NL1003076C2 - Composition containing a secondary amine and use of primary amines as inhibitors for the formation of N-nitrosamines. - Google Patents

Description

Composition containing a secondary amine and use of primary amines as inhibitors for the formation of N-nitrosamines

The present invention relates to a functional liquid or a cosmetic agent containing a secondary amine and to the use of specific primary amines with at least one primary amine group and at least one hydroxyl group as inhibitors for the formation of N-nitrosamines.

U.S. Pat. No. 4,331,468 discloses a process for inhibiting nitrosamine formation in nitroherbicide formulations containing at least one monoalkanolamine RCH (OH) - (CH2) n-CHR'-NH2, where n is an integer from 0 to 5 and R and R 'are independently a hydrogen atom or a C 1 -C 5 alkyl group. The method is applicable to cutting fluids and cosmetics.

JP 56008495 discloses a composition for a water-soluble cutting fluid comprising a polyfunctional alcoholic amine of 3-6 carbon atoms, the sum of the NH2 and OH groups being 3 to 4.

It is a known fact that, under certain conditions, secondary amines in the presence of nitrosating agents, such as nitrite and certain nitrogen oxides, contribute to the formation of N-nitrosamines. Other compounds, such as aldehydes, aldehyde releasing biocides and ketones, can act as catalysts in the formation of N-nitrosamines. The carcinogenic effect of N-nitrosamines in humans has not yet been established, but there is a general consensus among researchers in this field that it is fully justified, based on circumstantial evidence, to consider preventive measures against N-nitrosamines, as during animal 25 tests have shown to be carcinogenic.

To reduce the expected negative effects of secondary amines, such as diethanolamine, commonly used in functional fluids, such as metalworking fluids, and in cosmetics, an article entitled "N-nitros-amine formation in aqueous metal-working fluids in the presence of monoethanol-30 amine "from Brian C Challis et al., published on the 8th International Colloquium Tribology, Tribology 2000, January 14-16, 1992, Technical Academy Esslingen, Ostfildem, Germany, proposed the use of monoethanolamine. The effects of monoethanolamine in reducing the formation of N-nitrosamines 1003076 2 are significant, but there is a need for further improvements. Furthermore, the patent publication EP-A 1-344.564 discloses the use of primary aromatic amines, which do not result in carcinogenic nitrosamines in a reaction with NOx, or the use of secondary amines, which contain scavenger groups for the nitrosating agents. Patent publication US 4,273,937 discloses that 1,4-naphthoquinone, 1,4-naphthohydroquinone and alkyl-substituted derivatives of the quinones can be used as inhibitors of nitrosamine formation.

It is also known to use amidosulfonic acid and its salts as inhibitors for the formation of N-nitrosamines. In DE-A1-3,939,475, claim 4, 10, the use of amidosulfonic acids, their alkali metal, alkaline earth metal and ammonium salts as well as their salts with primary amines (C2-C, 8), which are substituted with one or more hydroxyl or amino groups. The primary amines in the salts are, in particular, monoethanolamine, ethylenediamine, 1-aminopropanediol and 2,3-tris (hydroxymethyl) aminomethane. The active compound is the acid and its salts. The description also mentions that tri (hydroxymethyl) aminomethane and monoethanolamine themselves have a good inhibitory effect on the formation of N-nitrosamines. The patent application does not mention the inhibitory effects of ethylenediamine and 1-aminopropanediol.

According to the present invention, it has now been found that the formation of N-nitrosamines in an aqueous composition with secondary amines is further reduced by the presence of a primary amine of the formula H2NCH, CHOHCH2NH2 (I), CH2X, CHX2CH2NH2 (II), 25 wherein X, and X2 are independently hydrogen or hydroxyl, with the proviso that at least one of the groups X, and X2 is hydroxyl, or GNH2 (III), wherein G is a saccharide group, the weight ratio of the secondary amine and the total amount of the primary amines of the formulas I, II and 30 III is 5: 1 to 1: 100, preferably 2: 1 to 1:20. Preferred specific examples of primary amines as inhibitors of N-nitrosamines are glycylamines, 2-hydroxy-1-aminopropane, 3-hydroxy-1-aminopropane and 2-hydroxy-1,3-diaminopropane. The saccharide group may be derived from monosaccharides, too 76 76 disaccharides and polysaccharides. These are preferably selected from galactose, L-rhamnose, fucose, D-mannose, glucose, fructose, lactose, xylose, arabinose, maltose and melibiose, but a large number of other saccharides can also be used. Furthermore, the ring structure of the saccharide can be opened, e.g. by hydrogenation. Preferably, such an aqueous composition, whether intentionally or accidentally as a result of impurities, contains a secondary amine of the formula

R, H

10 HN

R2H

wherein R 1 and R 2 are independently a poly or monoalkyleneoxy group of 2 to 4 carbon atoms or a divalent hydrocarbon group of 1 to 20 carbon atoms or R, H 15 and R 2 H together with the nitrogen atom form a 6 membered ring group , 5 to 20 carbon atoms and 1-3 oxygen and / or nitrogen atoms. Preferably R is ethyleneoxy or propyleneoxy and R2 is ethyleneoxy, propyleneoxy or an alkylene group of 1-12 carbon atoms. Usually, the amount of the secondary amine is from 0.01 wt% to 10 wt%. Common examples of secondary amines are diethanolamine, dipropanolamine and morpholine.

In addition, the aqueous composition according to the invention can also contain an aldehyde or a so-called "aldehyde-releasing" compound; for example a formaldehyde releasing biocide such as 1,3,5-tris-hexahydroethyl-s-triazine, a ketone and / or a nitrosating agent, such as nitrite, in amounts of 0.001-5 wt%, preferably 0.005-2 wt% .% of the composition. It is not necessary that the aqueous composition prepared as such contains a nitrosating agent to form N-nitrosamines since air contains nitrogen amines which have a nitrosating effect. These oxides can be absorbed by the aqueous composition of the invention. Therefore, it is essential that an N-30 nitrosamine inhibitor is always present when a composition contains a secondary amine.

Aqueous compositions containing secondary amines are widely used and two main types of compositions are functional fluids such as metalworking fluids and cosmetics. Cosmetics are usually in the form of an emulsion and during use, the absorption of nitrosating agents from the air can result in the formation of N-nitrosamines.

A metalworking fluid according to the invention preferably has a pH of at least 8, most preferably between 8 and 10, and usually contains 5 in addition to secondary amine and the primary amines of the formula I, II and III lubricants and other corrosion inhibitors.

The corrosion inhibitors in a ready-to-use composition are usually present in an amount of 0.1-10% by weight, preferably 0.2-3% by weight, of the metal working fluid. Examples of suitable corrosion inhibitors are, in addition to the primary amines of the formulas I, II and III and the secondary amines, other amine compounds, such as mono-, di- or triethanolamine, and the primary amines described in WO 94 / 12028 and WO 94/13765, alkali metal hydroxides, triazole and thiadiazole compounds, monocarboxylic acids of preferably 6-18 carbon atoms, such as heptanoic or isononic acid, dicarboxylic acids, preferably 6-12 carbon atoms, such as azelaic acid or sebacic acid, alkyl or arylsulfonamidocarboxylic acids; inorganic acids, such as boric acid; and the usual reaction products between boric acid and / or carboxylic acids with organic compounds, such as alkanolamines. Examples of corrosion inhibitors are also the amine compounds, which are described in European Publication No. 180,561.

In order to increase the friction-reducing capacity, the metal working fluids may also contain lubricants. They are usually selected from the group consisting of oils; esters or amides of mono- or dicarboxylic acids with at least 10 carbon atoms in the acyl groups; monocarboxylic acids with 12 or more carbon atoms; dicarboxylic acids with more than 12 carbon atoms; organic phosphate esters with one or two hydrocarbon groups of 6-18 carbon atoms; nonionic alkylene oxide adducts with a molecular weight greater than 400, such as polypropylene glycol or randomly distributed polypropylene ethylene glycols or block polymers of ethylene and propylene oxide and mixtures thereof. The amount of lubricant is 0.05-10 wt%, preferably 0.1-2 wt%, of the metal working fluid. Preferably, the monocarboxylic acid lubricants are coconut fatty acids, oleic, peanut and rapeseed acids, and esters and amides of these acids with polyols, such as glycerol, trimethylolpropane, pentaerythritol and polyalkylene glycols, and alkanolamines, respectively. The hydrocarbon groups of the organic phosphate esters 1003076 can be octyl, nonyl, decyl, dodecyl, tetradecyl and hexadecyl as well as the corresponding unsaturated alkenyl groups thereof. Anionic lubricants also have a corrosion-preventing ability against iron.

The metalworking fluids containing an oil as a lubricant often take the form of an emulsion or a colloidal solution. By the term "oil" is meant here a class of substances of synthetic, inorganic, vegetable or animal origin. Usually these are petroleum derived or petroleum derived, but synthetic hydrocarbons such as polyalphaolefins (PAOs) or alkylates such as alkylbenzenes are also used.

These compositions usually also contain 0.1-5 wt% emulsifiers, which are usually non-ionic and / or anionic surfactants. Examples of anionic surfactants are alkylaryl sulfonates, such as dodecylbenzene sulfonates; alkyl sulfates, such as sulfates of alcohols or alkoxylated alcohols; sulfated esters, such as sulfated castor oil; 15 and phosphates of alcohols or ethoxylated alcohols. Examples of nonionic surfactants are alkoxylated alkyl phenols, alcohols, carboxylic acids, alkanolamines, alkyl amines and alkyl amides. The alkoxylating agent is usually an alkylene oxide of 2-4 carbon atoms. Preferably at least 50% of the alkyleneoxy groups are ethyleneoxy groups and may be arranged in blocks or randomly distributed. In a preferred embodiment, the polyoxyalkylene glycol is end-charged with propyleneoxy and / or butylene-oxy units to obtain a low foaming surfactant. The anionic and non-ionic surfactants are usually selected to contain 8-20 carbon atoms in a hydrocarbon group. The HLB balance can be further controlled by the amount of ethylene oxy units in the surfactant.

In addition to corrosion inhibitors and lubricants, the metal working fluid can advantageously also contain, in known manner, pH-regulating agents, stabilizing agents for metal complexes, defoaming agents, perfumes, viscosity-controlling and solubility-improving agents. Suitable solubility-enhancing agents are glycols, such as hexylene glycol; alcohols such as tridecanol and oleyl alcohol; and glycol ethers, such as butyl dioxitol and butyl trioxitol.

The present invention is further illustrated by the following 1003076 6 examples.

Example I

An aqueous solution containing 2 wt.% Of a triethanolamine-diethanolamine mixture (85:15), 0.05 wt.% NO2 \ added as NaNO2, and 0.5 wt.% Of an inhibitor according to the table below was stored at 60 ° C for two weeks. For comparison, the same aqueous composition, but without the inhibitors, was prepared. The pH of these compositions was adjusted by adding 10 acetic acid so that they have the same pH as the inhibitor samples.

The formation of N-nitrosamines was monitored every other day. The formation rate was determined between the uninhibited sample and the inhibited sample and the relative inhibition was calculated according to the formula% relative inhibition = (1 - speed inhibited / speed uninhibited) x 100 The following results were obtained

Tests Inhibitor Relative inhibition,% 20 1 2,3-dihydroxy-1-aminopropane 42 2 2-hydroxy-1-aminopropane 51 3 3-hydroxy-1-aminopropane 4 0 4 2-hydroxy-1,3-diaminopropane 51 A monoethanolamine 20 25

The results show that the inhibitors of the invention were superior to monoethanolamine.

Example II 30

The same tests as in Example I were performed, but all samples also contained 0.01% by weight of formaldehyde.

The following results were obtained 100 3076 7

Tests Inhibitor Relative inhibition,% 5 --- 1 1 2,3-dihydroxy-1-aminopropane 6 4 2 2-hydroxy-1-aminopropane 64 3 3 -hydroxy-1-aminopropane 71 4 2-hydroxy-1,3- diaminopropane 87 10 5 glucosylamine 84 6 glucosylamine (opened) 80 A monoethanolamine 50 15 The results show that the inhibitors according to the invention also have excellent inhibitory effects on the formation of N-nitrosamines in the presence of formaldehyde.

1003076

Claims (11)

Functional liquid or cosmetic containing secondary amine-5 compound, characterized in that the functional liquid or cosmetic contains a primary amine of the formula H2NCH2CHOHCH2NH2 (I), CH2X, CHX2CH2NH2 (II), wherein X, and X2 are independently hydrogen or hydroxyl, with the proviso that at least one of the groups X, and X2 is hydroxyl, or GNH2 (III), wherein G is a saccharide group, the weight ratio of the secondary amine and the total amount of the primary amines of formulas I, II and III is 5: 1 to 1: 100, preferably 2: 1 to 1:20, the primary amine inhibiting the formation of N-nitrosamine. A functional liquid or cosmetic agent according to claim 1, characterized in that the amount of secondary amine is 0.05% to 10% by weight of the functional liquid or cosmetic agent. 20 Functional liquid or cosmetic according to claim 1 or 2, characterized in that the secondary amine has the formula ^ R, H HN ^ (IV) R2H has wherein R 1 and R 2 are independently a poly- or monoalkyleneoxy group of 2-4 carbon atoms or a divalent hydrocarbon group of 1-20 carbon atoms or R, H and R2H together with the nitrogen atom form a six-membered ring group, 5 to 20 carbon atoms and 1-3 oxygen and / or nitrogen atoms. 30 100 3076 Functional liquid or cosmetic according to claim 3, characterized in that R is ethyleneoxy or propyleneoxy and R2 is ethyleneoxy, propyleneoxy or an alkylene group having 1-12 carbon atoms. 5 Functional liquid or cosmetic according to claims 1-4, characterized in that the composition contains an aldehyde, an aldehyde releasing compound, a ketone and / or a nitrite. Functional liquid according to any one of claims 1 to 5, characterized in that the functional liquid is an alkaline metalworking liquid. Aqueous metalworking fluid according to claim 6, characterized in that the fluid contains 0.1-10 wt.% Of at least one corrosion inhibitor and 0.05-10 wt.% Of at least one lubricant. Aqueous cosmetic formulation according to any one of the preceding claims, characterized in that the formulation is in the form of an emulsion. 9. Use of a primary amine compound of the formula H 2 NCH, CHOHCH 2 NH 2 (I), CH 2 X, CHX 2 CH 2 NH 2 (II), wherein X, and X 2 are independently hydrogen or hydroxyl, with the proviso that at least one of the groups X, and X2 is hydroxyl, or GNH2 (III), in which G is a saccharide group, as an inhibitor for the formation of N-nitrosamine. 1003076