range of technically significant macromolecular materials corresponds to a relatively wide range of substances or mixtures based on them, applied as blowing agents. For a given lightened composition, one, less often two individually dosed blowing agents are applied in the vast majority; the production and application of blowing agents based on two or more active ingredients is very little widespread in technical practice.

The present invention relates to the production of a mixed blowing agent with the active ingredients 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacyclooctane and azodicarbonamide, wherein the blowing agent may also contain other modifying ingredients. The weight ratio of the first-mentioned active ingredient to the second is 10:1 to 1:1 and the weight ratio of both active ingredients to the other components of the blowing agent is greater than 0.5:1.

The advantage of this invention is primarily the possibility of choosing the mutual ratio of active ingredients, quality and quantity of modifying additives, in a relatively wide range to influence the utility properties of the resulting blowing agent. At the same time, a very fine pore structure in the lightened material can be achieved, which is not possible to achieve by applying the technically and economically available 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacyclooctane alone. When applying the blowing agent according to this invention in rubber technology, azodicarbonamide also appears as a deodorant component, which is another advantage of the invention.

As modifying components, in the production of the blowing agent according to the present invention, it is possible to apply additives that are common in the production of blowing agents based on 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacyclooctane, but preferably water-insoluble urea-formaldehyde condensates and/or substances generated from oxirane, including modified and/or unmodified polyethylene terephthalate oligomers.

The yield of gaseous products from the thermolysis of the active components of the blowing agent according to the present invention can be influenced by the application of azodicarbonamide decomposition catalysts, such as accelerators based on 1,2,4-triazole derivatives, some tertiary amines, and the like.

The process according to the present invention is documented by the following examples, which, however, in no way exclude possible variability of the process.

Example 1

A bulk mixture is prepared from technical 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacyclooctane (hereinafter referred to as DNPT) and technical azodicarbonamide (code ADK) with a content (% by weight): 71.42 % DNPT and 28.58 % ADK (weight ratio of the first to the second 2.49 : 1j. Using non-isothermal differential thermal analysis (DTA), operating with a linear temperature rise rate of 5 °C/min, a measuring range of 1 mV per scale scale and sample weights of 80 to 90 mg, the beginnings of exothermic decompositions were determined at:

— starting DNPT 134.1 °C (see also example 4) — starting ADK 143.9 °C (see also example 4) — mixtures 117.5 °C

Example 2

From the starting materials as in Example 1, polyethylene glycol with an average molecular weight of 600 (PEG-600) and water, a paste is prepared with the composition (w/w): 54.75 percent DNPT, 22.2 w/ _w ADK, 15.2% PEG-600 and 7.79% water. Using DTA as in Example

1 is found in this paste: — beginning of exo-TOZklad — beginning of endo-change 85.2°C water evaporation 95.9°C — water evaporation peak 113.1°C Example 3 From raw materials such as in the example

1, water-insoluble powdered urea-formaldehyde condensate, corresponding on average to tetramethylene pentaurea, and polyethylene terephthalate oligomers containing 7.5% by weight of ethylene glycol, a semi-loose mixture is prepared with the composition (% by weight): 28.86% DNPT, 11.44% ADK, 28.86% urea-formaldehyde condensate, 27.74% of polyethylene terephthalate and ethylene glycol oligomers and 3.1% water. Using DTA as in Example 1, the onset of exothermic decomposition is found at 79.9 °C and its peak at 129.6 °C.

Example 4

From the starting materials as in Example 1, from polyethylene terephthalate oligomers as in Example 3 and rubber kaolin, a semi-solid mixture is prepared with the composition (% by weight): 40% DNPT, 20% ADK, 20% kaolin and 20% polyethylene terephthalate oligomers with ethylene glycol. Using DTA as in Example 1, the onset of exothermic decomposition is found at 80.1 °C and its peak at 130.6 °C.

Using non-isothermal differential thermal analysis on a Derivatograf Q 1500 D instrument, operating with a linear temperature rise rate of 5 °C/min, a measurement range of 0.1 mV per scale scale and sample weights of 50—70 mg, the following was found for this mixture:

beginning of endo-change 20 °C peak of endo-change 61 °C beginning of exo-decomposition 78 °C peak of exothermic decomposition 173 °C, while from the derived course of the exotherm a change in the kinetics of heat release is noticeable at 123 °C (peak of decomposition of 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacyclooctane) and at a temperature of 137 °C. For the starting azodicarbonamide, the beginning of exothermic decomposition is found with the help of the above-mentioned device at 150 °C with a peak of this decomposition at 192 °C. The starting l,5-methano-3,7-dinitroso-1,3,5,7-tetraazacyclooctane (DNPTJ is analogously characterized by the beginning of exothermic decomposition at 138 °C with a peak of this decomposition at 172 °C.

Example 5

From the starting materials as in Example 3, a semi-loose mixture is prepared with the composition (% by weight): 35.2% DNPT, 4.1% ADK, 31.1% urea-formaldehyde condensate and 29.6% polyethylene terephthalate oligomers with ethylene glycol. Using DTA on the Derivatograf Q 1500 D device as in Example 4, the following is found:

beginning of endo-change 18 °C peak of endo-change 70 °C beginning of exothermic decomposition 84 °C peak of exothermic decomposition 184 °C, while from the derived course of the exotherm, a change in the kinetics of heat release is noticeable at 126 °C (peak of DNPT decomposition) and at a temperature of 153 °C.

Example 6

From the starting materials as in Example 1, rubber kaolin and water, a semi-loose mixture is prepared with the composition (% by weight): 40% DNPT, 20% ADK, 32% kaolin and 8% water. Using DTA on the Derivatograf Q 1500 D device as in Example 4, it is found:

beginning of endo-change 22 °C peak of endo-change 48 °C beginning of exothermic decomposition 114 °C peak of exothermic decomposition 173 °C, while from the derived course of the exotherm a change in the kinetics of heat release at 158 °C (peak of DNPT decomposition) is noticeable.

Example 7

From the starting materials as in Example 3 and water, a semi-loose mixture is prepared with the composition (% by weight): 29.75 0/ ₀ DNPT, 11.0 % ADK, 28.55 % urea-formaldehyde condensate, 29.0 % oligomers from the production of polyethylene terephthalate with ethylene glycol and 1.7 percent water. Using DTA on the Derivatograf Q 1500 D device as in Example 4, it is found:

beginning of endo-change 25 °C peak of endo-change 68 °C beginning of exothermic decomposition 80 °C first peak of exothermic decomposition 132 °C second peak of exothermic decomposition 185 °C

The weight losses (integrated) corresponding to the individual changes in the DTA record are:

endo-change 5.88% first exotherm 30.88% second exotherm - 17.67%

Using DTA as in Example 1, the onset of exothermic decomposition is found at 79.9°C and its peak at 129.6°C.

Example 8

The mixtures according to examples 4, 5 and 6 are tested under standard conditions from the point of view of the lightening of rubber products, in relation to the commercial deodorized mixture Chempor PC-65 (consists of 65% by weight of 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacyclooctane, 20.5% by weight of urea complex with methylolurea or methylenebilurea and 14.5% by weight of water). The mixing of blowing agents into the rubber mixture, growth properties, vulcanization safety, deodorizing ability and pore structure are assessed. The numerical values of the results are presented in Table No. 1, which also lists the gas numbers of the mixtures under standard conditions.

The mixing of the mixture according to Examples 4, 5 and 6 into the rubber mixture on a double roller is good, only the blowing agent according to Example 4 sticks slightly to the rear roller.

The deodorizing properties of the mixtures according to Examples 4, 5 and 6 are comparable to the deodorizing properties of the commercial mixture Chempor PC-65.

The pore structure, assessed on the cross-section of the lightened vulcanized plate, is the same for the mixture according to example 4 as for the application of the Chempor PC-65 mixture, while for the mixture according to example 6 this structure is better than in the case of the application of the commercial mixture.

3 5 5 S 1 ' Chempor PC-65 and in the mixture according to example 5 the pore structure is very fine, incomparably better than when applying the mixture Chempor PC-65.

Results for example 8

Mixture Gas number (ml.g ^-1 ) Load (g) Growth properties for vulcanization Processing mixtures calculated per mixture per 1 kg at 155 °C safety

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Claims (1)

SUBJECT A blowing agent based on a mixture of 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacyclooctane with azodicarbonamide, optionally containing modifying components, characterized in that the weight ratio of 1,5-methano-3,7 The diamide of the amide is 10: 1 to 1: 1, preferably 8.58:: 1 to 2: 1, with the ratio of the sum of the weight of the active components of the blowing agent to the sum of the other components of the mixture. it is greater than 0.5: 1, preferably equal to or greater than 0.64: 1.