EP0511163A1 - Pourable aqueous dispersions of polycarboxylic acid corrosion inhibitors - Google Patents
Pourable aqueous dispersions of polycarboxylic acid corrosion inhibitors Download PDFInfo
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- EP0511163A1 EP0511163A1 EP92810280A EP92810280A EP0511163A1 EP 0511163 A1 EP0511163 A1 EP 0511163A1 EP 92810280 A EP92810280 A EP 92810280A EP 92810280 A EP92810280 A EP 92810280A EP 0511163 A1 EP0511163 A1 EP 0511163A1
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- polycarboxylic acid
- corrosion inhibitor
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- acid
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
Definitions
- the invention relates to flowable, high-percentage aqueous dispersions of polycarboxylic acid corrosion inhibitors and to a special process for their preparation.
- polycarboxylic acids are well suited as corrosion inhibitors for aqueous systems which are in contact with metals, for example the heterocyclic polycarboxylic acids described in US Pat. No. 4,402,907 or EP-A-129,506.
- Aqueous systems that are in contact with metals are e.g. Cooling water systems, steam generating plants, metalworking agents or aqueous hydraulic fluids. Since most polycarboxylic acids have only limited solubility in water, the polycarboxylic acids are used in the form of their water-soluble salts, that is to say they are neutralized before use or they are added to a basic water system.
- the free polycarboxylic acids are, however, generally the storage and commercial forms.
- the free polycarboxylic acids are generally solid substances. During their manufacture, they are usually isolated from an aqueous phase by filtration. The filtered product is usually washed with water and then subjected to drying. In order to save the energy required for drying, the moist filter cake, which contains about 50% water, has recently been offered as a commercial form for use in aqueous systems.
- the moist filter cake has the disadvantage that it is not flowable. It cannot be poured or poured, but is e.g. manually dosed or decanted with the shovel.
- the invention therefore relates to flowable aqueous dispersions of a solid polycarboxylic acid corrosion inhibitor, containing 25-57% by weight of the corrosion inhibitor, 40-72% by weight of water, 0.1-2% by weight of a dispersant and 0.01 to 0.5% by weight. % of a thickener.
- Dispersions containing 40-53% by weight of a compound of the formula I, II or III, 45-58% by weight of water, 0.1 to 2% by weight of a dispersant and 0.01 to 0.5% by weight of a thickener are preferred contain.
- the polycarboxylic acid corrosion inhibitors are preferably di- or tricarboxylic acids of the formula I, II or III, HOOC- (CH2) n -COOH III wherein Z is C1-C11 alkylene, cyclohexylene or phenylene, R1 and R2 independently of one another are H, C1-C4-alkyl or a group -Z-COOH, R3 is C1-C12-alkyl, phenyl or a group -N (R4) (R5), -OR6 or -SR6, R4 and R5 independently of one another H, C1-C12-alkyl, C2-C4-hydroxyalkyl, cyclohexyl, Is phenyl or a group -Z-COOH or R4 and R5 together are C4-C6alkylene or 3-oxapentylene, R6 is hydrogen, C1-C12-alkyl or phenyl, m is zero or 1, X is
- the dispersion contains salts of polycarboxylic acids, it can be partial salts or full salts. Above all, sodium salts are suitable as alkali metal salts.
- Amine salts can be salts of primary, secondary or tertiary amines, e.g.
- the corrosion inhibitors are particularly preferably compounds of the formula I, II or III, in which Z is C1-C8-alkylene, R1 and R2 are hydrogen or C1-C4-alkyl, R3 is a group -N (R4) (R5), R4 is hydrogen, cyclohexyl or C1-C12-alkyl, R5 is C1-C12-alkyl, phenyl or a group -Z-COOH or R4 and R5 together are 1,5-pentylene or 3-oxa-1,5-pentylene, m is zero or 1, X is sulfur, R7 is hydrogen, methyl or chlorine, R8 and R10 are hydrogen, R9 and R11 are carboxyl or C2-C4-carboxyalkyl and n is 4-8, as well as the alkali metal, ammonium or amine salts of such polycarboxylic acids.
- Corrosion inhibitors of the formulas I, II or III are particularly advantageously used, in which Z is pentamethylene, R1 and R2 hydrogen, R3 is a group -NH- (CH2) 5-COOH, X sulfur, R7 hydrogen, m zero or 1, R8 and R10 hydrogen , R9 carboxyl, R10 carboxymethyl and n 8, or an alkali metal, ammonium or amine salt of such a polycarboxylic acid.
- the compounds of the formula I are known as corrosion inhibitors for aqueous systems from US Pat. No. 4,402,907. References are also given there, in which the preparation of these compounds is described.
- Examples of compounds of the formula I are: 2,4,6-tris (5'-carboxypentylamino) - 1,3,5-triazine, 2,4,6-tris (carboxymethylamino) - 1,3,5-triazine, 2,4,6-tris (3rd 'Carboxypropylamino) - 1,3,5zin, 2,4,6-tris (2'-carboxyethylamino) -1,3,5-triazine, 2,4,6-tris (4'-carboxybutylamino) 1,3,5 -triazine, 2,4,6-tris (11'-carboxyundecylamino) - 1,3,5-triazine, 2,4,6-tris (5'-carboxypentyl-N-methylamino) - 1,3,5- triazine, 2,4,6-tris (carboxymethyl-N-methylamino) - 1,3,5-triazine, 2,4,6-tris (3
- the compounds of formula II are known as corrosion inhibitors for aqueous systems from EP-A-129 506. Their preparation is also described there.
- Examples of individual compounds of the formula II are benzthiazol-2-ylthiosuccinic acid, 5-methylbenthiazol-2-ylthiosuccinic acid, 6-ethylbenzthiazol-2-ylthiosuccinic acid, 4-isopropylbenzthiazol-2-ylthiosuccinic acid, 7-t-butylbenzthiazol-2-ylthiosuccinic acid, 6-methoxybenzthiazol-2-ylthiosuccinic acid, 7-ethoxybenzthiazol-2-ylthiosuccinic acid, 4-fluorobenzoththosolothsuccinic acid, Bromobenzothiazol-2-ylthiosuccinic acid, 6-chlorobenzthiazol-2-ylthiosuccinic acid, 6-nitrobenzthiazol-2-ylthiosuccinic acid, 5-carboxybenzthiazol-2-ylthiosuccinic acid, 6-aminobenzthia
- the compounds of formula III are known compounds that are commercially available and are suitable for various uses.
- Examples of individual compounds of the formula III are succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid or decan-1, 10-dicarboxylic acid, and their salts, in particular their sodium salts.
- 2,4,6-Tris (5-carboxypentylamino) is particularly preferred as a polycarboxylic acid corrosion inhibitor.
- 1,3,5-triazine or benzothiazol-2-yl-thiosuccinic acid is particularly preferred.
- the corrosion inhibitor can contain 10-50%, in particular 20-40%, of anthranilic acid.
- All surface-active compounds are suitable as dispersants, in particular anionic and nonionic tenides.
- R is an aliphatic hydrocarbon residue with 8 to 22 carbon atoms or a cycloaliphatic or aliphatic-aromatic hydrocarbon residue with 10 to 22 carbon atoms
- a -O-, -NH- or -CO-O- Q is the acid residue of an inorganic, polybasic acid or the rest a polybasic carboxylic acid and p is a number from 1 to 20, in particular 1 to 5.
- the rest RA- is derived, for example, from higher alcohols such as decyl, lauryl, tridecyl, myristyl, cetyl, stearyl, oleyl, arachidyl, hydroabietyl alcohol or behenyl alcohol; also of fatty amines such as S tearylamine, palmitylamine or oleylamine; of fatty acids, such as caprylic, capric, lauric, myristic, palmitic, stearic, arachine, behen, coconut oil (C8-C18), decene, dodecene, tetradecene, hexadecene, oil , Linoleic, linolenic, eicotonic, docosonic or clupanodonic acid; or of alkylphenols, such as butyl, hexyl, n-octyl, n-nonyl, p-tert-octy
- the acid residue Q is usually derived from low molecular weight dicarboxylic acids, such as maleic acid, malonic acid, succinic acid or sulfosuccinic acid, and is connected via an ester bridge to the rest RA- (CH2CH2O) p -.
- Q is derived from inorganic polybasic acids such as orthophosphoric acid and sulfuric acid.
- the acid residue Q is preferably in salt form, ie, for example, as an alkali metal, ammonium or amine salt. Examples of such salts are sodium, potassium, ammonium, trimethylamine, ethanolamine, diethanolamine or triethanolamine salts.
- the anionic dispersants are normally in the form of their alkali metal salts, their ammonium salts or their water-soluble amine salts. It is expedient to use low-electrolyte qualities.
- Copolymers of synthetic monomers in particular of monomers with carboxyl groups, for example copolymers of 2-vinylpyrrolidone with 3-vinylpropionic acid or maleic acid copolymers and their salts.
- the thickeners stabilize the dispersions, so they can also be called stabilizers.
- examples of usable thickeners are, above all, modified polysaccharides of the xanthan, alginate, guar or cellulose type. These include, for example, cellulose ethers, such as methyl cellulose or carboxylmethyl cellulose, or heteropolysaccharides which carry, for example, mannose or glucuronic acid groups in the side chains. Such thickeners are commercially available.
- the dispersions according to the invention may also contain other auxiliaries, for example hydrotropic agents, such as e.g. Urea or sodium xylene sulfonate; Antifreezing agents, e.g. Ethylene or propylene glycol, diethylene glycol, glycerin or sorbitol; Humectants, e.g. Polyethylene glycols or glycerin; Biocides such as Chloroacetamide, formalin or 1,2-benzisothiazolin-3-one; or complexing agents, e.g. Trisodium nitrilotriacetate.
- hydrotropic agents such as e.g. Urea or sodium xylene sulfonate
- Antifreezing agents e.g. Ethylene or propylene glycol, diethylene glycol, glycerin or sorbitol
- Humectants e.g. Polyethylene glycols or glycerin
- Biocides such as Chloro
- biocides especially fungicides, which are intended to prevent fungal growth in the aqueous dispersion.
- the biocid is preferably used in an amount of 0.05 to 0.5% by weight of the dispersion.
- the filter cake already has the desired water content, then of course you do not need to add water.
- the polycarboxylic acid can be pressed so strongly that only 40% or less water remains in the filter cake.
- the filter cake is stirred, enough water is slowly added to produce a flowable dispersion. Once you have determined the optimal amount, you can choose the pressure when filtering so that the filter cake already has the desired water content.
- the stirring can be done in conventional stirrers, especially in stirrers in which a greater pressure is exerted on the material to be stirred.
- the following are usable e.g. Agitators with a stirring spindle, tooth mills, colloid mills or screw agitators.
- the stirring is preferably carried out at room temperature, but it can be advantageous in certain cases to slightly cool the material to be stirred.
- the dispersions thus produced are stable for several months at room temperature and at temperatures up to 40 ° C. They keep their fluidity and do not separate. This is important for the storage and transportation of the dispersions Property.
- the dispersions can be handled as a liquid and e.g. can be pumped during dosing. Another advantage is that the dispersions dissolve very quickly in alkaline aqueous systems. If the dispersions consist of the salts of the polycarboxylic acids, they also dissolve in neutral aqueous systems. The dissolution can be accelerated by stirring.
- aqueous systems in which the dispersions according to the invention can be used are cooling water systems, air conditioning systems, steam generating systems, seawater desalination systems, heating and cooling water circuits, aqueous hydraulic fluids, but above all aqueous metalworking fluids.
- a dispersant based on a 40% aqueous solution of dinaphthylmethane disulphosaem sodium (Dispersant CC, Ciba-Geigy AG) is added and after stirring for a further 15 minutes, 0.1 part of a polysaccharide of the xanthan type (Rhodopol® 23 , Rhone-Poulenc) as a thickener and 0.2 part of a 35% aqueous dispersion of 1,2-benzisothiazolin-3-one (Proxel® BD, JCJ Ltd.) as a biocide and stirred for another 15 minutes.
- a dispersant based on a 40% aqueous solution of dinaphthylmethane disulphosaem sodium (Dispersant CC, Ciba-Geigy AG) is added and after stirring for a further 15 minutes, 0.1 part of a polysaccharide of the xanthan type (Rh
- the resulting dispersion contains approximately 50% water and has a viscosity of 170 mPa.s ⁇ 1 at 20 ° C. (measured with a rotary viscometer with measuring system DIN 25). To check the stability, the dispersion is stored at room temperature and at 40 ° C. No phase separation occurred after 6 weeks.
- Example 2 The procedure is as in Example 1. 90.6 parts of a Reocor® 190 filter cake with 50% water content are mixed with 1 part of an anionic surfactant based on a formaldehyde condensation product of an aromatic sulfonic acid 10% aqueous solution (Dispersant H, Ciba-Geigy AG), 0.2 parts Rhodopol® 23 and 0.2 parts Proxel® BD. The resulting dispersion has a viscosity of 250 mPa.s ⁇ 1 and shows no change after 4 months storage at 20 ° C.
- an anionic surfactant based on a formaldehyde condensation product of an aromatic sulfonic acid 10% aqueous solution (Dispersant H, Ciba-Geigy AG), 0.2 parts Rhodopol® 23 and 0.2 parts Proxel® BD.
- the resulting dispersion has a viscosity of 250 mPa.s ⁇ 1 and shows no change after 4 months storage at 20 ° C
- the resulting dispersion has a viscosity of 250 mPa / s.
- Example 1 The procedure is as in Example 1 with variation of the dispersant and the quantitative composition.
- a lignin sulfonate (Reax® 85-A) are dissolved in 44 g of water in a 1.5 liter glass vessel with a stainless steel screw agitator. At a stirring speed of approx. 50-70 rpm, 900 g of a filter cake of Reocor® 190 containing approx. 50% water are added within 15 minutes. This creates a liquid dispersion, which for approx. 30 min at 50 -70 U / pM is homogenized. To do this, add the solution of 1 g Rhodopol® 23 in 50 g water. The dispersion is then stirred at 75 rpm for 1 h. The dispersion prepared in this way has a viscosity of 200 mPa.s ⁇ 1 (at 25 ° C). The dispersion contains 45% of the corrosion inhibitor; 54.5% water, O.3% dispersant, 0.1% thickener.
- a lignin sulfonate (Reax® 85-A) is dissolved in 91 g of water in a 600 ml glass vessel with a stainless steel screw agitator. At a stirring speed of approx. 50-70 rpm, 256 g of a filter cake of Reocor® 190 containing approx. 50% water are added within 15 minutes. This results in a liquid dispersion to which 32 g of anthranilic acid are added within 15 minutes. The mixture is then homogenized at 50-70 U / pM for 30 minutes. Add the solution of 0.4 g Rhodopol® 23 in 19.6 g water. The dispersion is then stirred at 75 rpm for 1 h.
- the dispersion prepared in this way has a viscosity of 200 mPa.s (1 (at 25 ° C).
- the dispersion contains 40% of the corrosion inhibitor (ratio 80 parts Reocor 190 and 20 parts anthranilic acid); 59.6% water, O, 3% dispersant, 0.1% thickener.
- a lignin sulfonate (Reax® 85-A) is dissolved in 123 g of water.
- 192 g of a filter cake of Reocor® 190 containing approx. 50% water are added within 15 minutes
- Liquid dispersion to which 64 g of anthranilic acid (99% content) are added within 15 minutes.
- the mixture is then homogenized at 50-70 rpm for 30 minutes.
- the dispersion prepared in this way has a viscosity of 200 mPa.s ⁇ 1 (at 25 ° C).
- the dispersion contains 40% of the corrosion inhibitor (ratio 60 parts Reocor 190 and 40 parts anthranilic acid); 59.6% water, O, 3% dispersant, 0.1% thickener.
- a lignin sulfonate (Reax® 85-A) are dissolved in 19 g of water in a glass vessel (600 ml) with a stainless steel screw agitator. At a stirring speed of approx. 50-70 U / pm, 360 g of a filter cake of Reocor® 190 (monosodium salt *) containing approx. 50% water are added within 15 minutes. This creates a liquid dispersion that is homogenized for 30 minutes at 50-70 rpm. Add the solution of 0.4 g Rhodopol® 23 in 19.6 g water. The dispersion is then stirred at 75 rpm for 1 h.
- Reax® 85-A a lignin sulfonate
- the dispersion prepared in this way has a viscosity of 200 mPa.s ⁇ 1 (at 25 ° C).
- the dispersion has a content of 45% of the corrosion inhibitor, 54.6% water, O, 3% dispersant, 0.1% thickener.
- a solution of disodium hydrogen phosphate is added to the Reocor 190 filter cake in aqueous suspension; the monosodium salt formed is isolated and can be liquefied using Reax as the dispersant.
- a lignin sulfonate (Reax® 85-A) are dissolved in 19 g of water in a glass vessel (600 ml) with a stainless steel screw agitator. 360 g of a filter cake of approx. 50% water containing Reocor® 190 (monodiethanolamine salt #) are added within 15 minutes at a stirring speed of approx. 50-70 rpm. This creates a liquid dispersion that is homogenized for 30 minutes at 50-70 rpm. Add the solution of 0.4 g Rhodopol® 23 in 19.6 g water. The dispersion is then stirred at 75 rpm for 1 h.
- Reax® 85-A a lignin sulfonate
- the dispersion has a content of 45% of the corrosion inhibitor, 54.6% water, O, 3% dispersant, 0.1% thickener. #) The stoichiometric amount of diethanolamine is added to Reocor 190 filter cake in aqueous suspension; the mono-diethanolamine salt formed is isolated and can be liquefied using Reax as a dispersant.
Abstract
Description
Die Erfindung betrifft fließfähige hochprozentige wäßrige Dispersionen von Polycarbonsäure-Korrosionsinhibitoren, sowie ein spezielles Verfahren zu ihrer Herstellung.The invention relates to flowable, high-percentage aqueous dispersions of polycarboxylic acid corrosion inhibitors and to a special process for their preparation.
Es ist bekannt, daß sich bestimmte Polycarbonsäuren als Korrosionsinhibitoren für wäßrige Systeme, die mit Metallen in Kontakt sind, gut eignen, beispielsweise die im US-A-4 402 907 oder EP-A- 129 506 beschriebenen heterocyclischen Polycarbonsäuren. Wäßrige Systeme, die im Kontakt mit Metallen stehen, sind z.B. Kühlwassersysteme, Dampferzeugungsanlagen, Metallbearbeitungsmittel oder wäßrige Hydraulikflüssigkeiten. Da die meisten Polycarbonsäuren in Wasser nur eine beschränkte Löslichkeit haben, verwendet man die Polycarbonsäuren in Form ihrer wasserlöslichen Salze, das heißt man neutralisiert sie vor dem Gebrauch oder man setzt sie einem basischen Wassersystem zu. Lager- und Handelsform sind jedoch im allgemeinen die freien Polycarbonsäuren.It is known that certain polycarboxylic acids are well suited as corrosion inhibitors for aqueous systems which are in contact with metals, for example the heterocyclic polycarboxylic acids described in US Pat. No. 4,402,907 or EP-A-129,506. Aqueous systems that are in contact with metals are e.g. Cooling water systems, steam generating plants, metalworking agents or aqueous hydraulic fluids. Since most polycarboxylic acids have only limited solubility in water, the polycarboxylic acids are used in the form of their water-soluble salts, that is to say they are neutralized before use or they are added to a basic water system. The free polycarboxylic acids are, however, generally the storage and commercial forms.
Die freien Polycarbonsäuren sind im allgemeinen feste Stoffe. Bei ihrer Herstellung werden sie meist durch Filtration aus einer wäßrigen Phase isoliert. Das filtrierte Produkt wird üblicherweise mit Wasser gewaschen und dann einer Trocknung unterzogen. Um die für die Trocknung benötigte Energie zu sparen, hat man neuerdings für die Verwendung in wäßrigen Systemen den feuchten Filterkuchen, der etwa 50 % Wasser enthält, als Handelsform angeboten.The free polycarboxylic acids are generally solid substances. During their manufacture, they are usually isolated from an aqueous phase by filtration. The filtered product is usually washed with water and then subjected to drying. In order to save the energy required for drying, the moist filter cake, which contains about 50% water, has recently been offered as a commercial form for use in aqueous systems.
Der feuchte Filterkuchen hat jedoch den Nachteil, daß er nicht fließfähig ist. Er kann nicht geschüttet oder gegossen werden sondern wird z.B. mit der Schaufel manuell dosiert oder umgefüllt .However, the moist filter cake has the disadvantage that it is not flowable. It cannot be poured or poured, but is e.g. manually dosed or decanted with the shovel.
Es wurde gefunden, daß man hochprozentige Dispersionen solcher fester Polycarbonsäure-Korrosionsinhibitoren durch ein spezielles Verfahren aus den feuchten Filterkuchen herstellen kann. Diese Dispersionen sind fließfähig und können daher mit den für Flüssigkeiten üblichen Geräten transportiert und dosiert werden. Diese physikalischen Eigenschaften behalten die so hergestellten Dispersionen über Zeiträume von mehreren Monaten bei, d.h. sie neigen nicht zu einer Entmischung oder Verfestigung.It has been found that high-percentage dispersions of such solid polycarboxylic acid corrosion inhibitors can be produced from the moist filter cake by a special process. These dispersions are flowable and can therefore be transported and metered with the usual equipment for liquids. The dispersions produced in this way retain these physical properties over periods of several months, ie they do not tend to separate or solidify.
Gegenstand der Erfindung sind daher fließfähige wäßrige Dispersionen eines festen Polycarbonsäure-Korrosionsinhibitors, enthaltend 25-57 Gew.-% des Korrosionsinhibitors, 40-72 Gew.-% Wasser, 0.1-2 Gew.-% eines Dispergiermittels und 0.01 bis 0.5 Gew.-% eines Verdickungsmittels.The invention therefore relates to flowable aqueous dispersions of a solid polycarboxylic acid corrosion inhibitor, containing 25-57% by weight of the corrosion inhibitor, 40-72% by weight of water, 0.1-2% by weight of a dispersant and 0.01 to 0.5% by weight. % of a thickener.
Bevorzugt sind Dispersionen, die 40-53 Gew.-% einer Verbindung der Formel I, II oder III, 45-58 Gew.-% Wasser, 0.1 bis 2 Gew.-% eines Dispergiermittels und 0.01 bis 0.5 Gew.-% eines Verdickungsmittels enthalten.Dispersions containing 40-53% by weight of a compound of the formula I, II or III, 45-58% by weight of water, 0.1 to 2% by weight of a dispersant and 0.01 to 0.5% by weight of a thickener are preferred contain.
Bei den Polycarbonsäure-Korrosionsinhibitoren handelt es sich vorzugsweise um Di- oder Tricarbonsäuren der Formel I, II oder III,
HOOC-(CH₂)n-COOH III
worin Z C₁-C₁₁-Alkylen, Cyclohexylen oder Phenylen bedeutet,
R₁ und R₂ unabhängig voneinander H, C₁-C₄-Alkyl oder eine Gruppe -Z-COOH bedeutet,
R₃ C₁-C₁₂-Alkyl, Phenyl oder eine Gruppe -N(R₄)(R₅), -OR₆ oder -SR₆ bedeutet,
R₄ und R₅ unabhängig voneinander H, C₁-C₁₂-Alkyl, C₂-C₄-Hydroxyalkyl, Cyclohexyl,
Phenyl oder eine Gruppe -Z-COOH bedeuten oder R₄ und R₅ zusammen C₄-C₆-Alkylen oder 3-Oxapentylen bedeuten,
R₆ Wasserstoff, C₁-C₁₂-Alkyl oder Phenyl bedeutet,
m null oder 1 ist, X Schwefel, Sauerstoff oder NH bedeutet,
R₇ Wasserstoff, C₁-C₄-Alkyl, Halogen, C₁-C₄-Alkoxy, Carboxy, Amino oder Nitro bedeutet,
R₈, R₉, R₁₀ und R₁₁ unabhängig voneinander Wasserstoff, C₁-C₁₂-Alkyl, C₁-C₄-Hydroxyalkyl, C₂-C₆-Carboxyalkyl, C₂-C₁₀-Alkoxyalkyl, Carboxyl, Phenyl oder Benzyl bedeuten oder R₈ und R₉ zusammen eine direkte Bindung bedeuten, wobei mindestens 2 der Gruppen R₈, R₉, R₁₀ und R₁₁ eine Carboxyl- oder Carboxylalkylgruppe sind, und n 2-10 ist, sowie um die Alkalimetall-, Ammonium- oder Aminsalze solcher Polycarbonsäuren.The polycarboxylic acid corrosion inhibitors are preferably di- or tricarboxylic acids of the formula I, II or III,
HOOC- (CH₂) n -COOH III
wherein Z is C₁-C₁₁ alkylene, cyclohexylene or phenylene,
R₁ and R₂ independently of one another are H, C₁-C₄-alkyl or a group -Z-COOH,
R₃ is C₁-C₁₂-alkyl, phenyl or a group -N (R₄) (R₅), -OR₆ or -SR₆,
R₄ and R₅ independently of one another H, C₁-C₁₂-alkyl, C₂-C₄-hydroxyalkyl, cyclohexyl,
Is phenyl or a group -Z-COOH or R₄ and R₅ together are C₄-C₆alkylene or 3-oxapentylene,
R₆ is hydrogen, C₁-C₁₂-alkyl or phenyl,
m is zero or 1, X is sulfur, oxygen or NH,
R₇ is hydrogen, C₁-C₄-alkyl, halogen, C₁-C₄-alkoxy, carboxy, amino or nitro,
R₈, R₉, R₁₀ and R₁₁ independently of one another are hydrogen, C₁-C₁₂-alkyl, C₁-C₄-hydroxyalkyl, C₂-C₆-carboxyalkyl, C₂-C₁₀-alkoxyalkyl, carboxyl, phenyl or benzyl or R₈ and R₉ together mean a direct bond, where at least 2 of the groups R₈, R₉, R₁₀ and R₁₁ are a carboxyl or carboxylalkyl group, and n 2 -10, and the alkali metal, ammonium or amine salts of such polycarboxylic acids.
Soferne die Dispersion Salze von Polycarbonsäuren enthält, kann es sich um Partialsalze oder Vollsalze handeln. Als Alkalimetallsalze kommen vor allem Natriumsalze in Frage. Aminsalze können Salze von primären, sekundären oder tertiären Aminen sein, z.B. Salze von Butylamin, Octylamin, Dodecylamin, Tridecylamin, Tetradecylamin, Octadecylamin, Diethylamin, Dibutylamin, Dihexylamin, Dioctylamin, Triethylamin, Tributylamin, Trihexylamin, Cyclohexylamin, Piperidin, Morpholin, Ethanolamin, Propanolamin, Di- oder TriethanolaminIf the dispersion contains salts of polycarboxylic acids, it can be partial salts or full salts. Above all, sodium salts are suitable as alkali metal salts. Amine salts can be salts of primary, secondary or tertiary amines, e.g. Salts of butylamine, octylamine, dodecylamine, tridecylamine, tetradecylamine, octadecylamine, diethylamine, dibutylamine, dihexylamine, dioctylamine, triethylamine, tributylamine, trihexylamine, cyclohexylamine, piperidine, morpholine, ethanolamine, triethanamine or di-
Besonders bevorzugt handelt es sich bei den Korrosionsinhibitoren um Verbindungen der Formel I, II oder III, worin
Z C₁-C₈-Alkylen bedeutet, R₁ und R₂ Wasserstoff oder C₁-C₄-Alkyl bedeuten,
R₃ eine Gruppe -N(R₄)(R₅) ist, R₄ Wasserstoff, Cyclohexyl oder C₁-C₁₂-Alkyl bedeutet,
R₅ C₁-C₁₂-Alkyl, Phenyl oder eine Gruppe -Z-COOH bedeutet oder R₄ und R₅ zusammen 1,5-Pentylen oder 3-Oxa-1,5-pentylen bedeuten,
m null oder 1 ist, X Schwefel ist, R₇ Wasserstoff, Methyl oder Chlor bedeutet, R₈ und R₁₀ Wasserstoff sind,
R₉ und R₁₁ Carboxyl oder C₂-C₄-Carboxyalkyl bedeuten und n 4-8 ist, sowie um die Alkalimetall-, Ammonium- oder Aminsalze solcher Polycarbonsäuren.The corrosion inhibitors are particularly preferably compounds of the formula I, II or III, in which
Z is C₁-C₈-alkylene, R₁ and R₂ are hydrogen or C₁-C₄-alkyl,
R₃ is a group -N (R₄) (R₅), R₄ is hydrogen, cyclohexyl or C₁-C₁₂-alkyl,
R₅ is C₁-C₁₂-alkyl, phenyl or a group -Z-COOH or R₄ and R₅ together are 1,5-pentylene or 3-oxa-1,5-pentylene,
m is zero or 1, X is sulfur, R₇ is hydrogen, methyl or chlorine, R₈ and R₁₀ are hydrogen,
R₉ and R₁₁ are carboxyl or C₂-C₄-carboxyalkyl and n is 4-8, as well as the alkali metal, ammonium or amine salts of such polycarboxylic acids.
Besonders vorteilhaft werden Korrosionsinhibitoren der Formeln I, II oder III eingesetzt, worin Z Pentamethylen, R₁ und R₂ Wasserstoff, R₃ eine Gruppe -NH-(CH₂)₅-COOH, X Schwefel, R₇ Wasserstoff, m null oder 1, R₈ und R₁₀ Wasserstoff, R₉ Carboxyl, R₁₀ Carboxymethyl und n 8 bedeuten, oder ein Alkalimetall-, Ammonium- oder Aminsalz einer solchen Polycarbonsäure ist.Corrosion inhibitors of the formulas I, II or III are particularly advantageously used, in which Z is pentamethylene, R₁ and R₂ hydrogen, R₃ is a group -NH- (CH₂) ₅-COOH, X sulfur, R₇ hydrogen, m zero or 1, R₈ and R₁₀ hydrogen , R₉ carboxyl, R₁₀ carboxymethyl and n 8, or an alkali metal, ammonium or amine salt of such a polycarboxylic acid.
Die Verbindungen der Formel I sind als Korrosionsinhibitoren für wäßrige Systeme bekannt aus dem US-A-4 402 907. Dort sind auch Literaturstellen angegeben, in denen die Herstellung dieser Verbindungen beschrieben ist.The compounds of the formula I are known as corrosion inhibitors for aqueous systems from US Pat. No. 4,402,907. References are also given there, in which the preparation of these compounds is described.
Beispiele für Verbindungen der Formel I sind:
2,4,6-Tris(5′-carboxypentylamino)- 1,3,5-triazin, 2,4,6-Tris(carboxymethylamino)- 1,3,5-triazin, 2,4,6-Tris(3′carboxypropylamino)- 1,3,5zin, 2,4,6-Tris(2′-carboxyethylamino)-1,3,5-triazin, 2,4,6-Tris(4′-carboxybutylamino)1,3,5-triazin, 2,4,6-Tris-(11′-carboxyundecylamino)- 1,3,5-triazin, 2,4,6-Tris(5′-carboxypentyl-N-methylamino)- 1,3,5-triazin, 2,4,6-Tris(carboxymethyl-N-methylamino)- 1,3,5-triazin, 2,4,6-Tris-(3′-carboxypropyl-N-methylamino)- 1,3,5-triazin, 2,4-Bis(5′-carboxypentylamino)-6-ethylamino- 1,3,5-triazin, 2,4-Bis(5′-carboxypentylamino)-6-n-octylamino- 1,3,5-triazin, 2,4-Bis(5′-carboxypentylamino)-6-cyclohexylamino- 1,3,5-triazin, 2,4-Bis(5′-carboxypentylamino)-6-diethylamino- 1,3,5-triazin, 2,4-Bis(5′-carboxypentylamino)-6(2˝-hydroxyethylamino)- 1,3,5-triazin, 2,4-Bis(2′-carboxyethylamino)-6-n-octylamino-1,3,5-triazin, 2,4-Bis(2′-carboxyethylamino)-6-diethylamino- 1,3,5-triazin, 2,4-Bis(2′-carboxyethylamino)-6-butylamino- 1,3,5-triazin, 2,4-Bis(2′-carboxyethylamino)-6-ethylamino- 1,3,5-triazin, 2,4-Bis(5′-carboxypentylamino)-6-anilino-1,3,5-triazin, 2,4-Bis(3′-carboxypropylamino)-6-ethylamino- 1,3,5-triazin, 2,4-Bis(3′-carboxypropylamino)-6-n-octylamino- 1,3,5-triazin, 2,4-Bis(3′-carboxypropylamino)-6-n-propylamino- 1,3,5-triazin, 2,4-Bis(carboxymethyl)-6-n-octylamino- 1,3,5-triazin, 2,4-Bis(carboxymethyl)6-cyclohexylamino- 1,3,5-triazin, 2,4-Bis(carboxymethyl)-6-dodecylamino- 1,3,5-triazin, 2,4-Bis(5′-carboxypentyl-n-methylamino)-6-ethylamino- 1,3,5-triazin, 2,4-Bis(3′-carboxypropyl-N-methylamino)-6-n-octylamino- 1,3,5-triazin, 2,4-Bis(carboxymethyl-N-methylamino)-6-n-octylamino-1,3,5-triazin, 2,4-Bis(2′-carboxyethyl-N-methylamino)-6-n-octylamino- 1,3,5-triazin, 2,4-Bis(5′-carboxypentylamino)-6-(2˝-carboxyethylamino)- 1,3,5-triazin, 2,4-Bis(5′-carboxypentylamino)-6-(carboxymethylamino)- 1,3,5-triazin, 2,4-Bis(3′-carboxypropylamino)-6-(2˝-carboxyethylamino)- 1,3,5-triazin, 2,4-Bis(2′-carboxyethylamino)-6-(5˝-carboxypentylamino)-1,3,5-triazin, 2,4-Bis(3′-carboxypropylamino)-6-(5˝-carboxypentylamino)-1,3,5-triazin, 2,4-Bis(5′-carboxypentylamino)-6-methoxy-1,3,5-triazin, 2,4-Bis(2′-carboxyethylamino)-6-butylthio-1,3,5-triazin, 2,4-Bis(2′-carboxypentylamino)-6-n-octyloxy-1,3,5-triazin, 2,4-Bis(3′-carboxypropylamino)-6-n-dodecyllthio- 1,3,5-triazin, 2,4-Bis(5′-carboxyethylamino)-6-phenyoxy- 1,3,5-triazin, 2,4-Bis(5′-carboxypentylamino)-6-methylthio- 1,3,5-triazin, 2,4-Bis(5′-carboxypentylamino)6-ethoxy- 1,3,5-triazin sowie Salze dieser Säuren.Examples of compounds of the formula I are:
2,4,6-tris (5'-carboxypentylamino) - 1,3,5-triazine, 2,4,6-tris (carboxymethylamino) - 1,3,5-triazine, 2,4,6-tris (3rd 'Carboxypropylamino) - 1,3,5zin, 2,4,6-tris (2'-carboxyethylamino) -1,3,5-triazine, 2,4,6-tris (4'-carboxybutylamino) 1,3,5 -triazine, 2,4,6-tris (11'-carboxyundecylamino) - 1,3,5-triazine, 2,4,6-tris (5'-carboxypentyl-N-methylamino) - 1,3,5- triazine, 2,4,6-tris (carboxymethyl-N-methylamino) - 1,3,5-triazine, 2,4,6-tris (3'-carboxypropyl-N-methylamino) - 1,3,5- triazine, 2,4-bis (5'-carboxypentylamino) -6-ethylamino- 1,3,5-triazine, 2,4-bis (5'-carboxypentylamino) -6-n-octylamino- 1,3,5- triazine, 2,4-bis (5'-carboxypentylamino) -6-cyclohexylamino-1,3,5-triazine, 2,4-bis (5'-carboxypentylamino) -6-diethylamino-1,3,5-triazine, 2,4-bis (5'-carboxypentylamino) -6 (2˝-hydroxyethylamino) - 1,3,5-triazine, 2,4-bis (2'-carboxyethylamino) -6-n-octylamino-1,3, 5-triazine, 2,4-bis (2'-carboxyethylamino) -6-diethylamino-1,3,5-triazine, 2,4-bis (2'-carboxyethylamino) -6-butylamino-1,3,5- triazine, 2,4-B is (2'-carboxyethylamino) -6-ethylamino-1,3,5-triazine, 2,4-bis (5'-carboxypentylamino) -6-anilino-1,3,5-triazine, 2,4-bis ( 3'-carboxypropylamino) -6-ethylamino-1,3,5-triazine, 2,4-bis (3'-carboxypropylamino) -6-n-octylamino-1,3,5-triazine, 2,4-bis ( 3'-carboxypropylamino) -6-n-propylamino-1,3,5-triazine, 2,4-bis (carboxymethyl) -6-n-octylamino-1,3,5-triazine, 2,4-bis (carboxymethyl ) 6-cyclohexylamino-1,3,5-triazine, 2,4-bis (carboxymethyl) -6-dodecylamino-1,3,5-triazine, 2,4-bis (5'-carboxypentyl-n-methylamino) - 6-ethylamino-1,3,5-triazine, 2,4-bis (3'-carboxypropyl-N-methylamino) -6-n-octylamino-1,3,5-triazine, 2,4-bis (carboxymethyl- N-methylamino) -6-n-octylamino-1,3,5-triazine, 2,4-bis (2'-carboxyethyl-N-methylamino) -6-n-octylamino-1,3,5-triazine, 2 , 4-bis (5'-carboxypentylamino) -6- (2˝-carboxyethylamino) - 1,3,5-triazine, 2,4-bis (5'-carboxypentylamino) -6- (carboxymethylamino) - 1,3, 5-triazine, 2,4-bis (3'-carboxypropylamino) -6- (2˝-carboxyethylamino) - 1,3,5-triazine, 2,4-bis (2'-carboxyethyl) mino) -6- (5˝-carboxypentylamino) -1,3,5-triazine, 2,4-bis (3'-carboxypropylamino) -6- (5˝-carboxypentylamino) -1,3,5-triazine, 2 , 4-bis (5'-carboxypentylamino) -6-methoxy-1,3,5-triazine, 2,4-bis (2'-carboxyethylamino) -6-butylthio-1,3,5-triazine, 2,4 Bis (2'-carboxypentylamino) -6-n-octyloxy-1,3,5-triazine, 2,4-bis (3'-carboxypropylamino) -6-n-dodecyllthio-1,3,5-triazine, 2 , 4-bis (5'-carboxyethylamino) -6-phenyoxy-1,3,5-triazine, 2,4-bis (5'-carboxypentylamino) -6-methylthio-1,3,5-triazine, 2,4 -Bis (5'-carboxypentylamino) 6-ethoxy-1,3,5-triazine and salts of these acids.
Die Verbindungen der Formel II sind als Korrosionsinhibitoren für wäßrige Systeme bekannt aus der EP-A-129 506. Dort ist auch ihre Herstellung beschrieben.The compounds of formula II are known as corrosion inhibitors for aqueous systems from EP-A-129 506. Their preparation is also described there.
Beispiele für einzelne Verbindungen der Formel II sind Benzthiazol-2-ylthiobernsteinsäure, 5-Methylbenthiazol-2-ylthiobernsteinsäure, 6-Ethylbenzthiazol-2-ylthiobernsteinsäure, 4-Isopropylbenzthiazol-2-ylthiobernsteinsäure, 7-t-Butylbenzthiazol-2-ylthiobernsteinsäure, 6-Methoxybenzthiazol-2-ylthiobernsteinsäure, 7-Ethoxybenzthiazol-2-ylthiobernsteinsäure, 4-Flurorobenzthiazol-2-ylthiobernsteinsäure, 5-Chlorobenzthiazol2-ylthiobernsteinsäure, 7-Bromobenzthiazol-2-ylthiobernsteinsäure, 6-Chlorobenzthiazol-2-ylthiobernsteinsäure, 6-Nitrobenzthiazol-2- ylthiobernsteinsäure, 5-Carboxybenzthiazol-2-ylthiobernsteinsäure, 6-Aminobenzthiazol-2-ylthiobernsteinsäure, 1-(Benzthiazol-2-ylthio)-propan- 1,2-dicarbonsäure, 3-(Benzthiazol-2-ylthio)-propan- 1,2-dicarbonsäure, 3-(6-Aminobenzthiazol-2-yl)-propan- 1,2-dicarbonsäure, 1 -(Benzthiazol-2-ylthio)propan- 1,3-dicarbonsäure, 2-(Benthiazol-2-ylthio)-propan- 1,3-dicarbonsäure, 2-(Benzthiazol-2-ylthio)-butan-2,3-dicarbonsäure, 1-(Benzthiazol-2-ylthio)-butan-2,4-dicarbonsäure, 4-(Benzthiazol-2-ylthio)-butan- 1,2,3-tricarbonsäure, 1-(Benzthiazol-2-ylthio)hexan- 1,6-dicarbonsäure, 1-(Benzthiazol-2-ylthio)-propan- 1,2,3-tricarbonsäure, 1-(Benzthiazol-2-ylthio)-3-hydroxypropan- 1,2-dicarbonsäure, 1 -(Benzthiazol-2-ylthio)-2-phenylbernsteinsäure, 1-(Benzthiazol-2-ylthio)-2-benzylbernsteinsäure, Benzoxazol-2-ylthiobernsteinsäure, 5-Methylbenzoxazol-2-ylthiobernsteinsäure, 4-Isopropylbenzoxazol-2-ylthiobernsteinsäure, 6- Ethoxybenzoxazol-2-ylthiobernsteinsäure, 5-Chlorobenzoxazol-2-ylthiobernsteinsäure, 5-Carboxybenzoxazol-2-ylthiobernsteinsäure, 6-Aminobenzoxazol-2-ylthiobernsteinsäure, 1-(Benzoxazol-2-ylthio)-propan- 1,2-dicarbonsäure, 3-(Benzoxazol-2-ylthio)-propan- 1,2-dicarbonsäure, 2-(Benzoxazol-2-ylthio)-propan- 1,3-dicarbonsäure, 2-(Benzoxazol-2-ylthio)-butan-2,3-dicarbonsäure, 1-(Benzoxazol-2-ylthio)-propan- 1,2,3-tricarbonsäure, Benzimidazol-2-ylthiobernsteinsäure, 1-(Benzimidazol-2-ylthio)-propan- 1,2-dicarbonsäure, 3-(Benzimidazol-2-ylthio)propan- 1,2-dicarbonsäure, 1-(Benzimidazol-2-ylthio)-propan- 1,3-dicarbonsäure, 1-(Benzimidazol-2-ylthio)-butan- 1,2-dicarbonsäure, 4-(Benzimidazol-2-ylthio)butan- 1,2,3-dicarbonsäure, 2-(Benzimidazol-2-ylthio)-butan-2,3-dicarbonsäure, 1 -(Benzimidazol-2-ylthio)-propan- 1,2,3-tricarbonsäure, 1 -(Benzimidazol-2-ylthio)phenylbernsteinsäure sowie Salze dieser Säuren.Examples of individual compounds of the formula II are benzthiazol-2-ylthiosuccinic acid, 5-methylbenthiazol-2-ylthiosuccinic acid, 6-ethylbenzthiazol-2-ylthiosuccinic acid, 4-isopropylbenzthiazol-2-ylthiosuccinic acid, 7-t-butylbenzthiazol-2-ylthiosuccinic acid, 6-methoxybenzthiazol-2-ylthiosuccinic acid, 7-ethoxybenzthiazol-2-ylthiosuccinic acid, 4-fluorobenzoththosolothsuccinic acid, Bromobenzothiazol-2-ylthiosuccinic acid, 6-chlorobenzthiazol-2-ylthiosuccinic acid, 6-nitrobenzthiazol-2-ylthiosuccinic acid, 5-carboxybenzthiazol-2-ylthiosuccinic acid, 6-aminobenzthiazol-2-ylthioprostiazonic acid, 1,2-dicarboxylic acid, 3- (benzothiazol-2-ylthio) propane-1,2-dicarboxylic acid, 3- (6-aminobenzthiazol-2-yl) propane-1,2-dicarboxylic acid, 1 - (benzothiazol-2 -ylthio) propane-1,3-dicarboxylic acid, 2- (benthiazol-2-ylthio) propane-1,3-dicarboxylic acid, 2- (benzthiazol-2-ylthio) butane-2,3-dicarboxylic acid, 1- ( Benzthiazol-2-ylthio) butane-2,4-dicarboxylic acid, 4- (benzthiazol-2-ylthio) butane-1,2,3-tricarboxylic acid, 1- (benzthiazol-2-ylthio) hexane 1,6- dicarboxylic acid, 1- (benzthiazol-2-ylthio) -p ropan-1,2,3-tricarboxylic acid, 1- (benzothiazol-2-ylthio) -3-hydroxypropane-1,2-dicarboxylic acid, 1 - (benzothiazol-2-ylthio) -2-phenylsuccinic acid, 1- (benzothiazol-2 -ylthio) -2-benzylsuccinic acid, benzoxazol-2-ylthiosuccinic acid, 5-methylbenzoxazol-2-ylthiosuccinic acid, 4-isopropylbenzoxazol-2-ylthiosuccinic acid, 6-ethoxybenzoxazol-2-ylthiosuccinic acid, 5-chlorobenzoxoxysloxane, 5-chlorobenzoxoxysiloxa 2-ylthiosuccinic acid, 6-aminobenzoxazol-2-ylthiosuccinic acid, 1- (benzoxazol-2-ylthio) propane-1,2-dicarboxylic acid, 3- (benzoxazol-2-ylthio) propane-1,2-dicarboxylic acid, 2- (Benzoxazol-2-ylthio) propane-1,3-dicarboxylic acid, 2- (benzoxazol-2-ylthio) butane-2,3-dicarboxylic acid, 1- (benzoxazol-2-ylthio) propane-1,2, 3-tricarboxylic acid, benzimidazol-2-ylthiosuccinic acid, 1- (benzimidazol-2-ylthio) propane-1,2-dicarboxylic acid, 3- (benzimidazol-2-ylthio) propane-1,2-dicarboxylic acid, 1- (benzimidazole- 2-ylthio) propane-1,3-dicarboxylic acid, 1- (benzimidazol-2-ylthio) butane-1,2-dicarb ononic acid, 4- (benzimidazol-2-ylthio) butane-1,2,3-dicarboxylic acid, 2- (benzimidazol-2-ylthio) butan-2,3-dicarboxylic acid, 1 - (benzimidazol-2-ylthio) propane - 1,2,3-tricarboxylic acid, 1 - (benzimidazol-2-ylthio) phenylsuccinic acid and salts of these acids.
Die Verbindungen der Formel III sind bekannte Verbindungen, die im Handel erhältlich sind und für verschiedene Verwendungen geeignet sind.The compounds of formula III are known compounds that are commercially available and are suitable for various uses.
Beispiele einzelner Verbindungen der Formel III sind Bernsteinsäure, Glutarsäure, Adipinsäure, Korksäure, Azelainsäure, Sebacinsäure oder Decan-1, 10-dicarbonsäure, sowie deren Salze, insbesondere deren Natriumsalze.Examples of individual compounds of the formula III are succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid or decan-1, 10-dicarboxylic acid, and their salts, in particular their sodium salts.
Besonders bevorzugt als Polycarbonsäure-Korrosionsinhibitor ist 2,4,6-Tris(5-carboxypentylamino)- 1,3,5-triazin oder Benzthiazol-2-yl-thiobernsteinsäure.2,4,6-Tris (5-carboxypentylamino) is particularly preferred as a polycarboxylic acid corrosion inhibitor. 1,3,5-triazine or benzothiazol-2-yl-thiosuccinic acid.
In einer bevorzugten Anwendung kann der Korrosionsinibitor 10-50%, insbesondere 20-40% Anthranilsäure enthalten.In a preferred application, the corrosion inhibitor can contain 10-50%, in particular 20-40%, of anthranilic acid.
Als Dispergiermittel eignen sich alle oberflächenaktiven Verbindungen, insbesondere anionische und nichtionische Tenide.All surface-active compounds are suitable as dispersants, in particular anionic and nonionic tenides.
Beispiele für erfindungsgemäß verwendbare Dispersionsmittel sind die folgenden Verbindungsklassen.The following classes of compounds are examples of dispersants which can be used according to the invention.
- 1.1 Kondensationsprodukte von aromatischen Sulfonsäuren mit Formaldehyd, wie Kondensationsprodukte aus Formaldehyd und Naphthalinsulfonsäuren oder aus Formaldehyd, Naphthalinsulfonsäure und Benzolsulfonsäure, oder ein Kondensationsprodukt aus Rohkresol, Formaldehyd und Naphthalinsulfonsäure.1.1 condensation products of aromatic sulfonic acids with formaldehyde, such as condensation products of formaldehyde and naphthalenesulfonic acids or of formaldehyde, naphthalenesulfonic acid and benzenesulfonic acid, or a condensation product of crude cresol, formaldehyde and naphthalenesulfonic acid.
- 1.2 Ligninsulfonate, z.B. solche, die nach dem Sulfit- oder Kraft-Verfahren gewonnen werden. Vorzugsweise handelt es sich um Produkte, die z.T. hydrolysiert, oxidiert oder desulfoniert und nach bekannten Verfahren fraktioniert werden, z.B. nach dem Molekulargewicht oder nach dem Sulfonierungsgrad. Auch Mischungen aus Sulfit- und Kraftligninsulfonaten sind gut wirksam.1.2 lignin sulfonates, e.g. those obtained by the sulfite or Kraft process. They are preferably products that are partly hydrolyzed, oxidized or desulfonated and fractionated by known methods, e.g. by molecular weight or by degree of sulfonation. Mixtures of sulfite and kraft lignin sulfonates are also effective.
- 1.3 Dialkylsulfosuccinate, deren Alkylgruppen verzweigt oder unverzweigt sind, wie z.B. Di-propylsulfosuccinat, Di-isobutylsulfosuccinat, Di-amylsulfosuccinat, Bis-(2-ethylhexyl)-sulfosuccinat oder Di-octylsulfosuccinat.1.3 Dialkylsulfosuccinates, the alkyl groups of which are branched or unbranched, e.g. Di-propyl sulfosuccinate, di-isobutyl sulfosuccinate, di-amyl sulfosuccinate, bis (2-ethylhexyl) sulfosuccinate or di-octyl sulfosuccinate.
- 1.4 Sulfatierte oder sulfonierte Fettsäuren oder Fettsäureester von Fettsäuren, wie z.B. sulfatierte Oelsäure, Elaidinsäure oder Ricinolsäure bzw. deren niedere Alkylester, z.B Ethyl-, Propyl- oder Butylester. Sehr gut geeignet sind auch die entsprechenden sulfatierten oder sulfonierten Oele, wie z.B. Olivenöl, Rüböl und vor allem Ricinusöl.1.4 Sulfated or sulfonated fatty acids or fatty acid esters of fatty acids, e.g. sulfated oleic acid, elaidic acid or ricinoleic acid or their lower alkyl esters, e.g. ethyl, propyl or butyl esters. The corresponding sulfated or sulfonated oils, such as e.g. Olive oil, rape oil and above all castor oil.
- 1.5 Umsetzungprodukte von Ethylenoxid und/oder Propylenoxid mit gesättigten oder ungesättigten Fettsäuren, Fettalkoholen, Fettaminen, alicyclischen Alkoholen oder aliphatisch-aromatischen Kohlenwasserstoffen die endständig durch eine anorganische sauerstoffhaltige Säure oder eine mehrbasische Carbonsäure verestert sind. Und zwar handelt es sich vorzugsweise um Verbindungen der Formel1.5 Reaction products of ethylene oxide and / or propylene oxide with saturated or unsaturated fatty acids, fatty alcohols, fatty amines, alicyclic alcohols or aliphatic-aromatic hydrocarbons which are terminally esterified by an inorganic oxygen-containing acid or a polybasic carboxylic acid. In fact it is preferably compounds of the formula
R-A-(CH₂C₂HO)p-Q
worin R ein aliphatischer Kohlenwasserstoffrest mit 8 bis 22 Kohlenstoffatomen oder ein cycloaliphatischer oder aliphatisch-aromatischer Kohlenwasserstoffrest mit 10 bis 22 Kohlenstoffatomen, A -O-, -NH- oder -CO-O-, Q der Säurerest einer anorganischen, mehrbasischen Säure oder der Rest einer mehrbasischen Carbonsäure und p eine Zahl von 1 bis 20, insbesondere 1 bis 5, ist. Der Rest R-A- leitet sich z.B. ab von höheren Alkoholen wie Decyl-, Lauryl-, Tridecyl-, Myristyl-, Cetyl-, Stearyl-, Oleyl-, Arachidyl-, Hydroabietylalkohol oder Behenylalkohol; ferner von Fettaminen wie S tearylamin, Palmitylamin oder Oleylamin; von Fettsäuren, wie Capryl-, Caprin-, Laurin-, Myristin-, Palmitin-, Stearin-, Arachin-, Behen-, Kokosfett-(C₈-C₁₈), Decen-, Dodecen-, Tetradecen-, Hexadecen-, Oel-, Linol-, Linolen-, Eikosen-, Dokosen- oder Clupanodonsäure; oder von Alkylphenolen, wie Butyl-, Hexyl, n-Octyl-, n-Nonyl-, p-tert.Octyl, p-tert.Nonyl-, Decyl-, Dodecyl-, Tetradecyl- oder Hexadecylphenol.
RA- (CH₂C₂HO) p -Q
wherein R is an aliphatic hydrocarbon residue with 8 to 22 carbon atoms or a cycloaliphatic or aliphatic-aromatic hydrocarbon residue with 10 to 22 carbon atoms, A -O-, -NH- or -CO-O-, Q is the acid residue of an inorganic, polybasic acid or the rest a polybasic carboxylic acid and p is a number from 1 to 20, in particular 1 to 5. The rest RA- is derived, for example, from higher alcohols such as decyl, lauryl, tridecyl, myristyl, cetyl, stearyl, oleyl, arachidyl, hydroabietyl alcohol or behenyl alcohol; also of fatty amines such as S tearylamine, palmitylamine or oleylamine; of fatty acids, such as caprylic, capric, lauric, myristic, palmitic, stearic, arachine, behen, coconut oil (C₈-C₁₈), decene, dodecene, tetradecene, hexadecene, oil , Linoleic, linolenic, eicotonic, docosonic or clupanodonic acid; or of alkylphenols, such as butyl, hexyl, n-octyl, n-nonyl, p-tert-octyl, p-tert-nonyl, decyl, dodecyl, tetradecyl or hexadecylphenol.
Der Säurerest Q leitet sich in der Regel von niedermolekularen Dicarbonsäuren ab, wie z.B. Maleinsäure, Malonsäure, Bernsteinsäure oder Sulfobernsteinsäure, und ist über eine Esterbrücke mit dem Rest R-A-(CH₂CH₂O)p- verbunden. Insbesondere leitet sich Q jedoch von anorganischen mehrbasischen Säuren, wie Orthophosphorsäure und Schwefelsäure ab. Der Säurerest Q liegt vorzugsweise in Salzform, d.h. z.B. als Alkalimetall-, Ammonium- oder Aminsalz, vor. Beispiele für solche Salze sind Natrium-, Kalium, Ammonium-, Trimethylamin-, Aethanolamin-,Diethanolamin- oder Triethanolaminsalze.The acid residue Q is usually derived from low molecular weight dicarboxylic acids, such as maleic acid, malonic acid, succinic acid or sulfosuccinic acid, and is connected via an ester bridge to the rest RA- (CH₂CH₂O) p -. In particular, however, Q is derived from inorganic polybasic acids such as orthophosphoric acid and sulfuric acid. The acid residue Q is preferably in salt form, ie, for example, as an alkali metal, ammonium or amine salt. Examples of such salts are sodium, potassium, ammonium, trimethylamine, ethanolamine, diethanolamine or triethanolamine salts.
Normalerweise liegen die anionischen Dispergiermittel in Form ihrer Alkalisalze, ihrer Ammonimsalze oder ihrer wasserslöslichen Aminsalze vor. Man verwendet zweckmäßigerweise elekrolytarme Qualitäten.The anionic dispersants are normally in the form of their alkali metal salts, their ammonium salts or their water-soluble amine salts. It is expedient to use low-electrolyte qualities.
Ethylenoxid-Addukte aus der Klasse der Anlagerungsprodukte von Ethylenoxid an höhere Fettsäuren, gesättigte oder ungesätttige Fettalkohole, Mercaptane, Fettsäureamide, Fettsäurealkylolamide oder Fettamine oder an Alkylphenole oder Alkylthiophenole wobei auf 1 Mol der genannten Verbindungen bevorzugt 5 bis 100 Mol Ethylenoxid kommen, sowie Ethylenoxid-Propylenoxid-Blockpolymere und Ethylendiamin-Ethylenoxid-Propylenoxid-Addukte. Dazu gehören:
- 2.1 Umsetzungsprodukte von gesättigten und/oder ungesättigten Fettalkoholen mit 8 bis 20 C-Atomen, mit 20 bis 100 Mol Ethylenoxid je Mol Alkohol, vorzugsweise gesättigte lineare C₁₆-C₁₈-Alkohole mit 25 bis 80 insbesondere 25 Mol Ethylenoxid je Mol Alkohol;
- 2.2 Umsetzungsprodukte von gesättigten und/oder ungesättigten Fettsäuren mit 8 bis 20 C-Atomen mit 5 bis 20 Mol Ethylenoxid je Mol Säure;
- 2.3 Umsetzungsprodukte von Alkylphenolen mit 7 bis 12 C-Atomen im Alkylrest mit 5 bis 25 Mol Ethylenoxid je Mol phenolische Hydroxygruppe, vorzugsweise Mono- ode Dialkylphenole mit 10 bis 20 Mol Ethylenoxid je Mol phenolische Hydroxylgruppe;
- 2.4 Umsetzungsprodukte von gesättigten und/oder ungesättigten Fettsäureamiden mit 8 bis 20 C-Atomen mit 5 bis 20 Mol Ethylenoxid je Mol Säureamid, vorzugsweise Oelsäureamide mit 8 bis 15 Mol Ethylenoxid je Mol Säureamid.
- 2.5 Umsetzungprodukte von gesättigten und/oder ungesättigten Fettaminen mit 8 bis 20 C-Atomen mit 5 bis 20 Mol Ethylenoxid je Mol Amin, vorzugsweise Oleylamine mit 8 bis 15 Mol Ethylenoxid je Mol Amin;
- 2.6 Ethylenoxid-Propylenoxid-Blockpolymere mit 10- 80 % Ethylenoxid und Molekulargewichten von 1000-80000;
- 2.7 Ethylenoxid-Propylenoxid-Addukte an Ethylendiamin.
- 2.1 reaction products of saturated and / or unsaturated fatty alcohols with 8 to 20 carbon atoms, with 20 to 100 moles of ethylene oxide per mole of alcohol, preferably saturated linear C₁₆-C₁₈ alcohols with 25 to 80 in particular 25 moles of ethylene oxide per mole of alcohol;
- 2.2 reaction products of saturated and / or unsaturated fatty acids with 8 to 20 carbon atoms with 5 to 20 moles of ethylene oxide per mole of acid;
- 2.3 reaction products of alkylphenols with 7 to 12 carbon atoms in the alkyl radical with 5 to 25 moles of ethylene oxide per mole of phenolic hydroxyl group, preferably mono- or dialkylphenols with 10 to 20 moles of ethylene oxide per mole of phenolic hydroxyl group;
- 2.4 Reaction products of saturated and / or unsaturated fatty acid amides with 8 to 20 carbon atoms with 5 to 20 moles of ethylene oxide per mole of acid amide, preferably oleic acid amides with 8 to 15 moles of ethylene oxide per mole of acid amide.
- 2.5 reaction products of saturated and / or unsaturated fatty amines with 8 to 20 carbon atoms with 5 to 20 moles of ethylene oxide per mole of amine, preferably oleylamines with 8 to 15 moles of ethylene oxide per mole of amine;
- 2.6 ethylene oxide-propylene oxide block polymers with 10-80% ethylene oxide and molecular weights of 1000-80000;
- 2.7 Ethylene oxide-propylene oxide adducts with ethylenediamine.
Die Verdickungsmittel stabilisieren die Dispersionen, man kann sie daher auch als Stabilisatoren bezeichnen. Beispiele für verwendbare Verdickungsmittel sind vor allem modifizierte Polysaccharide vom Xanthan-, Alginat-, Guar- oder Cellulose-Typ. Dazu gehören, z.B. Celluloseether, wie Methylcellulose oder Carboxylmethylcellulose, oder Heteropolysaccharide, die in den Seitenketten z.B. Mannose- oder Glucuronsäure-Gruppen tragen. Solche Verdickungsmittel sind im Handel erhältlich.The thickeners stabilize the dispersions, so they can also be called stabilizers. Examples of usable thickeners are, above all, modified polysaccharides of the xanthan, alginate, guar or cellulose type. These include, for example, cellulose ethers, such as methyl cellulose or carboxylmethyl cellulose, or heteropolysaccharides which carry, for example, mannose or glucuronic acid groups in the side chains. Such thickeners are commercially available.
Außer dem Dispergiermittel und dem Verdickungsmittel können die erfindungsgemäßen Dispersionen noch weitere Hilfsmittel enthalten, beispielsweise hydrotrope Mittel, wie z.B. Harnstoff oder Natrium-xylolsulfonat; Gefrierschutzmittel, wie z.B. Ethylen- oder Propylenglykol, Diethylenglykol, Glycerin oder Sorbit; Feuchthaltemittel, wie z.B. Polyethylenglykole oder Glycerin; Biocide, wie z.B. Chloracetamid, Formalin oder 1,2-Benzisothiazolin-3-one; oder Komplexbildner, wie z.B. Trinatrium-nitrilotriacetat.In addition to the dispersant and the thickener, the dispersions according to the invention may also contain other auxiliaries, for example hydrotropic agents, such as e.g. Urea or sodium xylene sulfonate; Antifreezing agents, e.g. Ethylene or propylene glycol, diethylene glycol, glycerin or sorbitol; Humectants, e.g. Polyethylene glycols or glycerin; Biocides such as Chloroacetamide, formalin or 1,2-benzisothiazolin-3-one; or complexing agents, e.g. Trisodium nitrilotriacetate.
Von besonderer Bedeutung ist der Zusatz von Biociden, insbesondere von Fungiciden, die ein Pilzwachstum in der wäßrigen Dispersion verhindern sollen. Das Biocid wird vorzugsweise in einer Menge von 0,05 bis 0,5 Gew.-% der Dispersion verwendet.Of particular importance is the addition of biocides, especially fungicides, which are intended to prevent fungal growth in the aqueous dispersion. The biocid is preferably used in an amount of 0.05 to 0.5% by weight of the dispersion.
Zur Herstellung dieser Dispersionen geht man zweckmäßig vom feuchten Filterkuchen aus, setzt diesem das Dispergiermittel und das Verdickungmittel sowie gegebenenfalls die gewünschte Menge Wasser und gegebenenfalls sonstige Zusätze zu und rührt das Gemisch so lange bis eine fließfähige homogene Dispersion entstanden ist.To prepare these dispersions, it is advisable to start with a moist filter cake, add the dispersant and the thickener and, if appropriate, the desired amount of water and any other additives, and stir the mixture until a flowable, homogeneous dispersion has formed.
Hat der Filterkuchen bereits den gewünschten Gehalt an Wasser, so braucht man natürlich kein Wasser zusetzen. Man kann beim Filtrieren die Polycarbonsäure so stark abpressen, daß nur 40 % oder weniger Wasser im Filterkuchen verbleiben. Beim Rühren des Filterkuchens gibt man dann langsam so viel Wasser zu, daß eine fließfähige Dispersion entsteht. Hat man einmal die optimale Menge ermittelt, so kann man den Druck beim Filtrieren so wählen, daß der Filterkuchen bereits den gewünschten Wassergehalt hat.If the filter cake already has the desired water content, then of course you do not need to add water. When filtering, the polycarboxylic acid can be pressed so strongly that only 40% or less water remains in the filter cake. When the filter cake is stirred, enough water is slowly added to produce a flowable dispersion. Once you have determined the optimal amount, you can choose the pressure when filtering so that the filter cake already has the desired water content.
Das Rühren kann in üblichen Rührgeräten geschehen, vor allem in solchen Rührgeräten, bei denen auf das Rührgut ein stärkerer Druck ausgeübt wird. Brauchbar sind z.B. Rührwerke mit einer Rührspindel, Zahnmühlen, Kolloidmühlen oder Schneckenrührwerke.The stirring can be done in conventional stirrers, especially in stirrers in which a greater pressure is exerted on the material to be stirred. The following are usable e.g. Agitators with a stirring spindle, tooth mills, colloid mills or screw agitators.
Je nach dem verwendeten Rührwerk benötigt man zur Erzielung einer fließfähigen Dispersion etwa eine halbe bis zu einer Stunde. Das Rühren wird vorzugsweise bei Raumtemperatur durchgeführt, es kann aber in bestimmten Fällen von Vorteil sein, das Rührgut leicht zu kühlen.Depending on the agitator used, it takes about half an hour to an hour to achieve a flowable dispersion. The stirring is preferably carried out at room temperature, but it can be advantageous in certain cases to slightly cool the material to be stirred.
Die so hergestellten Dispersionen sind bei Raumtemperatur sowie bei Temperaturen bis zu 40°C mehrere Monate stabil. Sie behalten ihre Fließfähigkeit und entmischen sich nicht. Das ist für die Lagerung und den Transport der Dispersionen eine wichtige Eigenschaft.The dispersions thus produced are stable for several months at room temperature and at temperatures up to 40 ° C. They keep their fluidity and do not separate. This is important for the storage and transportation of the dispersions Property.
Für die Verwendung der Dispersionen in wässrigen Medien ist es von Vorteil, daß die Dispersionen als Flüssigkeit gehandhabt werden können und z.B. bei der Dosierung gepumpt werden können. Ein weiterer Vorteil ist, daß sich die Dispersionen sehr schnell in alkalisch-wäßrigen Systemen lösen. Bestehen die Dispersionen aus den Salzen der Polycarbonsäuren, so lösen diese sich auch in neutralen wäßrigen Systemen. Das Lösen kann durch Rühren beschleunigt werden.For the use of the dispersions in aqueous media it is advantageous that the dispersions can be handled as a liquid and e.g. can be pumped during dosing. Another advantage is that the dispersions dissolve very quickly in alkaline aqueous systems. If the dispersions consist of the salts of the polycarboxylic acids, they also dissolve in neutral aqueous systems. The dissolution can be accelerated by stirring.
Beispiele für wäßrige Systeme, in denen die erfindungsgemäßen Dispersionen eingesetzt werden können, sind Kühlwassersysteme, Klimaanlagen, Dampferzeugungsanlagen, Seewasserentsalzungsanlagen, Heizungs- und Kühlwasserkreisläufe, wäßrige Hydraulikflüssikeiten, vor allem aber wäßrige Metallbearbeitungsflüssigkeiten.Examples of aqueous systems in which the dispersions according to the invention can be used are cooling water systems, air conditioning systems, steam generating systems, seawater desalination systems, heating and cooling water circuits, aqueous hydraulic fluids, but above all aqueous metalworking fluids.
Die folgenden Beispiele illustrieren die Erfindung näher, ohne sie auf diese Beispiele beschränken zu wollen. Darin bedeuten Teile Gewichtsteile und Prozente Gewichtsprozente.The following examples illustrate the invention in more detail without wishing to restrict it to these examples. Parts in parts by weight and percentages mean percentages by weight.
99,2 Teile eines 50 % Wasser enthaltenden Filterkuchens von 2,4,6-Tris(5-carboxypentylamino)- 1,3,5-triazin (Reocor® 190, Ciba-Geigy AG) werden in einem Turbinenrührwerk der Fa-Polytron bei einer Rührgeschwindigkeit von 1000 U/min bis zur Fließfähigkeit gerührt. Dies dauert etwa 15 Minuten. Dann werden 0,5 Teile eines Dispergiermittels auf Basis einer 40 %igen wäßrigen Lösung von dinaphthylmethandisulfosaurem Natrium (Dispergator CC, Ciba-Geigy AG) zugegeben und nach weiteren 15 Minuten Rühren werden 0,1 Teile eines Polysaccharides von Xanthan-Typus (Rhodopol® 23, Rhone-Poulenc) als Verdicker und 0,2 Teile einer 35 %igen wäßrigen Dispersion von 1,2-Benzisothiazolin-3-on (Proxel® BD, JCJ Ltd. ) als Biocid zugegeben und nochmals 15 Minuten gerührt. Die entstandene Dispersion enthält ca. 50 % Wasser und hat eine Viskosität von 170 mPa.s⁻¹ bei 20°C. (gemessen mit einem Rotationsviskosimeter mit Meß-System DIN 25). Zur Prüfung der Stabilität wird die Dispersion bei Raumtemperatur und bei 40°C gelagert. Nach 6 Wochen ist keine Phasentrennung eingetreten.99.2 parts of a filter cake of 2,4,6-tris (5-carboxypentylamino) -1,3,5-triazine (Reocor® 190, Ciba-Geigy AG) containing 50% water are added in a turbine agitator from Fa-Polytron a stirring speed of 1000 rev / min until fluidity. This takes about 15 minutes. Then 0.5 part of a dispersant based on a 40% aqueous solution of dinaphthylmethane disulphosaem sodium (Dispersant CC, Ciba-Geigy AG) is added and after stirring for a further 15 minutes, 0.1 part of a polysaccharide of the xanthan type (Rhodopol® 23 , Rhone-Poulenc) as a thickener and 0.2 part of a 35% aqueous dispersion of 1,2-benzisothiazolin-3-one (Proxel® BD, JCJ Ltd.) as a biocide and stirred for another 15 minutes. The resulting dispersion contains approximately 50% water and has a viscosity of 170 mPa.s⁻¹ at 20 ° C. (measured with a rotary viscometer with measuring system DIN 25). To check the stability, the dispersion is stored at room temperature and at 40 ° C. No phase separation occurred after 6 weeks.
Es wird wie in Beispiel 1 gearbeitet. 90.6 Teilen eines Reocor® 190-Filterkuchens mit 50 % Wassergehalt werden mit 1 Teil eines anionischen Tensides auf Basis eines Formaldehyd-Kondensationsproduktes einer aromatischen Sulfosäure als 10 %ige wässrige Lösung (Dispergator H, Ciba-Geigy AG), 0,2 Teilen Rhodopol® 23 und 0,2 Teilen Proxel® BD verrührt. Die resultierende Dispersion hat eine Viskosität von 250 mPa.s⁻¹ und zeigt keine Veränderung bei 4 Monaten Lagerung bei 20°C.The procedure is as in Example 1. 90.6 parts of a Reocor® 190 filter cake with 50% water content are mixed with 1 part of an anionic surfactant based on a formaldehyde condensation product of an aromatic sulfonic acid 10% aqueous solution (Dispersant H, Ciba-Geigy AG), 0.2 parts Rhodopol® 23 and 0.2 parts Proxel® BD. The resulting dispersion has a viscosity of 250 mPa.s⁻¹ and shows no change after 4 months storage at 20 ° C.
Es wird wie in Beispiel 1 gearbeitet unter Mischen der folgenden Komponenten:
- 99,1
- Teile Reocor® 190-Filterkuchen mit 50 % Wassergehalt
- 0,5
- Teile eines Ethylenoxid-Propylenoxyd-Blockcopolymer (Pluronic® F 108, BASF-Wyandotte Corp.) als Dispergator
- 0.2
- Teile Rhodopol® 23 als Verdicker
- 0,2
- Teile Proxel® BD als Biocid
- 99.1
- Share Reocor® 190 filter cake with 50% water content
- 0.5
- Parts of an ethylene oxide-propylene oxide block copolymer (Pluronic® F 108, BASF-Wyandotte Corp.) as a dispersant
- 0.2
- Share Rhodopol® 23 as a thickener
- 0.2
- Share Proxel® BD as a biocid
Die resultierende Dispersion hat eine Viskosität von 250 mPa/s.The resulting dispersion has a viscosity of 250 mPa / s.
Es wird wie in Beispiel 1 gearbeitet unter Variation des Dispergators und der mengenmäßigen Zusammensetzung.
Alle Dispersionen sind bei 20°C 4 Monate lagerstabil.All dispersions are stable for 4 months at 20 ° C.
5 kg eines 54 % Wasser enthaltenden Filterkuchens von Benzthiazol-2-ylthiobernsteinsäure (Reocor® 152, Ciba-Geigy AG) werden wie in Versuch 1 beschrieben mit 25 g Dispergator CC und 5 g Rhodopol® 23 dispergiert. Die resultierende Dispersion hat eine Viskosität von 60 mPa.⁻¹ bei 25°C (gemessen mit einem Viscotester VT 500 bei einer Drehzahl von 8). Bei Raumtemperatw zeigt diese Dispersion bei 6 Wochen Lagerung keine Veränderung.5 kg of a filter cake containing 54% water of benzothiazol-2-ylthiosuccinic acid (Reocor® 152, Ciba-Geigy AG) are dispersed as described in experiment 1 with 25 g of CC dispersant and 5 g of Rhodopol® 23. The resulting dispersion has a viscosity of 60 mPa.⁻¹ at 25 ° C (measured with a Viscotester VT 500 at a speed of 8). At room temperature, this dispersion shows storage for 6 weeks no change.
In einem 1,5l Glasgefäß mit Schneckenrührwerk aus Edelstahl werden 3 g eines Ligninsulfonates (Reax® 85-A) in 44 g Wasser gelöst. Dazu gibt man bei einer Rührgeschwindigkeit von ca. 50-70 Upm innerhalb von 15 Minuten 900 g eines ca. 50 % Wasser enthaltenden Filterkuchens von Reocor® 190. Dabei entsteht eine flüssige Dispersion, welche während ca. 30 min bei 50 -70 U/pM homogenisiert wird. Dazu gibt man die Lösung von 1 g Rhodopol® 23 in 50 g Wasser. Anschließend wird die Dispersion 1 h bei 75 U/pm gerührt. Die so bereitete Dispersion hat eine Viskosität von 200 mPa.s⁻¹ (bei 25°C). Die Dispersion hat einen Gehalt von 45 % des Korrosionsinhibitors; 54,5 % Wasser, O,3 % Dispergiermittel, 0, 1 % Verdicker.3 g of a lignin sulfonate (Reax® 85-A) are dissolved in 44 g of water in a 1.5 liter glass vessel with a stainless steel screw agitator. At a stirring speed of approx. 50-70 rpm, 900 g of a filter cake of Reocor® 190 containing approx. 50% water are added within 15 minutes. This creates a liquid dispersion, which for approx. 30 min at 50 -70 U / pM is homogenized. To do this, add the solution of 1 g Rhodopol® 23 in 50 g water. The dispersion is then stirred at 75 rpm for 1 h. The dispersion prepared in this way has a viscosity of 200 mPa.s⁻¹ (at 25 ° C). The dispersion contains 45% of the corrosion inhibitor; 54.5% water, O.3% dispersant, 0.1% thickener.
Zu einer Lösung von 10 g Dispergator CC und 2 g Polyethylenoxid (MG 10⁶) in 135 g Wasser werden unter Rühren bei 50-60 U/pm innerhalb 15 Minuten 800 g eines ca. 50 % Wasser enthaltenden Filterkuchens von Reocor® 190 zugegeben. Dazu gibt man die Lösung von 1 g Rhodopol® 23 in 50 g Wasser und 2 g Proxel® BD. Anschließend wird die Dispersion 1 h bei 75 U/pm homogenisiert. Es entsteht eine fließfähige Dispersion mit einem Gehalt von 40 % des Korrosionsinhibitors, 59 % Wasser, 0,4 % Dispergiermittel, 0,1 % Verdicker, 0,2 % Biocid und 0,2 % Gleitmittel (Polyethylenoxid).800 g of a Reocor® 190 filter cake containing about 50% water are added to a solution of 10 g of dispersant CC and 2 g of polyethylene oxide (MW 10⁶) in 135 g of water with stirring at 50-60 rpm within 15 minutes. To do this, add the solution of 1 g Rhodopol® 23 in 50 g water and 2 g Proxel® BD. The dispersion is then homogenized at 75 rev / pm for 1 h. The result is a flowable dispersion containing 40% of the corrosion inhibitor, 59% water, 0.4% dispersant, 0.1% thickener, 0.2% biocide and 0.2% lubricant (polyethylene oxide).
In einem Glasgefäß 600 ml mit Schneckenrührwerk aus Edelstahl werden 1.2 g eines Ligninsulfonates (Reax® 85-A) in 91 g Wasser gelöst. Dazu gibt man bei einer Rührgeschwindigkeit von ca. 50-70 Upm innerhalb von 15 Minuten 256 g eines ca. 50 % Wasser enthaltenden Filterkuchens von Reocor® 190. Dabei entsteht eine flüssige Dispersion, der innerhalb von 15 Min 32 g Anthranilsäure zugegeben werden. Anschließend wird 30 Minuten bei 50-70 U/pM homogenisiert. Dazu gibt man die Lösung von 0.4 g Rhodopol® 23 in 19.6 g Wasser. Anschließend wird die Dispersion 1 h bei 75 U/pm gerührt Die so bereitete Dispersion hat eine Viskosität von 200 mPa.s⁻¹ (bei 25°C). Die Dispersion hat einen Gehalt von 40 % des Korrosionsinhibitors (Verhältnis 80 Teile Reocor 190 und 20 Teile Anthranilsäure); 59.6 % Wasser, O,3 % Dispergiermittel, 0, 1 % Verdicker.1.2 g of a lignin sulfonate (Reax® 85-A) is dissolved in 91 g of water in a 600 ml glass vessel with a stainless steel screw agitator. At a stirring speed of approx. 50-70 rpm, 256 g of a filter cake of Reocor® 190 containing approx. 50% water are added within 15 minutes. This results in a liquid dispersion to which 32 g of anthranilic acid are added within 15 minutes. The mixture is then homogenized at 50-70 U / pM for 30 minutes. Add the solution of 0.4 g Rhodopol® 23 in 19.6 g water. The dispersion is then stirred at 75 rpm for 1 h. The dispersion prepared in this way has a viscosity of 200 mPa.s (¹ (at 25 ° C). The dispersion contains 40% of the corrosion inhibitor (ratio 80 parts Reocor 190 and 20 parts anthranilic acid); 59.6% water, O, 3% dispersant, 0.1% thickener.
In einem Glasgefäß (600 ml) mit Schneckenrührwerk aus Edelstahl werden 1.2 g eines Ligninsulfonates (Reax® 85-A) in 123 g Wasser gelöst. Dazu gibt man bei einer Rührgeschwindigkeit von ca. 50-70 U/pm innerhalb von 15 Minuten 192 g eines ca. 50 % Wasser enthaltenden Filterkuchens von Reocor® 190. Dabei entsteht eine flüssige Dispersion, der innerhalb von 15 Min 64 g Anthranilsäure (Gehalt 99%) zugegeben werden. Anschließend wird 30 Minuten bei 50-70 UpM homogenisiert. Dazu gibt man die Lösung von 0.4 g Rhodopol® 23 in 19.6 g Wasser. Anschließend wird die Dispersion 1 h bei 75 U/pm gerührt. Die so bereitete Dispersion hat eine Viskosität von 200 mPa.s⁻¹ (bei 25°C). Die Dispersion hat einen Gehalt von 40 % des Korrosionsinhibitors (Verhältnis 60 Teile Reocor 190 und 40 Teile Anthranilsäure); 59.6 % Wasser, O,3 % Dispergiermittel, 0,1 % Verdicker.In a glass vessel (600 ml) with a stainless steel screw agitator, 1.2 g of a lignin sulfonate (Reax® 85-A) is dissolved in 123 g of water. At a stirring speed of approx. 50-70 U / pm, 192 g of a filter cake of Reocor® 190 containing approx. 50% water are added within 15 minutes Liquid dispersion to which 64 g of anthranilic acid (99% content) are added within 15 minutes. The mixture is then homogenized at 50-70 rpm for 30 minutes. Add the solution of 0.4 g Rhodopol® 23 in 19.6 g water. The dispersion is then stirred at 75 rpm for 1 h. The dispersion prepared in this way has a viscosity of 200 mPa.s⁻¹ (at 25 ° C). The dispersion contains 40% of the corrosion inhibitor (ratio 60 parts Reocor 190 and 40 parts anthranilic acid); 59.6% water, O, 3% dispersant, 0.1% thickener.
In einem Glasgefäß (600 ml) mit Schneckenrührwerk aus Edelstahl werden 1.2 g eines Ligninsulfonates (Reax® 85-A) in 19 g Wasser gelöst. Dazu gibt man bei einer Rührgeschwindigkeit von ca. 50-70 U/pm innerhalb von 15 Minuten 360 g eines ca. 50 % Wasser enthaltenden Filterkuchens von Reocor® 190 (Mononatriumsalz*) . Dabei entsteht eine flüssige Dispersion, die noch 30 Minuten bei 50-70 UpM homogenisiert wird. Dazu gibt man die Lösung von 0.4 g Rhodopol® 23 in 19.6 g Wasser. Anschließend wird die Dispersion 1 h bei 75 U/pm gerührt. Die so bereitete Dispersion hat eine Viskosität von 200 mPa.s⁻¹ (bei 25°C). Die Dispersion hat einen Gehalt von 45 % des Korrosionsinhibitors , 54.6 % Wasser, O,3 % Dispergiermittel, 0,1 % Verdicker.
*) Zu Reocor 190 Filterkuchen wird in wäßriger Suspension eine Lösung von Dinatriumhydrogenphosphat zugesetzt; das gebildete Mononatriumsalz wird isoliert und kann mit Reax als Dispergator verflüssigt werden.1.2 g of a lignin sulfonate (Reax® 85-A) are dissolved in 19 g of water in a glass vessel (600 ml) with a stainless steel screw agitator. At a stirring speed of approx. 50-70 U / pm, 360 g of a filter cake of Reocor® 190 (monosodium salt *) containing approx. 50% water are added within 15 minutes. This creates a liquid dispersion that is homogenized for 30 minutes at 50-70 rpm. Add the solution of 0.4 g Rhodopol® 23 in 19.6 g water. The dispersion is then stirred at 75 rpm for 1 h. The dispersion prepared in this way has a viscosity of 200 mPa.s⁻¹ (at 25 ° C). The dispersion has a content of 45% of the corrosion inhibitor, 54.6% water, O, 3% dispersant, 0.1% thickener.
*) A solution of disodium hydrogen phosphate is added to the Reocor 190 filter cake in aqueous suspension; the monosodium salt formed is isolated and can be liquefied using Reax as the dispersant.
In einem Glasgefäß (600 ml) mit Schneckenrührwerk aus Edelstahl werden 1.2 g eines Ligninsulfonates (Reax® 85-A) in 19 g Wasser gelöst. Dazu gibt man bei einer Rührgeschwindigkeit von ca. 50-70 U/pm innerhalb von 15 Minuten 360 g eines ca. 50 % Wasser enthaltenden Filterkuchens von Reocor® 190 (Monodiethanolaminsalz#) . Dabei entsteht eine flüssige Dispersion, die noch 30 Minuten bei 50-70 UpM homogenisiert wird. Dazu gibt man die Lösung von 0.4 g Rhodopol® 23 in 19.6 g Wasser. Anschließend wird die Dispersion 1 h bei 75 U/pm gerührt. Die Dispersion hat einen Gehalt von 45 % des Korrosionsinhibitors, 54.6 % Wasser, O,3 % Dispergiermittel, 0,1 % Verdicker.
#) Zu Reocor 190 Filterkuchen wird in wäßriger Suspension die stöchiometrische Menge Diethanolamin gegeben; das gebildete Mono-Diethanolaminsalz wird isoliert und kann mit Reax als Dispergator verflüssigt werden.1.2 g of a lignin sulfonate (Reax® 85-A) are dissolved in 19 g of water in a glass vessel (600 ml) with a stainless steel screw agitator. 360 g of a filter cake of approx. 50% water containing Reocor® 190 (monodiethanolamine salt #) are added within 15 minutes at a stirring speed of approx. 50-70 rpm. This creates a liquid dispersion that is homogenized for 30 minutes at 50-70 rpm. Add the solution of 0.4 g Rhodopol® 23 in 19.6 g water. The dispersion is then stirred at 75 rpm for 1 h. The dispersion has a content of 45% of the corrosion inhibitor, 54.6% water, O, 3% dispersant, 0.1% thickener.
#) The stoichiometric amount of diethanolamine is added to Reocor 190 filter cake in aqueous suspension; the mono-diethanolamine salt formed is isolated and can be liquefied using Reax as a dispersant.
Claims (13)
HOOC-(CH₂)n-COOH III
worin Z C₁-C₁₁-Alkylen, Cyclohexylen oder Phenylen bedeutet,
R₁ und R₂ unabhängig voneinander H, C₁-C₄-Alkyl oder eine Gruppe -Z-COOH bedeutet,
R₃ C₁-C₁₂-Alkyl, Phenyl oder eine Gruppe -N(R₄)(R₅), -OR₆ oder -SR₆ bedeutet,
R₄ und R₅ unabhängig voneinander H, C₁-C₁₂-Alkyl, C₂-C₄-Hydroxyalkyl, Cyclohexyl, Phenyl oder eine Gruppe -Z-COOH bedeuten oder R₄ und R₅ zusammen C₄-C₆-Alkylen oder 3-Oxapentylen bedeuten,
R₆ Wasserstoff, C₁-C₁₂-Alkyl oder Phenyl bedeutet,
m null oder 1 ist, X Schwefel, Sauerstoff oder NH bedeutet,
R₇ Wasserstoff, C₁-C₄-Alkyl, Halogen, C₁-C₄-Alkoxy, Carboxy, Amino oder Nitro bedeutet,
R₈, R₉, R₁₀ und R₁₁ unabhängig voneinander Wasserstoff, C₁-C₁₂-Alkyl, C₁-C₄-Hydroxyalkyl, C₂-C₆-Carboxyalkyl, C₂-C₁₀-Alkoxyalkyl, Carboxyl, Phenyl oder Benzyl bedeuten oder R₈ und R₉ zusammen eine direkte Bindung bedeuten, wobei mindestens 2 der Gruppen R₈, R₉, R₁₀ und R₁₁ eine Carboxyl- oder Carboxylalkylgruppe sind,
und n 2-10 ist, oder ein Alkalimetall-, Ammonium- oder Aminsalz einer solchen Polycarbonsäre ist.Dispersion according to Claim 1, characterized in that the polycarboxylic acid corrosion inhibitor is a compound of the formula I, II or III,
HOOC- (CH₂) n -COOH III
wherein Z is C₁-C₁₁ alkylene, cyclohexylene or phenylene,
R₁ and R₂ independently of one another are H, C₁-C₄-alkyl or a group -Z-COOH,
R₃ is C₁-C₁₂-alkyl, phenyl or a group -N (R₄) (R₅), -OR₆ or -SR₆,
R₄ and R₅ independently of one another are H, C₁-C₁₂-alkyl, C₂-C₄-hydroxyalkyl, cyclohexyl, phenyl or a group -Z-COOH or R₄ and R₅ together are C₄-C₆-alkylene or 3-oxapentylene,
R₆ is hydrogen, C₁-C₁₂-alkyl or phenyl,
m is zero or 1, X is sulfur, oxygen or NH,
R₇ is hydrogen, C₁-C₄-alkyl, halogen, C₁-C₄-alkoxy, carboxy, amino or nitro,
R₈, R₉, R₁₀ and R₁₁ independently of one another are hydrogen, C₁-C₁₂-alkyl, C₁-C₄-hydroxyalkyl, C₂-C₆-carboxyalkyl, C₂-C₁₀-alkoxyalkyl, carboxyl, phenyl or benzyl or R₈ and R₉ together mean a direct bond , wherein at least 2 of the groups R₈, R₉, R₁₀ and R₁₁ are a carboxyl or carboxylalkyl group,
and n is 2-10, or is an alkali metal, ammonium or amine salt of such a polycarboxylic acid.
Z C₁-C₈-Alkylen bedeutet, R₁ und R₂ Wasserstoff oder C₁-C₄-Alkyl bedeuten,
R₃ eine Gruppe -N(R₄)(R₅) ist, R₄ Wasserstoff, Cyclohexyl oder C₁-C₁₂-Alkyl bedeutet,
R₅ C₁-C₁₂-Alkyl, Phenyl oder eine Gruppe -Z-COOH bedeutet oder R₄ und R₅ zusammen 1,5-Pentylen oder 3-Oxa- 1,5-pentylen bedeuten,
m null oder 1 ist, X Schwefel ist, R₇ Wasserstoff, Methyl oder Chlor bedeutet, R₈ und R₁₀ Wasserstoff sind,
R₉ und R₁₁ Carboxyl oder C₂-C₄-Carboxyalkyl bedeuten und n 4-8 ist oder ein Alkalimetall-, Ammonium- oder Aminsalz einer solchen Polycarbonsäure ist.Dispersion according to claim 1, characterized in that the polycarboxylic acid corrosion inhibitor is a compound of formula I, II or III, wherein
Z is C₁-C₈-alkylene, R₁ and R₂ are hydrogen or C₁-C₄-alkyl,
R₃ is a group -N (R₄) (R₅), R₄ is hydrogen, cyclohexyl or C₁-C₁₂-alkyl,
R₅ is C₁-C₁₂-alkyl, phenyl or a group -Z-COOH or R₄ and R₅ together are 1,5-pentylene or 3-oxa- 1,5-pentylene,
m is zero or 1, X is sulfur, R₇ is hydrogen, methyl or chlorine, R₈ and R₁₀ are hydrogen,
R₉ and R₁₁ are carboxyl or C₂-C₄-carboxyalkyl and n is 4-8 or an alkali metal, ammonium or amine salt of such a polycarboxylic acid.
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CH1228/91 | 1991-04-24 | ||
CH122891 | 1991-04-24 |
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EP0511163A1 true EP0511163A1 (en) | 1992-10-28 |
EP0511163B1 EP0511163B1 (en) | 1995-07-26 |
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EP92810280A Expired - Lifetime EP0511163B1 (en) | 1991-04-24 | 1992-04-15 | Pourable aqueous dispersions of polycarboxylic acid corrosion inhibitors |
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US (1) | US5549847A (en) |
EP (1) | EP0511163B1 (en) |
JP (1) | JP3259185B2 (en) |
BR (1) | BR9201495A (en) |
CA (1) | CA2066806C (en) |
DE (1) | DE59203008D1 (en) |
ES (1) | ES2075671T3 (en) |
MX (1) | MX9201868A (en) |
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EP0553962A1 (en) * | 1992-01-18 | 1993-08-04 | Ciba-Geigy Ag | Corrosion inhibiting compositions |
DE19648843A1 (en) * | 1996-11-26 | 1998-06-04 | Zts Chemie Gmbh | Melamine polycarboxamides and their use as anti-corrosion agents |
US5780406A (en) * | 1996-09-06 | 1998-07-14 | Honda; Kenji | Non-corrosive cleaning composition for removing plasma etching residues |
EP0949253A1 (en) * | 1998-03-27 | 1999-10-13 | Stefan Graichen | Melamine-azomethine derivates and corrosion inhibitor containing these derivates |
US6413923B2 (en) | 1999-11-15 | 2002-07-02 | Arch Specialty Chemicals, Inc. | Non-corrosive cleaning composition for removing plasma etching residues |
WO2014005861A1 (en) * | 2012-07-03 | 2014-01-09 | Basf Se | 1,3,5-triazine derivatives as corrosion inhibitors for metallic surfaces |
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Also Published As
Publication number | Publication date |
---|---|
JPH05179243A (en) | 1993-07-20 |
US5549847A (en) | 1996-08-27 |
DE59203008D1 (en) | 1995-08-31 |
JP3259185B2 (en) | 2002-02-25 |
BR9201495A (en) | 1992-11-24 |
EP0511163B1 (en) | 1995-07-26 |
MX9201868A (en) | 1992-10-01 |
ES2075671T3 (en) | 1995-10-01 |
CA2066806C (en) | 2002-03-12 |
CA2066806A1 (en) | 1992-10-25 |
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