CS232633B1 - Modified 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacycloctane-based blowing agent - Google Patents

Abstract

The invention solves the modification of blowing mixtures based on 1,5-methane-3,7-dinitroso-1,3,-5,7-tetraazacyclooctane by adding oligomers and/or polymers based on oxirane derivatives in an amount of 1 to 60% by mass. to the weight of the resulting blowing agent, while the average molecular weight of the applied oligomers and/or polymers is 106.1 to 25,000. The blowing agents according to the invention are especially suitable for lightening products of the plastics industry.

Description

232633 3

BACKGROUND OF THE INVENTION The present invention relates to a modification of the blowing agent base with 1,5-methano-3,7-dinitroso-1,3,5,7-terrazazacyclooctane with oligomers and / or oxirane derivatives.

One of the negative properties of thermo-dynamically unstable substances commonly used as blowing agents in the rubber and plastics industry is their dustiness, most often eliminated by phlegmatization by mineral or silicone oils, or water. However, the phlegmatizers, the darkest, are not desirable in some applications, as they may adversely affect the quality of the article (e.g., epoxy hard foam products for electrical purposes). In the case of 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacyclooctane (code number DNPT), one of the most economically available blowing agents, another negative feature is the formation of unpleasant smelling products its thermolysis in relieving rubber products. Butter products can be suppressed by using additives to the blowing agent and / or the rubber composition capable of acting as reactants in the N-Mannich condensation or having the character of protogenic substances with a relatively low vapor pressure in the temperature range of 120 to 160 ° C (most often glycerol or ethylene glycol).

According to the present invention, the modification of the properties of a blowing agent based on 1,5-methano-3,7-nitroso-1,3,5,7-tetraazacycloctane is achieved by the addition of oligomers and / or polymers based on oxirane derivatives, %, preferably polyethylene glycols, polypropylene glycol or diglycerin, in an amount of 1 to 60% by weight, preferably 11.2 to 30% by weight. to the weight of the resulting blowing agent, wherein the average molecular weight of the oligomers and / or the polymer is from 106.1 to 25,000, preferably is 16 < RTI ID = 0.0 > < / RTI > it is only exceptionally necessary to exceed these amounts and molecular weights. An advantage of the present invention is the technical and economic availability of the modifying component. By selecting the appropriate molecular weight of the component, that is to say by using the additive of said type of viscous or waxy consistency or in the form of a powder, segregation of the blowing agent components can also be avoided by the high content of the modifier, which is another advantage of the present invention. The adhesion of the rubber articles to the present invention is clearly suppressed by the formation of unpleasantly odorous products, i.e. the non-toxic modifier of the base of oligomers and / or polymers of the oxirane derivatives can replace the toxic and pronounced more flammable ethylene glycol, which is also an advantage of the present invention.

According to the present invention, the modified blowing agent is particularly suitable for the production of hard epoxy integrated foams, for the dispersion, for controlling the specific charge weight of mixed explosives and the like.

A method of modification according to this invention of a 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacyclooctane based oligomer (s) based on oxirane derivatives has not been described in the literature so far, documented by the following examples. which, however, in no way preclude the possible variability of the method. EXAMPLE 1 Technical dry 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacycloctane (DNPT) and technical polyethylene glycol (MW) (PEG-600) are available. Of these raw materials, a semi-pasty mixture of (% by weight): 84.0% DNPT, 14.5% PEG-600 and 1.5% water is prepared in a malaxerip. By storing at 20-23 ° C for 90 days, this mixture does not change its consistency. Example 2 Technical 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacyclooctane (DNPT) is available as in Example 1, technical poly (propylene glycol) having an average molecular weight of 3000 (PPG-3000) and precipitated calcium carbonate. From these raw materials, a semi-particulate composition is prepared with a composition (per cent by weight): 64.7% DNPT, 11.2% PPG-3000.22.0% calcium carbonate and 1.1% water. or stacking for 90 days at 20 to 23 ° C. EXAMPLE 3 1,5-Metano-3,7-dinitroso-1,3,5,7-tetraazacyclosoctane is available as in Example 1, the water-insoluble urea-formaldehyde condensate with a urea-to-formaldehyde molar ratio of 1: 0.9 and a pure di- glycerine. Of these raw materials, a semi-powdery composition of (% by weight): 39.0% DNPT, 29.7% urea-formaldehyde condensate, 30% diglycerine, and 1.3% water is prepared in a malate mixer. The mixture does not change its consistency after storage for 90 days at 20 to 23 ° C. EXAMPLE 1. Technical 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacycloctane with 5.1 wt. water and polyethylene glycol with an average molecular weight of 20,000 (PEG-20,000 powder) is also available. Compositions of composition (% by weight): 47.5% DNPT, 49.8% PEG-20,000 and 2.7% water are prepared from the foregoing. The mixture does not change consistency after storage for 90 days at 20 to 23 ° C.

Claims (1)

EXAMPLE 5 A non-isothermal differential analysis (DTA) is available, operating at a linear temperature rise rate of 5 ° C .. min-1, a measuring range of 1 mV to scale and sample weighing of 80 to 90 mg. the thermal stability of the starting DNPT and the mixtures of the previous examples are specified, wherein the comparative mixture is commercially blown by the company name Chempor PC-65 (consisting of 65% by weight DNPT, 20.5% by weight of urea-methylolurea) methylenebismurea and 14.5% w / w). The results are presented in Table: Mixture of Exothermic Decomposition (° C) Starting DNPT 131.4 Chempor PC-65 62-68 Example 1 100.5; 105.8 * of Example 2 134.1 of Example 3 114.5 of Example 4 108.3 Note: * value after 7 days storage; Example 6 To 100 wt. of epoxy resin, heated to 100 ° C, is gradually mixed with 0.55 wt. parts of silane emulsifier emulsifier, 45 wt. parts of thawed tetrahydrophthalic anhydride, 0.3 wt. target-accelerator parts. of the amine and finally 1 part by weight of blowing agent according to Example 1. The homogenised mixture is poured into a mold heated to 130 ° C; curing at 130 ° C for 12 hours. This results in a product with the same physical-mechanical properties (except for the specific weight) that the product has. Example 7 To 100 wt. 100 parts by weight of the epoxy resin heated to 130 ° C. also parts of ground crystalline quartz (filler) also preheated- SUBSTANCE Modified blowing agent based on 1,5-methano-3,7-dinitroso-1,3,5,7-tetraazacyclooctane, characterized in that it contains oligomers and / or polymer base of oxirane derivatives, preferably it contains polyethylene glycols, polypropylene glycols te to 130 ° C, 0.55 wt. of a silane type emulsifier, 45 wt. of part-dehydrated tetrahydrophthalic anhydride and 0.4 wt. tertiary amine accelerator. After a thorough homogenization, during which the mass is gradually cooled, 0.5 wt% is added at 110-115 ° C. the blowing agent parts of Example 1. The good homogenized meat is then cast into a mold heated to 130 ° C; curing takes place for 12 h at 130 ° C. By this process, it is possible to save about 40% by weight. Example 8 Under standard conditions, the effect of the compositions of Examples 1, 2 and 3 of the rubber composition vulcanization system on the use of a commercial blowing agent ChemporPC-65 (composition see Example 5) as a blend is followed. Measurements are carried out with a Monsanto Cone rheometer at 155 ° C and their results are presented in the following table: Tbl (s) T90 (s) Chempor PC-65 380 1050 Example 1 290 760 Example 2 480 1050 Example 3 250 820 Table Tab. The review shows a known accelerating effect of polyethylene glycols vulcanization, reflecting both the vulcanization safety (tw values) and the optimum vulcanization (T90 values). The blowing ability of the compositions of Examples 1, 2 and 3 is comparable to the ChemporomPC-65 as well as the deodorizing ability. The characteristics of the mixtures are monitored with a Gottfert 125 ° C elastograph at the fifth minute of the test; The results are shown in the following table: Compressive Force (kN) Chempor PC-65 0.72 Example 1 0.70 Example 2 0.86 Example 3 0.83 EXTRACTED or diglycerin, in an amount of 1 to 60 wt. preferably in an amount of 11.2 to 30% by weight. to the weight of the resulting blowing agent, wherein the average molecular weight of the oligomers and / or polymers is 106.1 to 25,000, preferably is 166.1 to 20,000.