FI70203B - STABILIZER METHYLENCHLORID OCH DESS ANVAENDNING - Google Patents

Abstract

1. Halogenated hydrocarbon selected from the group consisting of methylene chloride, trichlorofluormethane and 1.1.1-trichloroethane, stabilized against decomposition by water, which comprises as stabilizer from 0.001 to 10% by weight of a tertiary amine of the formula RR**1 R**2 N with R being alkyl with 1 to 10 carbons and R**1 and R**2 , independent from one another, being isopropyl, butyl-(2), tertiary butyl or cyclohexyl.

Description

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'^ ^ (51) Kv.ik. * / Int.ci.4 C 07 c 1 Uhl, C 09 K 3/30, 15/18 FINLAND —- FINLAND (21) Patent application - Patentansökning 801 7 ^ 5 (22) Application date - Ansökningsdag 29.0 5 · 8 0 fFh '"(23) Starting date - Giltighetsdag 29.05.8 0 (41) Has become public - Bllvit offentlig 03.1 2.8 0

National Board of Patents and Registration The date of publication, ™ and date of publication. - 28.02 86 P & tGnt- och registerstyrelsen '' Ansökan utlagd och utl.skriften publicerad (32) (33) (31) Privilege requested - Begird priority 02.06.79 Germany 1i i ttotasavalta-Förbundsrepubliken Tyskland (DE) P 2922700.7 (71) Hoech , 6230 Frankfurt / Main 80,

The Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) (72) Elmar Heiskel, Dreieich, Wilhelm Lendle, Bad Soden am Taunus,

1 Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) (7 * 0 Oy Kolster Ab (5 * 0 Stabilized methylene chloride and its use -

Methylene chloride is stabilized and dissolved

The present invention relates to methylene chloride stabilized against the degradative action of water and its use. Methylene chloride, as well as other halogenated hydrocarbons, are used e.g. extraction, degreasing, metal cleaning and solvents for other substances. In many applications, a halogenated hydrocarbon, such as methylene chloride, then comes into contact with water, which can lead to its rapid or slow decomposition, resulting in the formation of a halogenated hydrocarbon. In this case, the metals present, such as the white sheet metal, corrode in many cases.

Halogenated hydrocarbons, especially methylene chloride and 1,1,1-trichloroethane, but also fluorotrichloromethane, are also used in aerosols as solvents for many active ingredients. In most cases, a halogenated hydrocarbon, for example methylene chloride, is used in admixture with other organic solvents such as alcohols or gasoline hydrocarbons. In the absence of 2 70203 water, stabilization of the halogenated hydrocarbon is generally easy or unnecessary. For example, insecticide and hair spray aerosols containing methylene chloride are generally anhydrous.

A major advantage of said halogenated hydrocarbons, in addition to dissolving a wide variety of substances, is that they have been considered non-combustible in the EG chamber on the basis of statutory analyzes of pressure packages. Thus, when used in spray compositions, in particular in combination with other flammable components, they meet the safety requirements for exempted products. (The flammability declaration must be made when the weight of the combustible components in the total filling volume is 45% or more).

The disadvantage of these chlorine-containing solvents is their considerable sensitivity to water. This also applies to many other halogenated hydrocarbons with a low degree of halogenation and less than 4 fluorine atoms in the molecule.

Even under the influence of small amounts of water in aerosol cans in 96% ethanol mixed with hydrocarbons, for example pure methylene chloride, especially in contact with metals, hydrolyses so strongly in a relatively short time that the hydrogen chloride formed as a decomposition product causes corrosion of the metallic pressure pack. The hydrochloric acid formed in the product in the package also has a chemical effect, so the entire contents of the package become unusable.

For this reason, many attempts have been made to find inhibitors to be added to halohydrocarbons which would stabilize compounds of particular importance in the manufacture of aerosols against the hydrolysis of methylene chloride and 1,1,1-trichloroethane. For example, epoxides and / or secondary amines have been added to halogenated hydrocarbons, especially methylene chloride. However, due to their toxicity, epoxides should be considered less desirable. Secondary amines in the presence of nitrite can lead to the formation of potentially carcinogenic nitrosamines. A further disadvantage is that the effect of these said stabilizers gradually decreases and is thus limited in time, since these stabilizers react with either the halogenated hydrocarbon or the halogenated hydrocarbon formed therefrom. It is also known to use N-methylpyrrole and N-alkylmorpholine to protect methylene chloride (in the absence of water) from the degradative action of metals or metal salts (GB Patent 932,438). Tertiary amines such as triethylamine have also been used for this purpose (U.S. Patent Application B 370,309).

Thus, there was a need to stabilize halohydrocarbons, and in particular methylene chloride, against hydrolysis with toxicly acceptable compounds so that the stabilizing effect lasts for a very long time.

The methylene chloride stabilized against the decomposing effect of water according to the invention is characterized in that 0.001 to 10% by weight of a tertiary amine of the formula: RR1R2N (I) in which R and R1 are independently alkyl groups having 1 to 10 carbon atoms and R is an isopropyl, butyl (2), tert-butyl or cyclohexyl group. Alkyl groups can be straight, branched or cyclic.

Preferred stabilizers are tertiary amines of the formula: RR 1 R 2 N (III) wherein R is an alkyl group having 1 to 10 carbon atoms and R 2. .

and R are independently isopropyl, butyl (2), tert-butyl or cyclohexyl.

R is preferably an alkyl group having 1 to 4 carbon atoms, especially methyl or ethyl. Due to their easy preparation, such tertiary compounds of formula (III) are preferred. . 1. 2 set amines in which R and R are the same, i.e. they have the formula RR * N (IV)

According to the invention, the tertiary amine is preferably added to a concentration of 0.005 to 5% by weight, in particular 0.01 to 1% by weight.

It has further been shown that the stabilizing effect of the tertiary amine is enhanced in the presence of ether. The ether used is preferably an aliphatic, straight-chain ether having a total of 2 to 6 carbon atoms, the weight ratio of methylene chloride / ether being 1: 2 to 100: 1 and the mixture containing 0.001 to 10% by weight of a tertiary amine of the formula I as stabilizer. Particularly preferred ethers in this regard are straight-chain dialkyl ethers having 2 to 6 carbon atoms, such as, for example, diethyl ether, dimethyl ether or methylethyl ether.

The invention further relates to the use of methylene chloride according to the invention, stabilized against the decomposing effect of water, in an aerosol can filling comprising at least one liquid halogenated hydrocarbon at room temperature, at least one liquefied Aero sol gas propellant at room temperature and normal pressure and hydrogen. This filler mixture may additionally contain other organic solvents and active ingredients. By "active substance" is meant here substances which do not belong to liquid halogenated hydrocarbons, organic solvents or propellants, but which are nevertheless essential for the use of the aerosol preparation. Examples of such are perfumes, dyes and binders (in varnish aerosols) and bactericides. These active substances generally have only a minor effect on the halohydrocarbons present. They may also be absent from the composition (e.g., methylene chloride based cooling sprays or paint stripping compositions).

Preferably, the stabilized methylene chloride of the invention is used in an aerosol can filler containing 70 to 89.5% by weight of halohydrocarbons, 0 to 75 "other organic solvents, 0.5 to 25" water, 0 to 35 "of active ingredients and - 70 "liquefied aerosol propellant, and each filler further contains 0.00001 to 0.1 parts by weight of a tertiary amine of the formula (I) per part by weight of halogenated hydrocarbon.

Of particular importance is the stabilization of the above aerosol composition when filled into a metal aerosol can. In this case, corrosion of the metal, e.g. white sheet metal, can be largely prevented for long periods of time.

The invention is illustrated by the following examples:

eXAMPLES

18-ounce (approximately 500 ml) aerosol cans made of welded white sheet without an internal varnish, sealed with a normal valve associated with a glossy valve plate, were filled with propellant and the cans were then stored upright at 40 ° C. After the specified storage times, usually 4, 8 and 12 weeks, the still full cans were cooled below the boiling point of the spent propellant, the lid part was pierced with a spike and the cans were allowed to warm to room temperature again in the fume hood, whereupon the propellant gradually evaporated. The remaining ingredients were poured into beakers, and the emptied cans were sawn open. Both the can filling (filling without propellant) and the open-cut tin can were optically examined for possible corrosion. By "no effect observed" is meant that the aerosol filling or can material, respectively, had remained unchanged with respect to the original filling.

The following tables show the relationship between the composition of the stabilizer and the aqueous methylene chloride, the storage time and the corrosion of the aerosol cans. Experiments 1-4 are comparative experiments and Experiments 5-7 are experiments according to the invention.

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Claims (10)

10 70203 Methylene chloride stabilized against the decomposing effect of water, characterized in that 0.001 to 10% by weight of a tertiary amine of the formula: RR1R2N (I) in which R and R1 are independently alkyl groups having 1 to 10 carbon atoms and R is used as a stabilizer isopropyl, butyl (2), tert-butyl or cyclohexyl group. Methylene chloride according to Claim 1, characterized in that a tertiary amine of the formula: RR 1 R 2 N (III) in which R is an alkyl group having 1 to 10 carbon atoms and R 1 and 2 R are independently isopropyl, butyl- (2) ), tert-butyl or cyclohexyl groups. Methylene chloride according to Claim 2, characterized in that the tertiary amine has the formula: RR 2 N (IV) Methylene chloride according to Claim 2, characterized in that R is an alkyl group having 1 to 4 carbon atoms. Methylene chloride according to one of Claims 1 to 4, characterized in that 0.01 to 1% by weight of tertiary amine is added as a stabilizer. Use of methylene chloride stabilized against the decomposing effect of water according to claim 1 in the presence of an aliphatic, straight-chain ether having a total of 2 to 6 carbon atoms, wherein the weight ratio of methylene chloride / 1170203 ether is 1: 2 to 100: 1 and the mixture has a stabilizer of 0.001 to 10 % by weight of a tertiary amine of the formula (I) in which R, R and R have the same meaning as in Claim 1. Use of methylene chloride stabilized against the decomposing effect of water according to claim 1 in an aerosol pack filler containing 10 to 89.5% by weight of halohydrocarbons, 0 to 75% by weight of other organic solvents, 0.5 to 25% by weight of water , 0 to 35% by weight of active ingredients and 10 to 70% by weight of liquefied aerosol propellant, and each filler additionally contains 0.00001 to 0.1 part by weight of a tertiary amine of the halogenated hydrocarbon having the formula (I), wherein R, R and R have the same meaning as in claim 1. Use according to Claim 7, characterized in that methylene chloride is used as the halohydrocarbon. Use of tertiary amines according to Claim 1 as stabilizers for methylene chloride against the degradative action of water. Use of tertiary amines according to Claim 1 as stabilizers for the decomposing action of water against mixtures of methylene chloride and aliphatic, straight-chain ethers having a total of 2 to 6 carbon atoms. 12 70203