EP0797692A1

EP0797692A1 - Nitrogen-free corrosion inhibitors with good buffering action

Info

Publication number: EP0797692A1
Application number: EP95941081A
Authority: EP
Inventors: Karlheinz Hill; Sigrid Igelmund; Bernd Stedry; Jürgen Geke; Andreas Wilde; Harald KÜSTER
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1994-12-16
Filing date: 1995-12-08
Publication date: 1997-10-01
Anticipated expiration: 2015-12-08
Also published as: WO1996018757A1; AU4260696A; DE4444878A1; TR199501574A2; EP0797692B1; ATE186080T1; US5795372A; DE59507145D1

Abstract

PCT No. PCT/EP95/04844 Sec. 371 Date Jun. 16, 1997 Sec. 102(e) Date Jun. 16, 1997 PCT Filed Dec. 8, 1995 PCT Pub. No. WO96/18757 PCT Pub. Date Jun. 20, 1996Nitrogen-free aqueous anticorrosion composition containing a) a carboxylic acid having 6 to 44 carbon atoms; and b) aromatic hydroxy compounds having a pKa value in the range of 7.0 to 11 for the hydroxy group, in a weight ratio of 1:2 to 20:1, in the form of a concentrate to be diluted with water by a factor of between 20 and 200 and in the form of a ready-to-use aqueous preparation that preferably contains 0.2 to 2 wt % component a) and 0.1 to 0.6 wt % component b) and has a pH value in the range of 7 to 11.

Description

"Nitrogen-free corrosion inhibitors with a good buffer effect '

The invention relates to corrosion protection agents for the temporary protection against corrosion of metallic, in particular iron-containing, surfaces which are present as an aqueous emulsion or preferably as an aqueous solution. For wastewater reasons, they are free of nitrogen and are characterized by a good buffering action, so that their alkaline pH can be maintained for a longer period of time despite possible acid entry and / or microbiological acid development.

The protection of metals at risk of corrosion such as iron, aluminum, zinc, copper or their alloys against corrosion is a wide-ranging technical task. It arises in particular when the metal parts are not or not yet covered with a permanently corrosion-protecting coating, such as a lacquer, for example, due to their processing condition or their area of use. Examples of this are metal parts during technical processing stages such as cutting or non-cutting shaping or cleaning as well as finished metal components such as heat exchangers or pipelines which come into contact with corrosive aqueous media during their function. In order to prevent or contain corrosion during or between the individual processing steps or during the intended use, the metal surfaces are brought into contact with corrosion inhibitors which provide temporary protection against corrosion. It is often necessary for technical reasons, for example in aqueous cooling or heating circuits, or for reasons of environmental protection, for example during or after aqueous cleaning of the metal surfaces, that the corrosion inhibitors are brought into contact with the metal surfaces in the aqueous phase can be. It is therefore a desirable property of corrosion inhibitors, water-soluble or to be at least dispersible in water.

A large number of inorganic and organic compounds are known as water-soluble or water-dispersible corrosion inhibitors. Inorganic corrosion inhibitors can be used, for example, on chromates. Nitrites or phosphates can be built up, which, however, are more or less disadvantageous for toxicological and ecological reasons. Organic corrosion inhibitors are often based on carboxylates, amines, amides or on nitrogen-containing heterocyclic compounds. There are serious toxicological concerns about the use of secondary amines or compounds which can split them off because of the possibility of nitrosamine formation. However, other nitrogen-containing compounds are also not toxicologically harmless or at least disadvantageous because of possible water pollution. Carboxylic acids do not have these disadvantages, but in practice they do not prove to be sufficiently long-term effective if the pH value is lowered by an acid input into the inhibitor baths or by microbiological processes to such an extent that the carboxylic acids instead of in the salt form the less effective acid form.

EP-B-341 536 describes a water-soluble corrosion inhibitor system containing alkenyl succinic acid, arylsulfonylanthranilic acid and alkanolin. This system does not meet the nitrogen-free requirement. From GB-B-1 238205 a water-soluble corrosion protection combination is known which consists of gluconate and benzoate or salicylate salts. Because of the strong hydrophilicity of the salts used, this combination has only limited effectiveness. EP-A-294649 teaches the use of partially or completely neutralized hydroxyaryl fatty acids as corrosion inhibitors. Although these have a good anti-corrosion effect, they are difficult to access.

The use of carboxylic acids as anticorrosive agents in, for example, cooling lubricants, cleaners and anticorrosive emulsions is widespread in the prior art. For example, DE-A-4229848 describes a cooling lubricant emulsion whose corrosion protection system is based on a combination of long-chain fatty acids, short-chain fatty acids, Dimer fatty acids and aromatic carboxylic acids such as benzoic acid or salicylic acid are based. Here, the carboxylic acids are neutralized with potassium hydroxide. This system does not contain a buffer component in the sense of the present invention.

German patent application P 4323909 teaches two-component agents for cleaning and / or passivating metal surfaces, one component containing the anticorrosive agents. The corrosion inhibitor active ingredients are selected from

i) at least one carboxylic acid of the general formula (III):

R-C00Y (III)

where R is a straight-chain or branched, saturated or unsaturated alkyl or alkenyl radical having 5 to 21 carbon atoms or a radical of the general formula (IV)

R'- ^^ - COCH-CH- (IV)

represents a straight-chain or branched alkyl radical having 6 to 18 carbon atoms saturated with R ¹ and Y represents hydrogen, an alkali metal ion equivalent or an ammonium ion,

ii) substituted benzoic acids, ii) benzenesulfonamidocarboxylic acids, iii) aliphatic dicarboxylic acids with 2 to 36 carbon atoms, and iiii) the salts of the acids mentioned under i) to iii) and their mixtures.

This system also does not contain any buffer components to stabilize the alkaline pH value when acid is introduced or when acid is formed.

Finally, EP-A-556087 reveals the knowledge that monocarboxylic acids with an odd number of carbon atoms, in particular heptanoic acid, nonanoic acid and undecanoic acid, are particularly effective corrosion inhibitors. The invention has for its object to provide nitrogen-free water-soluble or water-dispersible anticorrosive agents whose anticorrosive agent consists of carboxylic acids and which therefore have an increased service life and safety in use that they are stabilized against shifts in pH.

This object is achieved by containing a nitrogen-free aqueous corrosion protection agent

a) carboxylic acid anions with 6 to 44 C atoms and b) aromatic hydroxy compounds with a pKa value for the hydroxyl group in the range from 7.0 to 11

in a weight ratio of 1: 2 to 20: 1.

The aromatic hydroxy compound serves as a buffer component, which makes an additional contribution to the corrosion protection effect. The buffered corrosion protection system according to the invention is used in the form of an aqueous emulsion or, preferably, as an aqueous solution, the particularly effective pH range being from 8.5 to 10. The invention is based on the knowledge that the aromatic hydroxy compounds with a pKa value for the hydroxy group in the range from 7.0 to 11 in the stated pH range of the ready-to-use preparation have a particularly good buffering action. For use in the preferred pH range from 8.5 to 10 aromatic hydroxy compounds with a pK _s value for the group hydroxycarboxylic particularly favorable in the range of 8.5 to 10 degrees. Salicylic acid, which has a pKa value of 13.4 with respect to the hydroxyl group (N. Konopik, O. Leberl: "Dissociation constants of very weak acids", Monthly Bulletin 80 (1949), pp. 660-662) does not meet this condition.

The pKs value is known to be the negative decimal logarithm of the acid constant K $, which is generally known as the thermodynamic variable and is a measure of the completeness of the proton transfer reaction from the acid to water and thus of the acid strength. Details on this can be found in general chemistry textbooks. HRChristen may be mentioned as an example: "Basics of general and ganischen Chemie ", Verlag Sauerländer, Aarau and Disterweg. Alle, Frankfurt, 4th edition 1973, pp. 353-372. The pKa value for the hydroxyl group of the aromatic hydroxy compounds according to the invention relates to the acid-base reaction of the hydroxyl group the aromatic hydroxy compound with water The aromatic hydroxy compounds to be used according to the invention can carry carboxylic acid or sulfonic acid groups, the pK $ values of which are substantially lower and have no significance for the buffering effect used according to the invention, but can improve the corrosion protection effect of the overall system.

The anti-corrosion agent according to the invention comes in aqueous preparation, i.e. as an aqueous emulsion or preferably as an aqueous solution for use. This preparation preferably contains 0.2 to 2% by weight of component a), 0.1 to 0.6% by weight of component b) and, as the remainder, water and means for adjusting an alkaline pH, preferably Alkali metal hydroxides, with potassium hydroxide being preferred for reasons of solubility in the concentrate. Depending on the application, this aqueous preparation can contain further auxiliaries. The pH of the aqueous preparation is in the range from 7 to 11, preferably in the range from 8.5 to 10, for example 9.3.

Component a) is preferably selected from mono- or polybasic, preferably monobasic, saturated or mono- or polyunsaturated linear or branched carboxylic acids having 6 to 22 carbon atoms and / or unsaturated polybasic, preferably dibasic, carboxylic acids 36 to 44 carbon atoms. Examples of carboxylic acids with 6 to 22 carbon atoms are the unbranched saturated * carboxylic acids hexanoic acid, 0c-tanoic acid and decanoic acid and in particular the monocarboxylic acids with an odd number of carbon atoms to be preferably used according to the teaching of EP-A-556087, especially the heptanoic acid, nonanoic acid and undecanoic acid. Branched saturated carboxylic acids, in particular 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid and 2,2-dimethyloctanoic acid, also offer particular technical advantages. A preferred example of an unsaturated short-chain carboxylic acid is 1,4-hexadienoic acid (sorbic acid). Furthermore, there are generally saturated or unsaturated fatty acids with 12 to 22 carbon atoms in the molecule or technical mixtures of these can be used, such as those that occur during the splitting of natural fats and oils or are also accessible synthetically. Examples include oleic acid and the technical mixture of different fatty acids called tall oil fatty acid, which can be obtained from tall oil and which mainly consists of linoleic and conjugated C _j g fatty acids, oleic acid and 5,9,12-octadecatrienoic acid. Alkylphenyl-substituted unsaturated carboxylic acids of the type can also be used

R'- C6H4 - C (0) - CH = CH - COOH or R'- C6H4 - CH = CH - COOH

are used in which R 'is a linear or branched alkyl radical having 8 to 14 carbon atoms.

Unsaturated polybasic carboxylic acids with 36 to 44 carbon atoms, of which the dibasic representatives are preferably used, are also referred to as "dimer fatty acids". They are technically accessible through - generally acid-catalyzed - dimerization of suitable unsaturated fatty acids with 18 to 22 carbon atoms. The reaction products are generally mixtures of acids of different degrees of oligomerization together with unreacted or isomerized starting materials. Such products are commercially available, for example from Unichema under the product group name Pripol ^R or from Henkel KGaA under the product group name EmpolR.

In addition to the carboxylic acid components a), the corrosion-inhibiting effect of which is already known in the prior art, the aromatic hydroxy compound b), which acts as a buffer, is of particular importance in order to stabilize the corrosion inhibitor against acid entry or acid formation and thus without further care measures for one against unbuffered Keep systems usable for an extended period of time. The selected aromatic hydroxy compounds have the advantage over other conceivable buffer systems for the pH range 7 to 11 that they support the corrosion protection effect of the carboxylic acid components. Component b) is preferably selected from mono-, dinuclear or trinuclear aromatic hydroxy compounds of the general formula (I) HO - Aroma - X (I)

where X is selected from the substituents COOH, SO3H or SO2-C6H4-OH and "aroma" is a mono-, dinuclear or trinuclear carbocyclic aromatic six-ring system of the benzene, naphthalene, anthracene or phenanthrene type which represents further substituents X, OH and / or alkyl, hydroxyalkyl and / or hydroxyalkyl ether radicals having 1 to about 4 carbon atoms. Hydroxyalkyl ether residues such as, for example, ethylene glycol ether or propylene glycol ether residues can be obtained, for example, by ethoxylation or propoxylation of phenols.

Mononuclear aromatic hydroxy compounds, which can be described by the general formula (II), are preferably used as component b):

where X is selected from substituents COOH, SO3H or SO2-C6H4-OH and R ¹ , R ² , R3 and R ⁴ independently of one another a group X, H, OH or an alkyl, hydroxyalkyl or hydroxyalkyl ether radical with 1 to 4 C- Mean atoms.

Preferred compounds of the general formula (II) are those which contain only a single substituent X, which is preferably in the para position to the hydroxyl group and in which the substituents R ¹ , R ² , R3 and R ^{4 are} preferably hydrogen. The substituent X is preferably one of the groups COOH, SO3H or SO2-C6H4-OH. Particularly suitable examples of such compounds are 4-hydroxybenzoic acid, 4-phenolsulfonic acid and 4,4'-dihydroxydiphenylsulfone (bisphenol S).

Compounds with a carbon or sulfonic acid function are largely in the form under the pH conditions of the application solution in the range from 7 to 11 their carboxylate or sulfonate anions are present. Since, according to the invention, such hydroxy compounds are used whose pKs value for the hydroxyl group is in the range from 7.0 to 11, it can be expected that the hydroxyl groups in the selected pH range are partially deprotonated. For the possibility of determining the pKa values of the only weakly acidic hydroxyl groups, reference is made to the Konopik reference mentioned at the beginning. Further pKs regulations are contained in: B.Jones, JCSpeak to: "Thermodynamic Dissociation Constants of Hydroxy- and Alkoxy-benzoic Acids", J.Chem.Soc. 1944, pp. 19-20. Accordingly, m- and p-hydroxybenzoic acid have pKs values of 9.94 and 9.39, respectively. The pK $ value of 4-phenolsulfonic acid for the phenolic hydroxyl group was determined to be 8.9 and that of bisphenol S to 9.5. In contrast, the dissociation constant of salicylic acid with respect to the OH group is so low that it could not be determined by the method of potentiometric titration selected here using a glass electrode.

For the long-term stability of the ready-to-use aqueous corrosion protection solution or corrosion protection dispersion aimed at according to the task, it is preferred that it have a buffer capacity in the range from 1 to 8. The buffer capacity is defined as the consumption of 0.1 normal hydrochloric acid, measured in ml, in order to lower the pH value of 50 g of the corrosion protection agent by 1.3 units, for example by 50 g of the corrosion protection agent from a pH value of Titrate 9.3 to a pH of 8. Such buffer capacities can be achieved when using components a) by combining them with components b) according to the invention.

Buffer capacities of a similar magnitude could also be achieved if components a) were combined with other buffers, e.g. suitable amines, borates or phosphates combined. However, amines should not be used for the reasons mentioned at the beginning. The other inventive teaching can also dispense with the other ecologically disadvantageous buffer systems such as borates or phosphates.

The above-mentioned concentration data for the corrosion protection agents suitable for the use according to the invention relate to the ready-to-use aqueous preparations. In principle, these can be prepared on site by dissolving or dispersing the individual components in water in the specified concentration ranges. In the technical field concerned, however, it is customary to market such combinations of active substances in the form of concentrates which already contain all the components in the required proportions and from which the ready-to-use treatments are diluted with water on site solution baths are produced. Accordingly, the invention also relates to aqueous active ingredient concentrates which contain components a) and b) in the proportions specified in claim 1. The active substance concentrations in these concentrates are preferably adjusted such that an aqueous corrosion protection agent having the properties described above is obtained by diluting the concentrate with water by a factor of between about 20 and about 200.

embodiments

According to the table, active ingredient concentrates were prepared from the inhibitor component a) and the buffer component b) by dissolving or dispersing the individual components in the concentrations given in the table in deionized water and adding enough KOH to convert one with deionized water solution diluted by a factor of 50 had a pH of 9.3.

The buffer capacity was determined by titrating 50 g of the concentrate solution diluted 1:50 with 0.1 normal hydrochloric acid from pH 9.3 to pH 8. The required consumption of hydrochloric acid in ml is called the buffer capacity.

A plate climate test was carried out to check the corrosion protection effect. For this purpose, steel sheets of quality ST 1405 with the dimensions 5 cm × 10 cm were brushed with an aqueous surfactant solution, rinsed with water and alcohol and dried. The sheets were then immersed in the concentrate solutions diluted by a factor of 50 with demineralized water, drained and stored in a climatic chamber at 22 ° C. and a relative air humidity of 76%. All examples provided the required corrosion protection (less than 30% corrosion after 40 days of testing). The formulation according to Example 10 was also tested in a larger dilution. The required corrosion protection effect was achieved by diluting the concentrate by a factor of 75.

Table: Active substance concentrates: Figures in% by weight in water / KOH

Inhibitor a) Concentrated buffer b) Concentrated buffer capacity (%) (ml)

Compare 1 heptanoic acid 20 0.06

Compare 2 sorbic acid 20 0.03

Compare 3 heptanoic acid 20 salicylic acid 5 <0.1

Ex. 1 tall oil fatty acid 20 4-hydroxyben- 5 1.6 zoic acid

Ex. ² oleic acid 20 4-hydroxyben- 5 ² , 6 zoic acid

Ex. 3 dimer fatty acid 20 4-hydroxyben- 5 1.6 (EmpolR 1022, zoesäure Henkel KGaA)

Ex. 3 heptanoic acid 20 4-hydroxyben- 5 ² , 0 zoic acid

Ex. 4 sorbic acid 20 4-hydroxyben- 5 1.8 zoic acid

Ex. 5 sorbic acid 20 4-hydroxybene-10 5.0 zoic acid

Ex. 6 sorbic acid 20 4-hydroxybene 20 6.0 zoic acid

Ex. 7 Sorbic Acid 20 Bisphenol S 5 1.6 Table (continued): Active ingredient concentrates; Figures in% by weight in water / KOH

Inhibitor a) conc. Buffer b) conc

(%) quantity (ml)

Ex. 8 heptanoic acid 20 4-phenolsul- 5 1.6 fonic acid

Ex. 9 heptanoic acid 10 4-hydroxyben- 5 2.0

+ Sorbic acid 10 bolsulfonic acid

Example 10,5,5-trimethyl-10 4-hydroxybene-10 5.2 hexanoic acid bolsulfonic acid

+ Sorbic acid 10

Claims

claims

1. Containing nitrogen-free aqueous corrosion inhibitor

a) carboxylic acid anions with 6 to 44 C atoms and b) aromatic hydroxy compounds with a pK $ value for the hydroxy group in the range from 7.0 to 11

in a weight ratio of 1: 2 to 20: 1.

2. Corrosion protection agent according to claim 1, characterized in that it

0.2 to 2% by weight of component a), 0.1 to 0.6% by weight of component b) and

the remainder is water, means for adjusting an alkaline pH, preferably alkali metal hydroxides, in particular potassium hydroxide, and optionally further auxiliaries and is present as an emulsion or preferably as an aqueous solution.

3. Corrosion protection agent according to claim 2, characterized in that it has a pH in the range of 7 to 11.

4. Corrosion protection agent according to claim 3, characterized in that it has a pH in the range from 8.5 to 10.

5. Corrosion protection agent according to one or more of claims 1 to 4, characterized in that component a) is selected from mono- or poly-based saturated or mono- or polyunsaturated linear or branched carboxylic acids having 6 to 22 carbon atoms and / or unsaturated polybasic carboxylic acids with 36 to 44 carbon atoms.

6. Corrosion protection agent according to one or more of claims 1 to 5, characterized in that component b) is selected from mono-, di- or trinuclear aromatic hydroxy compounds of the general formula (I) HO - Aroma - X (I)

where X is selected from substituents COOH, SO3H or SO2-C6H4-OH and "aroma" is a mono-, dinuclear or trinuclear carbocyclic aromatic six-ring system of the benzene, naphthalene, anthracene or phenanthrene type which represents further substituents X, OH and / or can carry alkyl, hydroxyalkyl and / or hydroxyalkyl ether radicals having 1 to 4 carbon atoms.

7. Corrosion protection agent according to claim 6, characterized in that component b) is selected from aromatic hydroxy compounds of the general formula (II)

where X is selected from substituents COOH, SO3H or SO2-C6H4-OH and Rl, R ² , R ³ and R ⁴ independently of one another a group X, H, OH or an alkyl, hydroxyalkyl or hydroxyalkyl ether radical with 1 to 4 C- Mean atoms.

8. Corrosion protection agent according to claim 7, characterized in that component b) is selected from compounds of general formula (II) which contain only one substituent X and in which the substituents R, R ² , R3 and R ^{4 are} hydrogen .

9. Corrosion protection agent according to one or more of claims 2 to 8, characterized in that they have a buffering capacity in the range from 1 to 8, the buffering capacity being defined as the consumption of 0.1 normal hydrochloric acid, measured in ml, in order lower the pH of 50 g of the anti-corrosion agent by 1.3 units.

10. Corrosion protection agent according to claim 1, characterized in that it by diluting with water by a factor between 20 and 200 aqueous corrosion protection agent according to one or more of claims 2 to 9 results.