DE1620447C3 - Use of piperazine derivatives as a corrosion protection agent, coolant, lubricant or cutting agent - Google Patents

Description

H-N

RAW

RAW

where R and R 'each mean the same or a different, divalent aliphatic radical, which optionally has at least one side chain or is substituted, the chain length of R and R' in the respective amine being the same and each longest chain preferably consisting of 1 to 6 carbon atoms, have been prepared with orthoboric acid and adding a carboxylic acid or its derivatives to the complex boron-containing diamine formed in this reaction system, according to claim 1, as a corrosion protection agent, coolant, lubricant or cutting agent, optionally in a mixture with water, hydrocarbons and / or weak acids with a dissociation constant of less than 1 · ICT ⁴ (25 ° C).

The present invention relates to the use of piperazine derivatives as anti-corrosion agents, coolants, lubricants or cutting means, optionally in admixture with water, hydrocarbons and / or weak acids having a dissociation constant of less than 1 ■ 10 ~ ⁴ at 25 ⁰ C.

Especially recently, many inventions are concerned with improving working methods in the metalworking industry by using the cutting and non-cutting processing of metals instead of the cooling lubricants based on hydrocarbons or petroleum products, water-soluble or water-emulsifiable products, which have been used up to now. This is happening increasingly because it has been recognized that the cooling effect of water is superior to that of all other products, especially when the surface tension of the water is reduced by the wetting effect of other substances.

In order to achieve this effect, it has already been proposed in the aqueous cooling lubricants Bring soaps to use, especially those that differ from amino alcohols by adding higher levels sulfonated or unsulfonated fatty and naphthenic acids or those carboxylic acids that are used in the oxidation arise from hydrocarbons (CH-PS 2 24 652, US-PS 20 43 922 and 2174 907. DT-AS 11 00 217, 11 43 953, 11 23 422 and 10 33 825).

The use of such ethanolamine soaps is particularly advantageous because they are in aqueous solution have a pH of more than 9. In this way it becomes a certain anti-corrosive Effect achieved, which can be increased by adding other acids to these solutions or adding salts to strengthen the buffer effect, e.g. B. Alkylsulfonamidocarbonsäure and their Salts (DT-AS 11 43 953) or boric acid and its salts (US-PS 21 26 173 and 29 99 064).

An improvement in the anti-corrosion effect of such aqueous coolants, lubricants and cleaning agents is still achieved by the extremely toxic sodium nitrite, which in practice in almost is contained in all aqueous products (to which a number of patents also refer: US Pat. No. 2,999,064. DT-AS 10 33 825, DT-PS 8 85 295, 8 43 586 and 7 67 046).

From the point of view of occupational medicine, such an addition, which in practice amounts to 1 to 10% (in the Concentrates) is not responsible, because the lethal dose is with the adult humans only 4 g of sodium nitrite. Even if fatal poisoning with sodium nitrite is essentially only observed in the food preservation sector, it also occurs through inhalation methaemoglobinemia is associated with spray mist of such cooling lubricants containing sodium nitrite with drop in blood pressure and circulatory disorders (see R ö m ρ ρ, Chemie-Lexikon, Stuttgart 1962, p. 2035).

or even the smallest doses can cause liver damage from nitrous compounds (see Natural Sciences, 51, p. 637, 1964). Considered from this point of view alone, is the present one Invention suitable to establish a substantial technical advance.

The soaps recently described and claimed in the most varied of variations in combination with buffers and sodium nitrite as an anti-corrosive agent, from others Seen from the side, there are major disadvantages. One of these disadvantages is that in such Soaps used fatty acids with the alkaline earth metals to form sparingly soluble salts, thereby precipitating can arise that once let the solutions become cloudy or even "break" the can cause colloidal or finely dispersed solutions. Because of this, it is used in a number of Proposals dealt with the problem, such

to prevent precipitation or to stabilize such aqueous systems. In most of the cases it does in that a non-ion-forming emulsifier is added to the systems to counteract the poorly soluble Is able to disperse calcium salts. These non-ionic emulsifiers or wetting agents are chemically speaking, condensation products of alkylene oxides and various organic groups represents, where polyether alcohols, fatty alcohol polyglycol ethers, fatty acid amide polyglycol ethers or fatty acid polyglycol esters etc., to name a few. For example, in the US PS 29 99 064 describes an octylphenyl polyether alcohol mixed with the aforementioned substances, in DT-AS 11 43 954 a nonionic condensation product from amines with ethylene oxide, in DT-AS 11 29 647 a monobutyl ether of a condensation product of alkylene oxide with ethanolamine.

The mixtures just described have good wetting and dispersion properties and good corrosion protection properties. In order to be able to fully fulfill their task as a lubricant and lubricant, other additives are often used, in particular the lubricating effect is to be improved by the additives and bactericide to the mixtures and fungicidal properties are imparted and foaming of the solutions can be prevented. For improvement The lubricating and sliding effect, petroleum fractions, among other things, are used, which are often aromatic-free (DT-AS 1143 953 and 10 52 615).

To give these systems bactericidal and fungicidal properties and in particular that Phenol, cresol and triazine derivatives are usually used to prevent the growth of anaerobic bacterial strains or strongly antiseptic chlorine compounds (e.g. US Pat. No. 2,999,064) added. Just these additives however, have recently increased the incidence of skin diseases. you will be after Borelli, S. and Düngemann, H. in Berufsdermatosen "(Occupational Dermatoses), Vol. 12, No. 1, p. 1 (1964), regarded as the most common cause of occupational dermatoses. The ones used so far Substances are also very dangerous because they encourage bacterial growth in the sewage treatment plants in which the metalworking and cleaning agents are discharged after use, interfere and thus make the biological degradation of the discharged substances impossible at all.

The present invention is based on the object of providing a corrosion protection agent, coolant or cutting agent which, while avoiding the disadvantages of the prior art detailed above, has the advantage of being bactericidal and fungicidal in the concentrations in which it is used in practice, to work, combined with the property of being biodegradable in the degree of dilution in which it is discharged as waste water. Furthermore, the corrosion protection agent, coolant or cutting agent to be used according to the invention not only reliably destroys the causative agents of putrefaction and dermatoses, but also the most important carriers of bacteria, namely the insects, especially the flies, which particularly affect working people in the warm season annoy and cause the cooling lubricant to rot, switched off. It is particularly surprising for the person skilled in the art that the piperazine derivatives to be used according to the invention are not toxic to humans and also do not cause skin irritation. The object set out above, the present invention is achieved in that one piperazine derivatives, which by condensation reactions of an excess amino alcohols with orthoboric acid and adding a carboxylic acid or its derivatives to the complex boron-containing diamine formed in this reaction system, with a reaction between excess amino alcohol, the complex boron-containing diamine and not yet converted boric acid to the end products, have been produced, as a corrosion protection agent, coolant or cutting agent, optionally in a mixture with water, hydrocarbons and / or weak acids with a dissociation constant of less than 1 · 10 " ⁴ (25 ° C) used.

A preferred embodiment of the present invention is the use of piperazine derivatives, by condensation reactions of an excess secondary amino alcohols of the general formula

Η —Ν

RAW

RAW

where R and R 'each mean the same or a different, divalent aliphatic radical, which optionally has at least one side chain or is substituted, the chain length of R and R' in the respective amine being the same and each longest chain preferably consisting of 1 up to 6 carbon atoms, have been prepared with orthoboric acid and adding a carboxylic acid or its derivatives to the complex boron-containing diamine formed in this reaction system, as a corrosion protection agent, coolant, lubricant or cutting agent, optionally mixed with water, hydrocarbons and / or weak acids with a dissociation constant of less than 1 x 10 ^-4 (25 ° C).

The reaction on which the present invention is based is based on a conversion of boric acid (HjBO ₃ ) and its analogues with secondary amino alcohols of the general formula

H-N

RAW

RAW

with the formation of a complex boron-containing diamine of the general formula I

HN

R-O

R-O

O —R

O —R

R'-O Ο-R 'H

HN I N

R'-O O-R 'H

where R and R 'each mean the same or a different divalent aliphatic radical (—CH—; —CH _{2 —CH 2} - etc.), which optionally has at least one side chain or is substituted, where the chain length of R and R 'is the same size in the respective amine and each longest chain preferably consists of 1 to 6 carbon atoms.

Under the influence of possibly to be added higher molecular weight saturated and / or unsaturated carboxylic acids with a chain length of C ₁₂ to C ₂₂ and in the presence of amino alcohols, preferably di - ^ - hydroxyethylamine, with a relatively short reaction time of less than 4 hours and a reaction temperature of 160 up to 230 ⁰ C in addition to cation-active condensation products that react as wetting agents, the 1,4-di-ß-hydroxyethylpiperazine is formed.

It was previously known that under the influence of acidic condensing agents such. B. hydrohalic acids, Sulfuric acid, phosphoric acid, but also of low molecular weight carboxylic acids (M. P. BaI fe, J. K a η i ο η and E. M. T h a i η "Journal of the Chemical Society", London, 1952, p. 790) an alkylation aromatic bonded amino groups takes place. However, this reaction can also be used be to an alcoholic hydroxyl group versus an aliphatic, primary, secondary and / or tertiary Exchange amino group. So reacted 2 moles of di - /? - hydroxyethylamine (diethanolamine) in the presence of low molecular weight carboxylic acids at higher temperatures to 1,4-di- / f-hydroxyethylpiperazine (DT-PS 9 17 784 [1952], published documents by H 19 723 [1954]).

With the addition of 6 g of glacial acetic acid, the reaction leads to 105 g of diethanolamine over a period of time of 20 hours at a temperature of 200 ° C to 1,4-di-ß-hydroxyäthylpiperazin in one yield of «70%.

It is also known that 1,4-di- / miydroxyethylpiperazine Cation-active, surface-active substances are formed by etherification or esterification, which form the property to improve detergents (US-PS 24 21 707 and 24 94 827).

This reaction also forms such cation-active condensation products that are in the Overall system have the property of wetting agents. What is novel and inventive, however, is that under the influence of the product described in formula I and the carboxylic acids 1,4-di- / i-hydroxyäthylpipcrazine is formed in addition to its condensation products with carboxylic acids in such an amount, that it is with the product described by formula I and the others disclosed according to the invention Substances forms an ideal cooling, lubricating and cleaning concentrate, which among other things is a special represents anti-corrosive buffer mixture.

This buffer mixture, which is referred to below as "broadband buffer", is distinguished from the previously used buffer mixtures, in particular the salts of boric acid with alkylolamines described in US Pat. No. 2,990,064, which are present in a molar ratio of alkylolamine to boric acid = 2: 1 that it does not form any precipitations with calcareous waters and, even in a 1% aqueous solution, in a pH range between 9 and 7, is able to intercept 21 ml of n / 10 hydrochloric acid (titration curve A in A b b. I), while the best comparable product, namely the triethanolamine boric acid salt present in a molar ratio of 2: 1, can only trap 13.5 ml of n / 10 hydrochloric acid (titration curve C in A b b. I).

A mixture of the compound according to formula I with the boric acid salt of 1,4-di-ß-hydroxyethylpiperazine (titration curve ß in A b b. I) is capable of producing 12 ml of n / 10 hydrochloric acid or n / 10 at the neutral point pH 7 -Catch sodium hydroxide solution without changing the pH value, which can be seen from the extreme position of the two titration curves A and B.

It is also particularly important with regard to avoiding the causes of skin irritation as far as possible that the pH value of the solutions is below 9.

That actually the superior corrosion protection effect of this broadband buffer parallel with the Buffer effect is evident from the following experiments.

It became the anti-corrosive effect of boric acid triethanolamine salts (Molar ratio 2: 1) with that of the product labeled with formula I and the boric acid salt of 1,4-di - /? - hydroxyäthylpiperazine (Molar ratio 1: 1) compared.

When carrying out the tests, a test with milling chips from a cast iron is used, which has the following analytical data: 3.47% carbon (total), 2.33% silicon, .0.77% manganese, 0.29% phosphorus and 0.116% sulfur. The chips are made by dry milling a cast iron said composition and are in a length of about 5 to 7 mm and in a Thickness of about 1 mm before.

So much of these chips are placed on a watch glass with a diameter of about 100 mm that one Piles of around 40 mm in diameter and around 8 to 10 mm in height are created.

The solution of the product in question in distilled water is poured over the little pile in such a way that it is completely wetted. The excess solution is then poured off by holding the watch glass at an angle so that only as much solution remains as is retained by the chips. This heap of Gußspänen will leave at a temperature of 18 to 20 ^0C and a relative humidity of 50 to 60% itself. The judgment is made by first judging the formation of rust in a plan view and discriminating whether or not rust has formed. If rust has formed, the assessment in the table is: rust formation yes, otherwise no.

If no rust has formed, a further assessment is made by removing the watch glass viewed with the chips from below and the rust formation assessed below in the following way:

No rust
Under 5 rust spots
Below 25 spots of rust
over 25 rust spots

no

very little

little

strong

The values for the comparative assessment are contained in the following table I:

Table I.
Chip test

Composition of the product

Molar ratio 4% in distilled water.

of the components

up down

1. Triethanolamine N (CH ₂ -CH ₂ OH) ₃

2. 1,4-Di- / i-hydroxyethylpiperazine

no

no

<h

OH-CH ₂ -CH ₂ -N

3. Formula I.

CH ₂ -CH ₂ -C

HN

CH, -CH, -O

N-CH ₇ -CH ₇ -OH no

no

'(CH

2 * 2

c B

Ο —CH ₇ -H,

Ο —CH ₂ -]

4. Triethanolamine + H ₃ BO ₃

5. Triethanolamine + H ₃ BO ₃

6. Triethanolamine + H ₃ BO ₃

7. 1,4-Di- / i-hydroxyethylpiperazine + H ₃ BO ₃

8. 1,4-Di- / i-hydroxyethylpiperazine + H ₃ BO ₃

9. Triethanolamine + oleic acid

10. 1,4-Di - /? - hydroxyethylpiperazine + oleic acid

Table I (continued) Chip test

1: 1 2: 1 3: 1 3: 2 1: 2 1: 1 1: 1

no

no no no no no no no

no

very little

very little

no

no

very little

no

no

Composition of the product Rust formation 2% in distilled water. up down

I% in distilled water. up down

1. Triethanolamine N (CH ₂ -CH ₂ OH) ₃

2. 1,4-Di- / i-hydroxyethylpiperazine

(CH ₂ ),

OH-CH ₂ -CH ₂ -N N-CH ₂ -CH ₂ -OH

(CH ₂ ),

3. Formula I.

OH, CH-j O O CH-I HoC H

CH ₂ -CH ₂ -O 0 _{-CH 2} -H ₂ CH

4. Triethanolamine + H ₃ BO ₃

5. Triethanolamine + H ₃ BO ₃

little no strong

very little no little

/ \ _θ / \ _e

HN B N

no

No no

no little Yes 509 533/384 no little j »

continuation

10

Composition of the product

Rust formation least. 1% in aqua dest. 2% in aqua below above below above little Yes no very little Yes no very little no little no no no no no no no no no

6. Triethanolamine + H ₃ BO ₃

7. 1,4-Di- / i-hydroxyethylpiperazine + H ₃ BO ₃

8. 1,4-Di- / f-hydroxyethylpiperazine + H ₃ BO ₃

9. Triethanolamine + oleic acid

10. 1,4-Di- / i-hydroxyäthyIpiperazin + oleic acid

Table I (continued)
Chip test

Addition of the product

N-CH ₂ -CH ₂ -OH

1. Triethanolamine N (CH ₂ -CH ₂ OH) ₃

2.1 ^ -Di - ^ - hydroxyethylpiperazine

_/ (CH ₂ ) ₂ ^

OH-CH ₁ -CH ₂ -N

(CH ₂ ),

3. Formula I.

CH ₂ -CH ₂ -O 0 _{-CH 2} -H ₂ C

HN B

CH ₂ - CH ₂ - O

0-CH ₂ -H ₂ C

4. Triethanolamine -I- H ₃ BO ₃

5. Triethanolamine + H ₃ BO ₃

6. Triethanolamine + H ₃ BO ₃

7. 1,4-Di- / i-hydroxyethylpiperazine + H ₃ BO ₃

8. 1,4-Di- / i-hydroxyethylpiperazine + H ₃ BO ₃

9. Triethanolamine + oleic acid

10. 1,4-di- / f-hydroxyethylpiperazine + oleic acid

PH value
4%

11.0

9.7

9.8

8.5
9.0
9.5
8.5
8.3

8 7

8.3

2%

1%

10.5

9.6

10.0

9.5

9.3

The table clearly shows that the anti-corrosive effect of the compared products goes in parallel with the one in A b b. I described buffer effect. While for product 3 (first column of the Table I) the complex boron-containing diamine according to formula I in a dilution of 1% still does not have any Shows rust formation at a pH value below 9, occurs with the 4% solution of triethanolamine and boric acid a first rust formation as soon as the pH value falls below 9; that too 1,4-Di- / i-hydroxyäthylpiperazin shows despite a lower one pH value compared to triethanolamine better corrosion protection, which is particularly clear when the two "acid salts" of the two bases are compared with boric acid, that is, the two Results of product 4 and product 8 in the

Table I.

It compares products with each other in which a "basic" nitrogen atom is followed by an "acidic" Boron atom is coming. Despite the lower pH, in the case of the use of 1,4-di- / i-hydroxyethylpiperazine salts the rust protection values better (8.).

The compound described in formula I (see also

Example 1) is not a boric acid ester in the strict sense, as is normally the case in the reaction between a Alcohol or an amino alcohol is formed with boric acid in the absence of water. While the normal esters, as they are also described in US Pat. No. 2,441,063, almost under the influence of water instantly saponified (cf. W. Gerrard,

"The Organic Chemistry of Boron", New York 1961, p. 9), whereby boric acid and alcohol or amino alcohol are reformed, the complex boron-containing diamine characterized by formula I is stable in aqueous solution, even when the solutions are boiled. The fact that the titration curve A in A b b. I 'didn't change even if the solution was boiled for 2 hours. If the product were to hydrolyze, the titration curve / l would have to be converted into the titration curve D , which shows the behavior of an equal percentage aqueous solution of diethanolamine and boric acid (molar ratio 2: 1). However, this is not the case. The product according to formula I is saponified only by strong acids, in particular by fuming hydrochloric acid, the boric acid being recovered practically quantitatively in crystalline form under suitable reaction conditions. This procedure can be used for the determination of boric acid in this compound.

The substance identified by formula I and, among other things, characteristic of the reaction and behavior of the substance system also differs in particular from the substances that are formed in the reaction described in US Pat. No. 2,999,064. All reactions between amino alcohol and boric acid carried out there are carried out in the presence of water at room temperature. It is to be understood that can be formed under these reaction conditions not the body described with formula I, is novel and forms the exclusion of water, preferably at temperatures above 13O ⁰ C.

The following is the biological behavior of the piperazine derivatives to be used according to the invention or the systems to be used according to the invention are shown:

As is well known, the products, which are still widely used as coolants and lubricants, are still popular today Mineral oil-based skin irritation that is undesirable and detrimental to working people, which express themselves above all in the clinical picture of so-called "oil acne". Compare to this : W. Schneider and H. Wagne r, "Occupational Dermatoses", Vol. 2, No. 8, P. 207 (1954), J.E. Dal ton, J. American Medical Association, 147 (1951) and W. Morris and Cl. M a 1 ο ο f, New England Medical Journal, 247, 440 (1952). After these publications reached the skin diseases that are caused by petroleum products were already in 5th place in 1951 all skin diseases affecting the workers of a leading American oil company. This, although preventive measures in the form of protective skin ointments were used. Nevertheless caused 15% of all cutting oils based on mineral oil according to a study carried out in England industrial occupational dermatoses.

According to a statistical survey by G. W eber and H.H. Net t, "Occupational Dermatoses", Vol. 9, Issue 6, P. 293 (1961), the number of occupational skin diseases rose in the Federal Republic of Germany from 1739 cases in 1949 to 5648 cases in 1956, the group being metalworking Occupations in the second place of all skin disease traps moved.

In addition to petroleum as a skin-damaging factor, the additives or added to the mineral oil have an effect Additives are particularly aggressive when these petroleum products are replaced by sodium-alkaline soaps, Petroleum sulfonates, or emulsifiers in general, in water emulsifiable or brought into water-soluble form.

It is an important characteristic of the cooling, lubricating and cleaning concentrates disclosed in this invention, that these do not cause skin irritation, as the following studies show.

Tables show that the product is after Formula I as well as 1,4-di- / miydroxyethylpiperazine and like the cooling, lubricating and cleaning concentrate produced in Example 1, none Show irritant effect on human skin in the dilutions in which the products are practical Application. The experiments were carried out on a group of people who Had over-sensitized diseased skin. For this purpose, 1% solutions of the example were used 1 produced and characterized by formula I product, one produced according to Example 2 Ready-to-use mixture and the pure 1,4-di- / Miydroxyäthylpiperazins isolated according to Example 3 checked by the so-called "lobule test". To do this, small lobules with a l% Solution of the products were soaked by means of a plaster on the back area of the skin-sick person glued on and observed the reaction after a residence time of 24 hours.

Table II dermatitis Substances used in the "lapping test" O-CH ₂ -H ₂ C \ @ /
N reaction Number of diagnosis Eczema / \ after 24 hours the superinfected cases and mycotic l% solutions of O - CH ₂ H ₂ C with none of the 6th Eczema
Mycoses CH ₂ - CH ₂ - O examined
Products could 8th Sporyasis / \ ,, /
HM R a specific one 5 Liehen Ruber ΓΊ IN D
\ / ^ Irritant effect on Pityriasis rosea CH ₂ -CH ₂ -O the human
Skin noted
will 3 1,4-di - // - hydroxyethylpiperazine VV vl UwI I 1 and mixture according to example 2 1 1 H
/ H

It is also known that cooling lubricants based on emulsified hydrocarbons are particularly suitable are susceptible to bacteria that occur in particular in the form of anaerobic bacteria and in are able to attack the sulfo groups of the emulsifiers, whereby these, with elimination of toxic and malodorous hydrogen sulfide. This causes the cooling lubricant to decompose with very detrimental consequences.

Measures have therefore been taken to avoid the occurrence of such decomposition phenomena. One of these measures consists, for example, in the cooling lubricant solutions continuously blowing air and adding buffering compounds to the solutions (DT-PS 9 41 091).

This extremely costly and economically cumbersome measure is used in the event of use the systems disclosed in this invention are avoided simply by not using sulfur or contain sulfur compounds and thus deprive such anaerobic bacteria of their breeding ground remains.

This simple measure can also be implemented using other material systems. According to the invention The cooling lubricants used have at the same time due to the special process of their production such a strong bactericidal, fungicidal and insecticidal property that not only gram-positive, but also

Table III

gram-negative bacteria are destroyed or their growth is prevented. Likewise, they become parasitic Fungi and the most important vectors of the bacteria and fungi mentioned, namely the insects, are destroyed.

The completely new way to better working conditions in the metalworking industry come, becomes particularly significant because these effects do not, as already described, is achieved by an allergy-producing effect on the human skin, which is what has been used up to now and disinfectants used on a large scale was the case (cf. also B ore Hi, S. and Düngemann, H., "Berufsdermatosen", Vol. 12, Issue 1, p. 1 [1964]).

It is also of great importance that these bactericidal, fungicidal and insecticidal properties Surprisingly not be achieved by the presence of such chemical groups in which contain halogens, phosphorus or metal compounds.

The bactericidal activity was demonstrated on the product obtained in Example 2. The experiments were carried out in such a way that small filter paper sheets with a diameter of 9 mm and soaked with the solutions were placed on blood agar culture media inoculated with bacteria. The nutrient media were then ^{incubated for 24 hours at 30 °} C. and then evaluated (see table III for results).

of the bacteria

Degree of dilution of the cooling, lubricating and cleaning concentrate obtained according to Example 2 5% 2.5% 1.0% 0.1%

Staphylococci
(gram positive)

bacterium

prodigiosum

(gram negative)

strength
Inhibiting effect

strength
Inhibiting effect

strong inhibiting effect

strong inhibiting effect strong

Inhibiting effect
strength
Inhibiting effect

low

Inhibiting effect
low
Inhibiting effect

The experiments show that in the dilutions in which those claimed according to the invention Mixtures of substances are in practical use, namely up to a dilution limit of 0.1%, a strong to marked bactericidal effect is present. However, this disappears in higher dilution, so that the solutions are then biodegradable.

The growth of parasitic fungi is also caused by the cooling, lubricating and lubricating agents claimed according to the invention Prevent cleaning concentrates, as the test results summarized in "Table IV show.

Name of the mushroom

45 Applied substance from
example 1
(%)

Limit of
Stunted growth

Pscudopeziza
tracheifila

Alternaria tennis

Table IV Applied
dete sub
punch out
Example I.
(%) Limit of
Stunted growth Name of the mushroom 0.5
0.1
0.05
0.02 no growth
no growth
no growth
Growth
0.02% Botrytis cinercra

55

60 1.0 'no growth
0.1 no growth

0.01 growth off

0.01%

1.0 no growth

0.1 no growth

0.02 growth

0.02%

The growth limit for these microorganisms is lower than for bacteria, namely at 0.02% or 0.01% concentrate.

Finally, there is a further and completely novel effect of the cooling, Lubricating and cleaning concentrates in that they are capable of contact in concentrations up to 0.5% using insects to kill these. This makes them the main carriers of bacteria and fungi eliminates and nuisance to working people by insects, especially during the warm season, turned off.

The biological behavior of those used according to the invention as cooling, lubricating and cleaning concentrates Piperazine derivatives is characterized in that, surprisingly, a single chemical process creates a system of substances that has a bactericide, fungicide and insecticide effect results in the dilutions in which the substance system comes into practical use, preferably in concentrations that are above 0.01%, but that these properties are lost, in the concentrations in which the product ends up in wastewater or sewage treatment plants, d. H. in concentrations below 0.001%. In these concentrations, the product no longer has an inhibitory effect Bacterial growth.

In the following, the mechanical-dynamic behavior is to be used according to the invention Piperazine derivatives or substance systems described:

For the practical use of a cooling, lubricating and cleaning concentrate in the metalworking industry Industry, it is particularly important that for a wide variety of work processes, such as turning, milling, Drilling, thread cutting, grinding, etc., the concentrate with one for all operations Amount of water is diluted because the supply of the individual machine is advantageous through a central one System takes place in which, of course, only one dilution can be kept ready for all machines.

The ifE device is described in more detail below (see also Fig. 2):

With the help of a steel band 1 surrounding the retaining ring and a cardanic suspension device, a cross blade 2 and a loading lever which is mounted on cutting edges 3, the Retaining ring 4 with its 2 fixed rollers 5 under different loads against the piston pin as a bearing pin Press exactly parallel to the axis. At the start of the test, there is pure line contact between the test bodies before. At the point of contact between fixed rollers 5 and test bolts 6, the following conditions exist of the "normal test" a sliding speed of 0.2 m / sec (i.e. 150 rpm).

The test is carried out over a period of 3 hours, continuously flooding the sliding parts with the cooling lubricant diluted 1:40 (1.25%) according to Example 2. During the test, the running smoothness is assessed, the sliding friction measured at the beginning (μ A) and at the end (μ E) , as well as the temperature near the test point at the beginning (T _A ) and at the end (T _E ) of the test. The appearance of the lane at the end of the test also contributes to the overall assessment.

If the surface is smooth and without grooves, the lubricating effect is particularly good. From a falling sliding friction (μ A> μ E) it can be concluded that a good lubricating film has built up. The cooling effect can be assessed from the temperature at the beginning and at the end of the experiment. If this is low, the cooling effect is particularly good.

The result of the experiment is shown in the following table. There are some products in it for comparison indicated, which are already known in the literature (see Table V).

Table V Labelling wear and tear tendency Lane condition Tem Tem Serial of the cooling lubricant ing 1 (T ⁴ the sliding friction temperature temperature No. at the at the μ A - »μ E beginning end Coolant off 21.8 falling very sharply smooth, weak 20 ° C 80 ° C 1 Example 2 Shouts 1:40 in water commercial cooling lubricants 227.0 increasing in grooves 20 ° C cooks 2 medium torn open 1:40 in water Alkyl polyglycol ethers
11 η diluted 44.0 constant rough, grooving 20 ° C 144 ° C 3 Uli VvI U U11111
Mineral oil based cutting oil 19.5 increasing rough, grooving 20 ° C 14O ⁰ C 4th with active Cl Mineral oil based cutting oil 5.4 increasing smooth, unchanged 20 ° C 186 ° C 5 with 2% sulfur Mineral oil based cutting oil 28.7 increasing smooth, unchanged 20 ° C 134 ° C 6th with active Cl and sulfur

Table V shows the results of a comparison between the prior art belonging lubricants and the concentrates used according to the invention or their dilutions listed with water. The falling sliding friction proves the build-up of a "lubricating film" which is caused by the good condition of the track and the low wear is underlined. The used for comparison, prior art cutting oils activated by additives show in some cases a slightly better running pattern, but with the cutting oils of the prior art the serious disadvantage that these oils are significantly lower Have heat dissipation capacity as the cooling lubricant according to the invention, whereby as a result of this low cooling effect, significantly shorter tool lives have to be accepted.

The disadvantageous increase in temperature in the cutting oils of the prior art takes place a rapid drop in viscosity and a corresponding increase in sliding friction.

509 533/384

The one listed in Table V, consecutive number 2 Commercially available cooling lubricants, which are dispersed in water, can already be used in a relatively low dilution of 1:40 can no longer be used, since the value of the sliding friction with this Dilution ratio is already insufficient. It should be emphasized that this is commercially available Cooling lubricant, as can be seen from Table V, under otherwise identical conditions, ten times the wear as the cooling lubricant according to the present invention has.

The production of the piperazine derivative systems to be used according to the invention is explained below:

The reaction is carried out in such a way that the substance described in formula I is initially bound in full and / or in part. In this regard, boric acid or boric acid products with at least 2 moles of di-ß-hydroxyethylamine (diethanolamine) are pre-condensed at a temperature of 130 ⁰ C. At least 1 and at most 3 mol of water are formed per mole of boric acid H ₃ BO _{3 used or per mole of boron used.} The reaction is carried out so that the water formed can escape from the reaction mixture. The complex diamine which forms in this reaction has the summary composition which corresponds to formula I (see analysis example 1).

The substance of the formula I has the property of reacting with excess amino alcohols in the presence of higher molecular weight saturated and / or unsaturated carboxylic acids with a chain length of preferably C ₁₂ to C ₂₂ at a reaction temperature of 150 to 230 ° C, with di- and polycondensation products 1,4-Di-ß-hydroxyäthylpiperazine and its derivatives are formed quickly and with good yield.

This second reaction stage is also carried out so that the water of reaction which is formed can easily escape, and if necessary also with can work under reduced pressure. The amount of water per mole of carboxyl group of the carboxylic acid used is obtained, can be between 1 mol and 8 mol of water.

45 Production of a used according to the invention

complex boric acid ester

945 g (9 mol) of di- / Miydroxyäthylamin (diethanolamine) are at a temperature of about 100 ° C with 122 g (2MoI) of powdered or gritty boric acid (H ₃ BO ₃ ) in a 2-liter flask with a descending condenser connected and fitted with an electric stirrer, mixed until all boric acid is dissolved. Then the condensation reaction is set in motion with vigorous heating, which begins at a temperature of 130 "C, during which the reaction mixture boils and water is split off. The split off water is collected in a measuring vessel via the descending cooler. Within a period of about 45 minutes to 1 hour will increase the temperature of the reaction mixture to 23O ⁰ C, wherein an amount of water is cleaved ml 100-108 and übcrdestilliert. This corresponds to an amount of 6 moles Reaktionswasscr, ie, per mol of the boric acid are obtained 3 mole of water.

The reaction mixture is then subjected to vacuum distillation to determine how much Mol di-ß-hydroxyethylamine were bound in the reaction. With a pressure of 2 mm / Hg 525 g of di-ß-hydroxyethylamine recovered, with a boiling point of 160 to 165 ° C. This shows that, surprisingly, in the condensation reaction according to this example, a compound arose when 1 mole of boric acid reacted with 2 moles of di-ß-hydroxyethylamine.

The reaction mixture remaining after the vacuum distillation is clear, initially in the cold glassy solidifying mass of honey-yellow color. This product is heated until it is just if it melts and stirs it with a glass rod, the crystalline form of a product is obtained.

The product shows the following analytical composition: carbon and hydrogen according to L i e b i g.

Found: C = 42.1%, 42.5%, calculated for formula C = 44.0%, found: H = 9.0%, 8.8%, calculated for formula H = 8.7%, found: N according to Dumas = 11.7%, 12.0%, calculated for formula I 12.8%, found: N according to Kj e 1 da h 1 = 12.2%, 12.2%, calculated for formula I 12.8 %, where R and R ' _{mean the - CH 2} - CH ₂ group.

Boron was determined to be boric acid after saponification with hot fuming hydrochloric acid. Found: 4.8%, 4.5% calculated 4.9%.

example 1

1,260 g (12 mol) of di- / Miydroxyäthylamin (diethanolamine) are in a 2.5-liter flask provided with an electric heating mantle, distillation head and condenser, and an electrical stirrer, at a temperature of about 100 ⁰ C. 244 g (4MoI) boric acid (H ₃ BO ₃ ) mixed in powder or semolina form until all boric acid is dissolved; the condensation reaction is then started with vigorous heating and starts at 130 ° C., the reaction mixture boiling and water being split off. The separated water is condensed through the descending condenser and collected in a measuring vessel. Over a period of about 45 minutes to 1 hour, the reaction temperature is increased to 23O ° C., an amount of water of 210 to 216 ml being split off and distilled over. The reaction mixture is then allowed to cool down to a temperature of 160 ^° C. by switching off the heating. The heating is then switched on again and at the same time 280 g of tall oil fatty acid at a temperature of 160 ^° C. is allowed to flow into the reaction mixture through an open tube. Good stirring ensures that the reactants are mixed quickly. After the addition, the tube is closed. When 180 "C is reached, the second stage of the condensation reaction occurs, which is designed in such a way that 65 to 72 ml of water are split off within a period of about 2 hours, the temperature not exceeding 230 to 240 ° C.

The reaction mixture obtained is then allowed to cool to a temperature of 80 to 120 ^° C. and the reaction mixture is then poured into a vessel with 1350 g of distilled water and the two components are mixed, resulting in an emulsion-like, viscous, pleasantly ester-like smelling liquid. This emulsion is added so much of an aromatic-free hydrocarbon of the following parameters, with constant stirring, until a completely clear, viscous yellow, pleasantly fruity

19 20

smelling liquid is created. For all parts by weight of spindle oil and 10 parts by weight of grease to clarify the initially emulsion-like solution, acid polydialkylolamide is required.
80 to 160 g.

Key figures for hydrocarbons _. ...

Example 4

Specific weight at 15 ° C / ⁸⁰⁵ 1st reaction stage as described in Examples 2 and 3

bieaepun. ; , · 7 ₄ iV ^ben · ² - reaction stage as in Examples 1 and 3

pf? "" ⁸⁸¹ E,, πα, but then at 200 ⁰ C 256g

ι H hl η m ( ^{! Mo1} ) added palmitic acid and within 30 mi

joazani. u, uj ^ _{nuten 5gg} ^ _{2 UqX) water au} condensed.

Anni point yi L, _{Dag product has se} if _s like character is at

Instead of this hydrocarbon, 80 ^° C. can still be clearly soluble in water. When cooling, other mineral oil fractions, glycols, polyglycols, however, solidify into a stable, pasty fatty acid amide, polyester, polyether, silicone or emulsion. This can be diluted with water as a coolant, all other substances that are used in position 15 lubricants and cleaning agents,
are, with an addition amount of a maximum of 20%, the In order to obtain a more manageable product, the emulsion can be transformed into a clear liquid. th, mix 100 parts by weight of the 1: 1 with water. The concentrate prepared according to Example 1 dissolves the diluted product with 70 parts by weight of spinach completely clear in every ratio with water, del oil.

does not foam much, does not form 20 even with hard water. .
Precipitates and represents an ideal cooling, lubricating, Example 5
and cleaning concentrate, which can be used up to dilution 1st reaction stage as described in Examples 1 and 3 in water of 0.05%. 2nd reaction stage as known in Examples 2 and 3, but this time 300 g of a Gemi-Example 2 25 cal of saturated C ₁₄ -C ₂₂ carboxylic acids (10 parts)

1 reaction stage ^{53 parts of} 8 ^{esätti ter} S Q ₈ carboxylic acid and 35 parts of saturated C ₂₀ -C ₂ 2-carboxylic acid was added and at 220 ° C

As in Example 1, the first reaction stage is 67 g of water (3.7 mol) over the course of 50 minutes.

described carried out, with 630 g of diethanoid condenses.

amine (6 mol) and 122 g boric acid H ₃ BOj (2MoI) 30 The reaction product has a soap-like character,

are used and 108 g of water (6 mol) dissolves in water at a ratio of 1: 1 at 80 ° C,

are condensed out. When it cools down, the mass solidifies into a stable one

. _r pasty emulsion. This can be diluted with water

2. Keaktionsstule _a , _{s Küh]} ^ _lubrication . _and detergents used

This will be described in the same way as in Example 1.

carried out, with 200 g of lauric acid (1 mol) for. .

Apply and 54 g of water (3 mol) removed. Example 6

will split. 1st reaction stage as described in Examples 2 and 3

The reaction product dissolves clearly in water and ben. 2nd reaction stage as in Examples 2 and 3 wets heavily. It is advantageously written in a ratio of 1: 1 40, but this time 280 g (1 mol) of pure water are diluted with distilled water and then oleic acid is added and within 25 minutes at a cooling, lubricating and 220 ° C temperature of 50 that is clearly soluble in water g of water (2.8 mol) condensed out.
Cleaning concentrate, to which you add 2% of the hydrocarbon and / mass described in The reaction product solidifies to a honey-like example 1, which is dissolved in a ratio of 1: 1 in distilled water or organic or inorganic acids with a 45, a clear in every ratio with water Dissociation constants of <5 · 10 ~ ⁴ to improve the buffer effect compared to cooling, lubricating and cleaning concentrate can be added. forms.

Example 7

Example _{3 50 (} Reaction stage as described in Example 1

1st reaction stage as in Example 2, whereby 630 g of 1260 g (12MoI) diethanolamine, 244 g (4MoI) boron-diethanolamine (6 mol) and 122g boric acid H ₃ BO ₃ acid reacted and 216 g (6 mol) water condensation ( 2 mol) are used and 108 g of water are sated.

(6 mol) are condensed out. 2nd reaction stage as described in Example 1,

2nd reaction stage as in Example 2, however, instead of the tall oil fatty acid, this time 280 g then 288 g of myristic acid were added, and pure oleic acid was used within (1 mol) and for 60 ml-20 Minutes at 225 ° C, 58 g of water (3.2 mol) are condensed out at 200 ° C 94 g (5.2 mol) of water, condensed out. The product is suitable in a ratio of 1: 1 with

The reaction product obtained is diluted soapy water, excellent as a coolant, smear resistant. Hot diluted 1: 1 with distilled water, 60 and cleaning concentrate.

it forms a stable emulsion, which can be further mixed with water.

can be diluted. substance, as described in Example 1, add.

A product diluted 1: 1 with water shows good results

Cooling, lubricating and cleaning properties with. ■ ^ ι ο

good anti-corrosion effect. 65 Example »

To produce a clear water-soluble product, 630 g (6 moles) of diethanolamine are kept at about 100 ° C

one adds 90 parts by weight of the in a ratio of 1: 1 mixed with 180 g (3 mol) of boric acid and then 420 g

Water dissolved product of this example was added to 25 Ge (about 1.5 moles) tall oil fatty acid.

The reaction between boric acid and diethanolamine starts at 13O ⁰ C. With vigorous heating drives the temperature for a period from 90 minutes to 220 ⁰ C, whereby 192 g (10,6MoI) water are condensed; then is allowed to a second vessel, a hot mixture of 315 g (3 moles) of diethanolamine with 300 g (2 moles) of triethanolamine run and then to react for 30 minutes at 220 ⁰ C., a further 70 g (3,9MoI) water is split off.

The reaction product is dissolved in a ratio of 1: 1 in distilled water and forms in this form and / or mixed with a hydrocarbon according to Example 1, an excellent cooling, lubricating and Cleaning concentrate.

A further embodiment of the invention consists in that the formation of 1,4-di- / i-hydroxyethylpiperazine and its derivatives is carried out in such a way that the carboxylic acid is added to the reaction mixture at the beginning, but the temperature is then reduced by throttling the heating Maintains a period of about 30 minutes at a temperature of 135 to 150 ^° C. until enough of the compound described according to formula I has formed, which then catalyzes the reaction which leads, inter alia, to the formation of 1,4-di- / mydroxyethylpiperazine will.

Example 9

840 g (8 mol) of diethanolamine are mixed as described in Example 8 at about 100 ⁰ C and 247 g (4 moles) of boric acid and then 560 g (2 mol%) tall oil fatty acid were added. Then carefully heated until it reaches a temperature of 135 ° C, and then, the heating so that about 30 minutes is required is exceeded until a temperature of 150 ⁰ C. The heating is then continued vigorously so that a temperature of 230 ^° C. is reached within a further period of 60 minutes. A total of 310 g (17.3 mol) of water is condensed out.

The reaction product dissolves in water in a ratio of 1: 1 and is an excellent one in this form Cooling, lubricating and cleaning concentrate.

The isolation of 1,4-di- / i-hydroxyäthylpiperazins can be carried out from all reaction mixtures which were described according to Examples 1 to 9. She succeeds in a simple form such that one of the reaction mixture described in formula I, among other things complex diamine, by repeated recrystallization from methoxy-hexanol (4-methoxy-4-methylpentanol-2) separates and then wins in pure form.

50 g of the pure, undiluted reaction product are mixed with 200 g of methoxy-hexanol at 100.degree Digested for 15 minutes and decanted from the insoluble, resinous residue while hot. The hot solution it is allowed to cool, whereby a sticky mass which clogs a filter is initially deposited. This is poured off after about 24 hours and the solution is concentrated to about half in vacuo. Twice the amount of petroleum ether is added and the decanting from the after about 2 hours The layer and solvent that are deposited at the bottom are removed and a first, contaminated one is obtained from it Crystal fraction that can be purified by recrystallization; one wins from the upper layer a very pure group.

Yield 6 g with a melting point of 130 ³ C.

Analysis and ultra-red spectrum confirm the identity with 1,4-di-ß-hydroxyethylpiperazine.

For this purpose 3 sheets of drawings

Claims (2)

Patent claims: 1. Use of piperazine derivatives which have been prepared by the condensation reaction of an excess amino alcohol with orthoboric acid and adding a carboxylic acid or its derivatives to the complex boron-containing diamine formed in this reaction system, with a reaction between excess amino alcohol, the complex boron-containing diamine and unreacted boric acid to the end products, as a corrosion protection agent, coolant, lubricant or cutting agent, if necessary in a mixture with water, hydrocarbons and / or weak acids with a dissociation constant of less than 1 · 10 ~ ⁴ (25 ° C). 2. Use of piperazine derivatives, the condensation reaction of an excess secondary amino alcohol of the general formula