CS243481B2 - Anticorrosionnagent - Google Patents

Abstract

Reaktionsprodukte aus Borsäure, Diethanolamin und einem Monoethanolamin der Formel R-NH-CH₂CHXOH, wobei R Wasserstoff oder C₁-C₁₀-Alkyl und X = H oder CH₃ bedeutet, im Molverhältnis von 1:0,5:2,5 bis 1:2,5:0,5. Diese Reaktionsprodukte eignen sich als Korrosionsschutzmittel.

Description

The present invention relates to a corrosion preservative consisting of the reaction product of boortic acid, diethanolarine and a nonootbanolenic derivative.

The durability of the capsaines used in machining metals essentially depends on their stability to milaro organisms. Almost ideal nutrient medium for microorganisms was sodium nitrite, which was previously used as a component of corrosion-free preservatives, but whose use is no longer possible for toxicological and environmental reasons. However, also numerous synthetic coiroxl protective agents that have been developed to replace nitrite, mostly carboxylic acid or phosphonic acid, generally lack protection against bacteria and fungi.

The use of conventional milkobicidal agents in metalworking fluids is limited for dermal reasons, since skin contact cannot be avoided and, in addition, all such compounds which, by virtue of their chemical structure, interact interactively with and protect against corrosion. Thus, for example, the quaternary ammonium compounds known as microbes may not be used in the presence of carboxylic acids, since they become ineffective due to the formation of a neutral salt.

U.S. Pat. No. 2,999,064 discloses mixtures of swelling acid, alpha-anoleic acid and unsaturated fatty acids as water-soluble cutting fluids with milkrobicidal properties. However, in addition to the inadequate corrosion protection effect, these mixtures have the disadvantage of foaming and, moreover, have insufficient fungicidal activity.

Also piperazine derivatives disclosed in German Patent 1,620,447, which are formed by condensation of amino alcohol, boric acid and carboxylic acids at high temperatures, e.g. they are not able to work sufficiently for the corrosion protection agents, coolants, means and cutting agents attacked by fungi, in particular of the species' Trichoderma. 'Likewise, protective agents of boric acid and diet0jO01aminu _from aryl optionally alkyl8uffonмidokjrioxylovýc0 kyselil (cf. German Patent No. 28 40 112) having iaktericidoí although good effects, but oedostajující fungicidal effects.

In addition, it is known that atoanlimines substituted with an α and nitrogen atom can adequately preserve various cooling and cutting capsules (cf. EO Berou t, J. Am. Soc. Lulbr. Eng. 35 (1979), 137-144), but - Lieeratra makes no mention of the chemical nature of the preserved appaio. At the same site, it is also observed that some coolants produce poor results, which may be due to the adverse interaction of the chokes that are typically used in cutting fluids.

It has now been found that the condensation products of boric acid, diethanolamine and a mono-halo-aniline derivative, as well as mixtures of these condensation products with aryl or alkenylsulphonic acid carboxylic acids, have both excellent corrosion protection and bactericidal and fungicidal effects which exceed the total effect of the individual components.

SUMMARY OF THE INVENTION The present invention provides a corrosion protection composition in the form of an aqueous solution comprising from about 0.5% to about 10% by weight, based on the weight of the aqueous solution, of the acid reaction product, diethylolmin, and a derivative thereof. of a monoethane-amine of formula

R-NH-CH2-CHXOH in m.p.

R denotes a hydrogen atom or an iltyl group with 2 to 5 aornic carbon and

X is in the form of hydrogen, CR, in a molar ratio of 1: 0.5: 2.5 to 1: 2.5: Q, 5.

Said reaction product is obtained by heating the three components in the absence of a solvent at a temperature of 70 to 130 ° C, preferably to 80 to 100 ° C.

The thus prepared rock products are then diluted with water & in this form they are used as corrosion protection agents for ferrous metals. These compositions not only have a good bactericidal effect in addition to their action as a corrosion protection agent, but also have a good fungicidal effect.

The aqueous solution of the reaction products described above may additionally also contain other conventional corrosion protection agents, such as, in particular, N - (benzene-stufonyl-N-methylauin) -n-caproic acid of the formula

-COOH and alkylϊSjuffinimiducarbonyl acids of the general formula

wherein ^R1 is an alkyl group having I to ⁴ to 17 atoms and ^uh -íku

R is hydrogen or -CH8COOH.

The preparation of aryl sulfonic acid oxoic acids is described in German patent specification

298 672.

^In ýhodným příktodem composites such as UV ^{day, and} Žfpoenzernsuifonyl-halmtnoJ Nm ^ n-topronová acid.

The preparation of alkyl or cycloaltyl sulfocarboxylic acids is described, for example, in German patent 900 041. It is carried out using saturated hydrocarbons having from 12 to 22 carbon atoms which are substantially derived from n-paraffinic hydrocarbons which are They may also include branched and / or cyclic poddly maai and boiling in the range of from about ²⁰⁰ to 35 ^{0 C,} the successors to react with ammonia and ^{1 to} Finite ondenzcaci with chl.frfctovfu acid. These products are obtained as a result of incomplete sulphation due to unreacted paraffin and / or chlorinated propyrafinocarbons; in general, it has a tartrate in the range of from about 40 to 60 mg of colloidal aryl or allyl sulfonic acid, and is generally about 10 to 50% ammonium, preferably 10 to 30%. These data are the reference for P ^ t ^ ^ uit three altylnebo cyklfaltylsuffnnmιddfkarbfxylfe ^r YCA tyseein the pure ester; After mixing with the reaction products of boltic acid, diethanolamine and the mofnothtanolauine derivative, the mixture is separated by phase separation from unreacted hydrocarbons or chlorinated paffinic hydrocarbons, which is an accompanying component of the following sulfonamide carboxylic acids. K uryclh.ení. phase separation was allowed to ^{account HeATING} settle at elevated encloses preferably ¹ at ^50-70 ° C.

products of the invention are clear in the water-soluble or readily emuugfvαtelnýui ^p roducts, wherein ^{E 1} is generally in the form vystytuuí ¹ ^ ^ tozní Capon. These products can be used particularly advantageously as corrosion protection agents in aqueous cooling and cleaning fluids, in particular drilling fluids, cutting fluids and rolling fluids. In order to prepare these aqueous coolants and lubricants, the reaction products are added to the required amount of water. The concentration of the boric acid product itself or a mixture thereof with the aryl and optionally the fatty acids in the aqueous drilling fluids, cutting fluids and rolling fluids used in the application is generally about 0.5 to 10% by weight, preferably about 2 to 10% by weight. 5% by weight, based on the weight of the aqueous composition. If desired, other active substances known for this purpose may also be added. Aqueous corrosion protection agents are non-foaming, clear aqueous solutions and emulsion-type liquids.

The invention is illustrated in more detail, but not by way of example.

Example 1

61.8 g (1 moo) booité acid are heated with 210 g (2 moo) of diethanolamine and 117 g (1 moo) utylethamola ^{b »i} nu at ^{90 °, and} to form a solution Mréh. Zism about 3 ⁸ 5 ^g of VISK ^ ^ i, in water to form a clear solution of a soluble kapeHny that operating manual can be as a means to protect against corrosion.

Example 2

From 61.8 g (1 mole) of booic acid, 158 g (1.5 mole) of diethanolamine and 176 g (1.5 mole) of butyl ether. about 390 g of a viscous liquid.

Example 3

From 61.8 g (1 moo) of booic acid, 210 g (2 moo) of diethanolamine and 131 g (1 mol) of pennylethanol amine, about 400 g of a viscous liquid are obtained in an analogous manner to that described in Example 1.

See Example 4

From 61.8 g (1 mol) of booic acid, 158 g (1.5 mol) of diethanolamine and 197 g (1.5 mol) of pentyl ethanol amine, about 410 g of a viscous liquid are obtained.

Example 5

From 61.8 g (1 mol) of taoic acid, 210 g (2 mol) of diethanolamine and 75.1 g (1 mol) of isopropylamine (1-amino-2-propanol), about 370 g of reaction product are obtained analogously to Example 1. .

EXAMPLE 6

From 61.8 g (1 mol) of booic acid, 158 g (1.5 mol) of diethanolamine and 92 g (1.5 moo) of monoethanol amine, about 310 g of a viscous liquid are obtained.

See Example 7

To 16 ⁰ g mixture of Example ^1, the pulse of ≤ ⁸⁰ ° C is added thereto ^under stirring 33 ^g 1; - (benzenesulftoyl-N-oettylemint) -n-caproic acid. The clear solution obtained is used as a corrosion protection agent.

Example

To 160 g of Example 1 was added at 60 ° C 55 g of alkyl disultonamide acid, which was prepared according to the specifications of Example 1 of German Patent Specification 900,041 but from a hydrocarbon consisting of straight chain paraffins of 14 to 17 carbon atoms. Oil fáue ^which landed a mixture pM at ⁶⁰ DEG ^C for 9 min, ⁰ married. ^September ská about 190 g tamvého solution which can be used! Ivat as a means to protect against corrosion.

The following products were used as comparative samples:

Comparative product

61.8 g (1 mol) of booic acid are heated with 315 g (3 mol) of diethiethylphiolemin at 90 ° C until a clear solution is formed.

Comparative product

To 160 g of the solution of reference product A is added at 80 ° C 33 g of ε - (benzenesulfonyl-N-methalo-amino) -n-caproic acid until a clear solution is obtained.

Comparative product

Analogously to Example 8, to 160 g of the solution of Comparative Product A 3e was added 55 g of alkylsulfonamidoacetic acid containing parirfinic hydrocarbons, whereupon the separated oil phase was separated.

The corrosion protection properties of the products were examined according to DIN 51 360, sheet 2, and compared with comparative agents. Aqueous preparations with an active substance content of 1.5%, 2.0% and 3% were used for testing.

Microbicidal efficacy was assessed by reducing the number of microorganisms in the various microorganisms tested using 3% aqueous sample solutions.

The results of these experiments are summarized in the table below.

Table corrosion protective effect on ^T est ^ f ^ im ^p trc Apiro according to DIN 51 360/2

1,5 2,0 3,0 mitarobicidal properties 3% aqueous solutions initial microorganisms 10 & microorganisms after 24 hours

2 3 4 5

comparative product AND 4 3 0 10 ³ <100 10 ⁶ 10 ⁷ 10 ' comparative product (B) 1 0 0 10 ³ <100 10 ⁶ 10 ⁷ 10 ^{* 1} comparative product C 0 0 0 10 ³ <100 Ю ⁶ 10 ⁶ 10 ' product from of Example 1 4 2 2 <100 <100 <100 <100 <100 of Example 2 4 2 0 <100 <100 <100 <100 <100 of Example 3 4 3 0 <100 <100 <100 <100 <100 of Example 4 3 2 0 <100 <100 <100 <100 <100 of Example 5 4 3 0 <100 <100 <100 <100 <100 of Example 6 4 2 0 <100 <100 <100 <100 <100 of Example 7 0 0 0 <100 <100 <100 <100 <100 of Example 8 0 0 0 <100 <100 <100 <100 <100

Table Explanations:

Corrosion protection is rated according to the scale:

= no corrosion = corrosion traces = all corrosion = mild corrosion = strong corrosion milarobicidal properties were tested using the following microorganisms:

= Eschheichia coli = ^: Pseudoaonas aeruginota = Aspperillut niger = Cimlida albleme = Trichoderma

Claims (3)

SUBJECT MATTERS LEZU 1. Protected rhuman smoke smoke! in the form of an aqueous solution, characterized in that it contains 0.5 to 10% by weight, based on the aqueous solution, the reaction product of the acid, diethersulfate and the moiety derivative of the general formula R = NH-CH3 - CHXOH in which R denotes arylalkyl or soyl of the group having from 2 to 5 thiol atoms; and X boob of water and / or CH3, in an aellar ratio of?: 0.5 with 2.5? 1: 2.5: 0.5. 2. The perch to the point 1 of the sieve, wherein the sulfate is a sulfonyl-N-methaline) -noappronova Oy®® of the formula ε - (benzene) - COOH. Third JProtředek PPOD bbdu 1 vyznaČujícC SIM that ddáe sd8ahhjj alloyLtulfcnamiddoorr fight ^ / pyrimidine carboxylic acid of the formula wherein ^R * is alkyl-C ^ ou te Toupin 14 ^and 17 atoms and R is hydrogen or -CHgCOOH.