Salts of alkaline earth metals, salts of transition metals or transition metal complexes ketocarboxylic acids, method for their preparation and composition for coating and method for the protection of the corroding metal substrate

 

(57) Abstract:

The proposed salts of alkaline earth metals, salts of transition metals or transition metal complexes, compounds of formula (I), where R1represents hydrogen; R2- R5represent, independently from each other, hydrogen, chlorine, bromine or C1-C8-alkyl; n represents 2, excluding the calcium salt of 3-(3-chloro-4-isopropylbenzyl) propionic acid. Metals are calcium, titanium, manganese, iron, cobalt, zinc, yttrium, zirconium, lanthanum or cerium. The method of obtaining salts or complexes interaction ketocarboxylic acids of the formula (1) or its alkali metal salt with a compound of alkaline earth metal or transition metal compound. Composition for coatings containing organic film-forming binder and a corrosion inhibitor. The way to protect correlated metal substrate, providing a coating on the substrate composition for coatings. 4 C. and 12 C.p. f-crystals, 10 PL.

The invention relates to new salts of alkaline earth metals, salts of transition metals and transition metal complexes ketocarboxylic acids, compositions for coatings, the corrosion inhibitors, as well as for use in compositions for coatings to protect metal surfaces.

The use of alkali, ammonium and amine salts ketocarboxylic acids as corrosion inhibitors in aqueous systems are known and are described, for example, in patent US-A-4909987 and European applications EP-A-412933 or EP-A-496555.

Now it has been found that salts of alkaline earth metals, salts of transition metals and transition metal complexes ketocarboxylic acids are particularly suitable as corrosion inhibitors in compositions for coatings to protect metal surfaces.

The present invention relates to the salts of alkaline earth metals, salts of transition metals or transition metal complexes of compounds of the formula I

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where R1represents hydrogen,

R2, R3, R4and R5independently of one another represent hydrogen, chlorine, bromine or C1-C8-alkyl,

n denotes 2,

excluding the calcium salt of 3-(3-chloro-4-isopropylbenzyl)propionic acid.

Alkaline earth metals are, for example, magnesium, calcium, strontium or barium. Preferred is calcium.

Transitional meta is organic, iron, cobalt, zinc, yttrium, zirconium, lanthanum or cerium. Especially preferred is zirconium.

Preferred are also the compounds of formula I where at least two, in particular 3, of the residues R1-R5represent hydrogen.

Preferred are also the compounds of formula I, where the metals are calcium, titanium, manganese, iron, cobalt, zinc, yttrium, zirconium, lanthanum or cerium.

Preferred are also the compounds of formula I, where the metal is zirconium.

Of particular interest are the compounds of formula I, where R1, R2, R4and R5represent hydrogen, R3denotes hydrogen, C1-C4-alkyl or chlorine, n represents 2, and metals are calcium, titanium, manganese, iron, cobalt, zinc, yttrium, zirconium, lanthanum or cerium.

Highly preferred are salts of alkaline earth metals, salts of transition metals or transition metal complexes of 3-(4-methylbenzoyl)propionic acid and 3- (4-chlorobenzoyl)propionic acid.

Salts of alkaline earth metals, salts of transition metals and transition metal complexes of compounds of the formula I Pescaia surfaces, as well as for pre-treatment of metal substrates.

Therefore, another object of the invention is also a composition for coating containing (a) an organic film-forming binder and (b) a corrosion inhibitor, which is used as at least salts of alkaline earth metals, salts of transition metals or transition metal complexes of compounds of the formula I,

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where R1represents hydrogen,

R2, R3, R4and R5independently of one another represent hydrogen, chlorine, bromine or C1-C8-alkyl,

n denotes 2.

The preferred composition for coating is a tool for coatings, particularly preferably an aqueous vehicle for coatings.

Also another object of the invention is a method of protection corrodium metal substrate, which is that the substrate is applied a composition for coating, which contains (a) an organic film-forming binder and b) as corrosion inhibitor, at least salt, alkaline earth metal, transition metal salt or complex of the transition metal compounds of the formula I, and then dried it is different metals compounds of the formula I according to the invention can be obtained in a known manner.

The invention relates also to a method for producing salts of alkaline earth metals, transition metal salts or transition metal complexes of compounds of the formula I, namely, that ketocarboxylic acid of the formula I or its salt of the alkali metal is subjected to interaction with the connection alkaline earth metal or transition metal compound.

The preferred method is that as the connection alkaline earth metal or transition metal compounds used salt, ORGANOMETALLIC compound or inorganic metal base.

Upon receipt of the transition metal complexes according to the invention, as, for example, complex compounds of zirconium, calculated from the compounds of formula I and zirconium carbonate, carry out the reaction in water without sodium hydroxide, at elevated temperature, in particular at temperatures from 50 to 100oC. a Particularly preferred temperature range from 70o95oC.

The reaction can also be accomplished in an organic solvent such as toluene, at a slightly elevated temperature. This method is particularly preferred if the compounds of alkaline earth metalloplasticine in the range of 20oup to 70oC, in particular from 40o60oC.

The compounds of formula I (free acid) interact with the compounds of alkaline earth and transition metals mainly in equimolar amounts. Salts of alkaline earth metals, salts of transition metals or transition metal complexes of compounds of the formula I according to the invention can be represented, for example, the General formula II

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where M denotes an alkaline earth or a transition metal and m is 2, 3, and 4.

In the case of salts of transition metals and complexes of transition metals, especially metals zirconium and titanium, especially when requiredno transformation, the end connections can take also different from formula II structure. Examples of this are provided below for the complex compounds of zirconium.

In the case of transition metal complexes according to the invention, especially of complex compounds of titanium and zirconium, it is possible to apply the compounds of formula I (free acid) relative to the introduced compounds of zirconium and titanium in excess equimolar ratio, or lacking. The molar ratio of ketocarboxylic acids of the formula I to the compound of the transition metal may be from 20:1 what s the invention relates to a method, in which the transition metal compound is a compound of zirconium or titanium.

Salts of alkaline earth metals, salts of transition metals and coordination compounds of transition metal compounds of the formula I can also form more complexes with the free acid (formula I), with water or with other anions hydroxide, which are available in the reaction medium. In the case of acetates of the metals or metal alcoholate anions acetates or alcoholate anions may be contained in the compounds of the formula I according to the invention.

Based on the above percentage by weight metal content in the compounds of the formula I according to the invention can be different. Thus, particularly preferred according to the invention, the complexes of zirconium 3-(4-methylbenzoyl)propionic acid can be a zirconium content of from 5 to 50 wt.%, mostly from 10 to 40 wt.%.

The structure of complexes of zirconium according to the invention are not completely understood. The total formula of the complexes of zirconium 3-(4-methylbenzoyl)propionic acid (R= 3-(4-methylbenzoyl)propionate) according to the invention are given in examples (cf. examples 2 to 14):

ZrO(OH)(O2CR)6,6 HO2CR; ZrO(OH)(O2CR) 2,9 HO2CR;

ZrO(OH)(O2CR)0,3 HO2CR; ZrO(OH)(O22CR)0,3 HO2CR; ZrO2ZrO(OH)(O2CR);

Zr(OC3H7)3(O2Cr);

ZrO(OH)(O2CR)0,48 HO2CR; Zr(OC3H7)2; Zr(OC4H9)3(O2CR) or

Zr(OC3H7)3O2CR.

Therefore, the present invention relates also to the products obtained by the conversion of the compounds of formula I or its alkali metal salt with a compound of alkaline earth metal or transition metal.

Especially, it is advisable to dissolve the compound of formula I with a base, for example, at least one equivalent of an aqueous solution of alkali metal hydroxide and then mixed with an aqueous solution of compounds of alkaline earth metal or transition metal. The compounds of formula I according to the invention is filtered or extracted from the reaction medium with an organic solvent, such as ethyl ester, acetic acid or dichloromethane.

The compounds of formula I (free acid and salts and complexes according to the invention are known, and many of them are commercially available, or they can be obtained, as described in Houben-Weyl, Methods der Organischen Chemie, volume VIII, page 382 (1952) and volume. E5 pages 398 - 399 (1985) - (Methods of organic chemistry). For example, allir is their anhydrides gives compounds of formula with excellent outputs.

Introduced compounds of alkaline earth metals or transition metals are, for example, salts, ORGANOMETALLIC compounds or inorganic base metals or mixtures thereof.

Examples of salts is the halides (especially chlorides), nitrates, carbonates, sulfates, and we can talk about the salts of bases, such as lanthanum chloride, yttrium chloride, ferric chloride, titanium tetrachloride, zinc chloride, calcium chloride, manganese chloride, cobalt chloride, cerium chloride, zinc nitrate, manganese nitrate, cobalt nitrate, cerium nitrate, iron nitrate, calcium nitrate, lanthanum nitrate, yttrium nitrate, zirconium sulfate, ferrous sulfate, manganese sulfate, cobalt sulfate, cerium sulfate, chloride of zirconium oxide, chloride oxides of titanium, zirconium acetate, zinc acetate, manganese acetate, cobalt acetate, lanthanum acetate, calcium acetate, zirconium carbonate, zinc carbonate, manganese carbonate, cobalt carbonate and calcium carbonate.

Examples organometallics compounds are primarily alcoholate, such as propoxy zirconium, isopropoxide zirconium, n-piperonyl zirconium, n-propoxy titanium, isopropoxide titanium, atoxic titanium and n-piperonyl titanium.

Examples n the tion and calcium amide.

As a solution of the alkali metal hydroxide solution using potassium hydroxide or sodium hydroxide, preferably sodium hydroxide solution.

The precipitation of the salts of alkaline earth metals and transition metal complexes of the formula I according to the invention is produced preferably at room temperature.

Salts of alkaline earth metals, salts of transition metals and transition metal complexes of compounds of the formula I according to the invention can be used as corrosion inhibitors in compositions for coatings. As such they can be added to all liquid or solid organic materials.

The preferred composition for coating is a paint and varnish material. Especially preferred water-based coating.

The paint tools are, for example, lacquers, paints or varnishes. They always contain an organic film-forming binder along with other optional components.

Preferred organic film-forming binder means are epoxy resin, polyurethane resin, polyester resin, acrylic resin and copolymer resins, polyvinyl resins, phenolic sredstva for coatings applied all the usual binders for solvent, but especially for water lacquer compositions. An example for such binders are epoxy resins, polyurethane resins, aminoplast resin or mixture of such resins; water dispersion or solution of an acidic resin.

Of particular interest are the organic film-forming binders for aqueous compositions for coating, as, for example, alkyd resins; acrylic resins; a two-component epoxy resins; polyurethane resins; polyester resins; which are usually saturated; water-soluble phenolic resin or formed dispersion, water-soluble urea resins; resins based on vinyl/crisoprodol.

In relation to specific characteristics of an alkyd resin may be a water-soluble system of alkyd resins, which can be used air-dried or in the form of hot drying in combination with water-soluble melamine resins; we can talk about dried by oxidation, air-dried, or thermal drying system, which choice is used in combination with the aqueous dispersions based on acrylic resins or copolymers, with vinylacetate etc.

Acrylic resin can depict the malls or copolymers with vinyl monomers, such as vinyl acetate, styrene or butadiene. These systems can be a dried up air systems or hot drying.

Water-soluble epoxy resin are used in combination with suitable polyaminoamide means of stitching excellent mechanical and chemical resistance. When applying liquid epoxy resins can be waived supplements from organic solvents to aqueous systems. The use of solid resins or dispersions, solid resins normally requires additives minor amounts of solvents to improve film formation.

Preferred epoxy resins are epoxy resins based on aromatic polyhydric alcohols, especially on the basis of bisphenol. Epoxy resin is used in combination with the means of stitching. When using the latter we can talk especially about amino or hydroxyquinoline compounds, acid, acid anhydride or acid Lewis. Examples of these are polyamides, polyaminoamide, polymers based on polysulfides, polyphenols, bertoldi and their complex compounds, polycarboxylic acid, 1,2-anhydrides of dicarboxylic acid or dianhydride pyromellitic acid.

Polyurethane lname groups, and secondly, from aliphatic or aromatic polyisocyanates.

Suitable polyvinyl resins are, for example, polyvinyl butyral, polyvinyl acetate or copolymers.

Suitable phenolic resins are synthetic resins in the synthesis of phenols which constitute a major component, therefore, primarily phenolic resin, crenoline resin, Xylenol resin and resorcinol-formaldehyde resins, alkylphenol resins and condensation products of phenols with acetaldehyde, furfural, acrolein or other aldehydes. Of interest also modified phenolic resin.

Compositions for coating may additionally contain one or more components from the group of pigments, dyes, fillers, controls fluidity, dispersants, thixotropic agents, adhesives, antioxidants, light stabilizers or catalysts for curing. They can also contain other known corrosion protection agents, such as anti-corrosive pigments such as phosphate or bortagaray pigments or pigments based on metal oxides, or other organic or inorganic corrosion inhibitors, for example salts of nitro the cops are, for example, titanium dioxide, iron oxide, aluminum pigment or phtalocyanine blue.

Examples of fillers are talc, alumina, aluminium silicate, barytes, mica or silica. The corrosion inhibitors according to the invention can also be applied to the media. This is especially suitable powdered fillers or pigments.

Means for monitoring the flow and thixotropic tools are based on modified bentonites.

A means of improving adhesion are based on silanes.

Next advantage is the addition of basic fillers or pigments, which are system-specific binding agents have a synergistic effect on the inhibition of corrosion. Examples of such basic fillers and pigments are calcium carbonate or magnesium carbonate, zinc oxide, zinc carbonate, zinc phosphate, magnesium oxide, aluminum oxide, aluminum phosphate, or mixtures thereof. The main examples of organic pigments are pigments based aminoanthraquinone.

The corrosion inhibitors according to the invention can be added to a paint and varnish material during its manufacture, for example during the distribution of the pigment grinding, or u can also apply for pre-treatment of metal surfaces.

Salts of alkaline earth metals, salts of transition metals and transition metal complexes of compounds of the formula I according to the invention should be used in amount of from 0.01 to 20 wt.%, mainly from 0.05 to 5 wt.% in terms of the total weight of the composition for coating.

Coating materials can be applied onto the substrate by conventional means, for example by spraying, dipping, smearing, or electrodeposition. Often put several layers. The corrosion inhibitors added to the first place in the ground layer (first coating layer), because they act primarily on the border of the metal layer of paint. But they can also be added to the intermediate layer or the covering layer. Depending on whether the binder is dried physically or chemically oxidized resin or thermosetting, or utverzhdenii irradiation of the resin, the curing of the coating is carried out at room temperature or by heating (thermal drying) or by irradiation.

Primarily the means for covering is a ground coating (first coating layer) for metal substrates, such as iron, steel, copper, zinc or aluminum, and their alloys.

Consequently, the developments of the formula I according to the invention have the advantage of they have a positive effect on the adhesion of the coating metal and not have any adverse effects on the storage stability of the composition for coatings according to the invention.

Therefore, the preferred embodiment of the present invention is the use of salts of alkaline earth metals, transition metal salts and transition metal complexes of compounds of the formula I as corrosion inhibitors in compositions for coating metal surfaces.

The following examples explain in detail the invention.

Example 1: Obtaining zinc salts 3-(4-methylbenzoyl)propionic acid (compound (101), table 1).

To a solution of 38.4 g (0.20 mol) of 3-(4-methylbenzoyl)propionic acid in 200 ml of 1.0 n sodium hydroxide solution is added dropwise with thorough stirring, a solution of 59.5 g (0.20 mol) of uranyl nitrate zinc [Zn(NO3)26H2O] in 200 ml of water. The precipitate is filtered, thoroughly washed several times with water and dried in a vacuum Cabinet at 50oC. Get a salt of zinc 3-(4-methylbenzoyl)propionic acid, melting point -220oC (compound (101), table 1).

By analogy with Example 1 from manganese nitrate, cobalt nitrate, cerium nitrate, Nitra connection from (102) to (108) cf. table 1).

The definition of R in Table 1 also applies to Examples 2 to 14 and 16.

Example 2: Obtain the zirconium complex of 3-(4-methylbenzoyl)propionic acid (compound (109)) zirconium sulfate.

In a solution of 19.2 g (0.10 mol) of 3-(4-methylbenzoyl)propionic acid in 100 ml of 1.0 n sodium hydroxide solution is added dropwise with thorough stirring, a solution of 18.3 g (0.05 mol) of zirconium sulfate (22,8% zirconium) in 40 ml of water. The precipitate is filtered, well washed several times with water and dried in a vacuum Cabinet at 50oC. Receive the zirconium complex of 3-(4-methylbenzoyl)propionic acid (compound (109)). Elemental analysis calculated for ZrO(OH)(O2CR) 6,6 HO2CR: Zr 5,8%; C 63,4%; H, 5.8 percent; HO2CR to 80.1%. Found: Zr 7,4%; C 58,6%; H, 5.6 percent; H2O 2.3 PERCENT; HO2CR 79,8%

Example 3: Obtaining zirconium complex of 3-(4-methylbenzoyl)propionic acid (compound (110) with zirconium sulfate.

In the solution 76.9 g (0.40 mol) of 3-(4-methylbenzoyl)propionic acid in 400 ml of 1.0 n sodium hydroxide solution is added dropwise with thorough stirring, a solution of 35.5 g (0,089 mol) of zirconium sulfate (22,8% zirconium) in 70 ml of water. The precipitate is filtered, well washed several times with water and dried in a vacuum Cabinet at 50oC. Sing for ZrO(OH)(O2CR) 2,9 HO2CR: Zr 10,4%; C 59,0%; H, 5.4 percent; HO2CR 63,8%. Found: Zr 9,4%; C 58,3%; H, 5.4 percent; H2O 2,0%; HO2CR 64.2% OF

Example 4: Obtaining zirconium complex of 3-(4-methylbenzoyl)propionic acid (compound (111) with chloride of zirconium oxide.

In the solution 57,7 g (0.30 mol) of 3-(4-methylbenzoyl)propionic acid in 300 ml of 1.0 n sodium hydroxide solution is added dropwise with thorough stirring, a solution of 28.1 g (0,115 mol) of the chloride of zirconium oxide (37,2% zirconium) in 55 ml of water. The precipitate is filtered, well washed several times with water and dried in a vacuum Cabinet at 50oC. Receive the zirconium complex of 3-(4-methylbenzoyl) propionic acid (compound (111)). Elemental analysis calculated for ZrO(OH)(O2CR) 0,3 HO2CR: ZR 24,5%; C 46,0%; H 4.2%; HO2CR 15.5 per cent. Found: Zr 25,2%; H 48,8%; N 4,6%; H2O 3.2 PERCENT; HO2CR 8,7%

Example 5: get the zirconium complex of 3-(4-methylbenzoyl)propionic acid (compound (112) with chloride of zirconium oxide.

In a solution of 19.2 g (0.10 mol) of 3-(4-methylbenzoyl)propionic acid in 100 ml of 1.0 n sodium hydroxide solution with thorough stirring, add dropwise a solution of 14.3 g (0,058 mol) of the chloride of zirconium oxide (37,2% zirconium) in 30 ml of water. The precipitate is filtered, well washed several times with water and dried in vacuumatic analysis, calculated for ZrO(OH)(O2CR) 0,7 HO2CR: Zr 20,3%; C to 49.9%; H, 4.6 percent; HO2CR 29,9%. Found: Zr 19,2%; C 48,3%; H, 4.7 percent; H2O 5,5; HO2CR 40,0%

Example 6: the Receipt of the zirconium complex of 3-(4-Methylbenzoyl)propionic acid (compound (113) with zirconium acetate.

In a solution of 19.2 g (0.10 mol) of 3-(4-methylbenzoyl)propionic acid in 100 ml of 1.0 n sodium hydroxide solution with thorough stirring, add dropwise a solution to 37.2 g (0,075 mol) of zirconium acetate (18,4% zirconium) in 60 ml of water. The precipitate is filtered, well washed several times with water and dried in a vacuum Cabinet at 50oC. Receive the zirconium complex of 3-(4-methylbenzoyl)propionic acid (compound (113)). Elemental analysis calculated for ZrO(OH)(O2CR)0,8(acetate)of 0.2: Zr of 31.6%; C 38,2%; H 3,6%; acetate of 4.1%. Found: Zr 32,6%; C and 38.6%; H, 4.1 per cent; H2O 2.5%; acetate of 5.7%.

Example 7: the Receipt of the zirconium complex of 3-(4-methylbenzoyl)propionic acid (compound (114) with zirconium acetate.

In a solution of 9.60 g (0.05 mol) of 3-(4-methylbenzoyl)propionic acid in 50 ml of 1.0 n sodium hydroxide thorough stirring, add dropwise a solution of 148, 8 persons g (0.30 mol) of zirconium acetate (18,4% zirconium) in 100 ml of water. Zadok was filtered, well washed several times with water and dried in in the. elementry analysis calculated for ZrO(OH)(O2CR)0,5(acetate)0,5: Zr 36,6%; C 31,3%; H 3.2%; acetate of 11.8%. Found: Zr 34,9%; C 29,7%; H, 3.8 percent; H2O 3,2%; acetate of 12.8%.

Example 8: the Receipt of the zirconium complex of 3-(4-methylbenzoyl)propionic acid (compound (115) with carbonate of zirconium.

A suspension of 15.0 g (56.0 mmol) of zirconium carbonate (34% zirconium) and 15.0 g (78,0 mmol) 3-(4-methylbenzoyl)propionic acid in 150 ml of water is heated under vigorous stirring for 2 hours to 90oC. Then the reaction mixture is cooled, water is decanted and the residue extracted with complex ethyl ester of acetic acid. The solvent is concentrated on rotary vacuum evaporation apparatus, and the residue is dried in high vacuum at 50oC. Receive the zirconium complex of 3-(4-methylbenzoyl)propionic acid (compound 115)). Elemental analysis calculated for ZrO(OH)(O2CR) 0,3 HO2CR: Zr 24,5%; C 46,0%; H 4.2%; HO2CR 15.5 per cent. Found: Zr 21,0%; C 48,1%; H, 4.6 percent; H2O 0,4%; HO2CR 16.5 per cent.

Example 9: receipt of the zirconium complex of 3-(4-methylbenzoyl)propionic acid (compound (116) with carbonate of zirconium.

Suspension of 45.0 g (168 mmol) of zirconium carbonate (34% zirconium) and 15.0 g (78,0 mmol) 3-(4-methylbenzoyl)propionic acid in 150 ml water load, continuum, the residue is extracted with complex ethyl ester, acetic acid and dried in high vacuum at 50oC. Receive the zirconium complex of 3-(4-methylbenzoyl)propionic acid (compound 116)). Elemental analysis calculated for ZrO2ZrO(OH)(O2CR): Zr 41,6%; C to 30.1%; H, 4.6 per cent. Found: Zr 37,7%; C 26,8%; H, 3.7%; and H2O 2,7%.

Example 10: the Receipt of the zirconium complex of 3-(4-methylbenzoyl)propionic acid (compound (117) with n-propoxide Zirconia.

The solution for 44.3 g (0.10 mol) of n-propoxide zirconium (20,6% zirconium) and 19.2 g (0.10 mol) of 3-(4-methylbenzoyl)propionic acid in 200 ml of dry toluene is stirred under nitrogen atmosphere for 12 hours at 50oC. Then the reaction mixture is cooled and concentrated by rotary vacuum evaporation apparatus, and the residue is dried in high vacuum at 50oC. Receive the zirconium complex of 3-(4-methylbenzoyl)propionic acid (compound (117)). Elemental analysis calculated for Zr(OC3H7)3(O2CR): Zr 19,8%; C 52,2%; H 7,03%. Found: Zr 20,0%; C 52,4%; H 6,75%.

Example 11: the Receipt of the zirconium complex of 3-(4-methylbenzoyl)propionic acid (compound (118) with carbonate of zirconium.

A suspension of 50.0 g (0.18 mol) of zirconium carbonate (32.8% zirconium) and 50 g (0.26 mol) of 3-(4-methylbenzoyl)propionic who eat the reaction mixture is stirred for 45 minutes at 83oC. warm the organic phase is separated and concentrated in a rotary vacuum apparatus to a residual volume of 200 ml. and Then the solution under vigorous stirring is introduced into 2000 ml of gasoline. Resulting precipitate is filtered off and dried in high vacuum at 50oC. Receive the zirconium complex of 3-(4-methylbenzoyl)propionic acid (compound (118)). Elemental analysis calculated for ZrO(OH)(O2CR) 0,48 HO2CR: Zr 22,4%; C 47,9%; H, 4.4 percent; HO2CR 22,65%. Found: Zr 22,2%; C 47,7%; H, 4.8 percent; H2O 0,75%; HO2CR 20,%.

Example 12: the Receipt of the zirconium complex of 3-(4-methylbenzoyl)propionic acid (compound (119) with n-propoxide Zirconia.

The solution for 44.3 g (0.10 mol) of n-propoxide zirconium (20,6% zirconium) and of 38.4 g (0.20 mol) of 3-(4-methylbenzoyl)propionic acid in 200 ml of dry toluene is stirred under nitrogen atmosphere for 12 hours at 50oC. Then the reaction mixture is cooled, concentrated on rotary vacuum evaporation apparatus, and the residue is dried in high vacuum at 50oC. Receive the zirconium complex of 3-(4-methylbenzoyl)propionic acid (compound (119)). Elemental analysis calculated for Zr(OC3H7)2(O2CR)2: Zr 15,4%; C 56,8%; H, 6.1 Per Cent. Found: Zr 15,1%; C 56,7%; H 6,2%.

Example 13: Getting Easter to 43.2 g (0.10 mol) of n-butoxide zirconium (21,1% zirconium) and 19.2 g (0.10 mol) of 3-(4-methylbenzoyl)propionic acid in 200 ml of dry toluene is stirred under nitrogen atmosphere for 12 hours at 50oC. Then the reaction mixture is cooled, concentrated on rotary vacuum evaporation apparatus, and the residue is dried in high vacuum at 50oC. Receive the zirconium complex of 3-(4-methylbenzoyl)propionic acid (compound (120)). Elemental analysis calculated for Zr(OC4H9)3(O2CR): Zr 18,2%; C 55,0%; H, 7.6 percent. Found: Zr 19,3%; C 54,2%; H 7,0%.

Example 14: the Receipt of the zirconium complex of 3-(4-methylbenzoyl)propionic acid (compound (121) isopropoxide Zirconia.

In a solution of 17.3 g (0.05 mol) of isopropoxide zirconium (26,4% zirconium) and 9.6 g (0.05 mol) of 3-(4-methylbenzoyl)propionic acid in 200 ml of dry toluene is stirred under nitrogen atmosphere for 12 hours at 50oC. Then the reaction mixture is cooled, concentrated on rotary vacuum evaporation apparatus, and the residue is dried in high vacuum at 50oC. Receive the zirconium complex of 3-(4-methylbenzoyl)propionic acid (compound (121)). Elemental analysis calculated for Zr(OC3H7)3(O2CR): Zr 19,8%; C 52,2%; H 7,0%. Found: Zr 23,8%; C 47,4%; H 5,8%.

Example 15: the Receipt of the zirconium complex of 3-(4-chlorobenzoyl)propionic acid (compound (122) with carbonate of zirconium.

A suspension of 30.0 g (to 0.108 mol) of zirconium carbonate (32.8% zirconium) and the s 30 minutes prior to the 90oC. Then the reaction mixture is stirred for 45 minutes at 90oC. Then decanted while hot and the residue is extracted with complex ethyl ester of acetic acid. The solvent is concentrated on rotary vacuum apparatus and the residue is dried in high vacuum at 50oC. Receive the zirconium complex of 3-(4-chlorobenzoyl)propionic acid (compound (122)). Elemental analysis calculated for ZrO(OH)(O2CR') 0,47 HO2CR: Zr 20,9%; C 40,5%; H 3,1%; Cl 12.0 percent; HO2CR' is 22.9%. Found: Zr 20,7%; C 40,1%; H 3,3%; Cl 11.6 percent; H2O 0,6%; HO2CR' 29,7%.

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Example 16: Obtaining complex titanium 3-(4-methylbenzoyl)propionic acid (compound 123) with n-propoxide titanium.

A solution of 14.2 g (50 mmol) of n-propoxide titanium (IV) and 9.6 g (50 mmol) 3-(4-methylbenzoyl)propionic acid in 100 ml of dry toluene is stirred under nitrogen atmosphere for 12 hours at 50oC. Then the reaction mixture is cooled and concentrated by rotary vacuum evaporation apparatus, and the residue is dried in high vacuum at 50oC. Get complex titanium 3-(4-methylbenzoyl)propionic acid (compound (123)). Elemental analysis calculated for Ti(OC3H7)3(O2CR): Ti 11,5%; C 57,72%; H, 7.8 per cent. Found: Ti 11,5%; C 56,5%; H, 7.6 Percent.

Example 17: IP is benzoyl)propionic acid in the acrylic dispersions based on Maincote HG-54 as corrosion inhibitors.

To obtain a composition for coatings based on Maincote HG-54 used parts 1 - 8 (without additives) or the components 1 to 9 (composition with an additive in the sequence (cf. Table 2).

The total solids content of 47%; pH value of 8 to 8.5; a)Methylcarbitol: simple diethylethylenediamine ether (Union Carbide); (b) Orotan 165: auxiliary dispersing agent (Rohm & Haas; c)Triton CF 10: non-ionic wetting agent (Rohm & Haas); d)Drew Plus TS 4380: defoamer (Drew Chem. Corp. ); e)Acrisol RM 8: nonionic thickener (Rohm & Haas; f)Bayferrox 130 M: red zhelezookisnye pigment (Bayer AG); g)Millicarb: calcium carbonate (Omya); h)Maincote HG-54: acrylic dispersion, 41.5% in deionized water (Rohm & Haas; i)Texanol: coalescent (Eastman Chem. Prod., Inc.); k) Dibutyl phthalate: plasticizer (Eastman Chem. Prod. , Inc. ) l) sodium nitrite: inhibitor rust (Fluka); m)Drew T 4310: non-ionic defoamer (Drew Chem. Corp.).

When using rapid mixer with the number 3000 revolutions/minute components is dispersed to the fineness of grind or grit grinding < 15 μm. The result of the dispersion thus obtained pigment paste appreciate the determination of corrosion according to the invention applies to the entire solid matter of the composition without the additive (all solid material: 47%). Therefore, the addition of 1% corrosion inhibitor in 100 g of a dispersion means, for example, the number of 0.47, For preparation of a composition for coating components 1 to 16 in Table 2 adds at low speed stirring (1000 rpm/minute) in a specified sequence. Then control the pH value of the composition and before applying, if necessary, establish by using ammonia solution (25%) the pH from 8 to 8.5.

Coating composition for coating can be performed without dilution by airless spray or after dilution with smearing, running or conventional spray. For the application of traditional spray formulations diluted to spraying viscosity of 22 to 23 seconds (Ford-Becher 4; DIN 53 211. Diluent: butylglycol/deionized water = 1:1 (g/g).

The composition is applied to steel sheets (10 times 15 cm) type Q-panel R (cold rolling, raw steel; manufacturer of The Q-Panel Company, Cleveland, USA) with a layer thickness, which after drying of 50 μm (drying conditions: 10 days at room temperature).

Before testing resistance applying device for radial sawing Apply (model 205; manufacturer/sales: firm Lau, 5870, Heme is for (i.e. in parallel to the longer edge of the sheet). Edges protected with protective edgesIcosit 255; manufacturer: Inertol AG, Winterhur, Switzerland).

Samples immediately after a quick test on resistance is tested in salt spray (DIN 50 021 SS) for 168 hours and tested in a humidity chamber ASTM D - 4585-87, American society for testing and materials) for 330 hours. The results are summarized in Tables 3-6. The evaluation of the results produced based on the relevant DIN standards for evaluation code indicating the ratio of the corrosion protection CPF (Corrosion Protection Factor). CPF is prepared by adding the evaluation of the coating (film) and assessment of steel and is a maximum of 12 points. Individual maximum values for the coating (film) and for steel is 6 points. The larger the number, the better protection against corrosion.

Example 18: a Test of salts of alkaline earth metals, transition metal salts and transition metal complexes of 3-(4-methylbenzoyl)propionic acid systems alkyd resin based on Bayhydrol B 130 H as corrosion inhibitors.

Similar to the description in Example 17 to obtain a composition for coatings based on Bayhydrol B 130 H used components 1-6 (composition without the obsession solids: 56,1%; a)Bayhydrol B 130 H: 30% in deionized water, alkyd resin, water-soluble (Bayer AG); b)Servosyn WEB (8%) of cobalt drier (8% metal) (Servo Delden B. V.); (c)Ascinin R: the inhibitor film on the basis of the oxime (Bayer AG); d) Bayferrox 130 M: red zhelezookisnye pigment (Bayer AG); e) Heladol 10: calcium carbonate (Lange); f)Mikrotalk AT Extra: micronized talc (Norwegian); g)Aerosil 300: thickener and thixotropic agent, chemically pure silicic acid (Degussa).

When using rapid mixer at 3000 revolutions/minute or when using, for example, horizontal ball mill components is dispersed to the fineness of grind or grit grinding < 15 μm. The result of the dispersion thus obtained pigment paste assess the extent of grandmere (ISO 1524). Introduced a number of corrosion inhibitors according to the invention applies to the entire solid matter of the composition without the additive (all solid: 56,1%). Therefore, the addition of 1% corrosion inhibitor in 100 g of the composition indicates, for example, the number of 0.56, For preparation of a composition for coating components 8 to 12 in Table 7 add at low speed stirring (1,000 rpm, the, sushestvennee tests in salt spray (168) hours and the determination of the coefficients of corrosion protection CPF produce analogous to Example 17. The results are summarized in Table 8. The larger the number, the better protection against corrosion.

Example 19: a test of salts of alkaline earth metals, transition metal salts and transition metal complexes of 3-(4-methylbenzoyl)propionic acid as a corrosion inhibitor in aqueous dispersions based on copolymers of ester of acrylic acid/styrene copolymer (Acronal S 760).

To obtain a composition for coatings based on Acronal S 760 components 1-5 first pre-mix, then add the components 7 and 8 (composition without corrosion inhibitor) or 6-8 (composition with corrosion inhibitor, compound (115), Example 8) in the sequence (cf. table 9).

The total solids content: 57%; a)Pigmentverteiler NL: auxiliary dispersant pigment (BASF AG); b)Acronal S 760: dispersion of a copolymer of ester of acrylic acid-styrene (water dispersion, (BASF AG); c)Shellsol D 60: lacquer gasoline (aliphatic solvent, Shell); d)Agitan 280: degasser and antifoam (Munzing Chemie GmbH); e)Millcarb: calcium carbonate BASF AG).

The resulting pigment paste is dispersed using a horizontal ball mill or similar to the grain size < 15 μm. The grain is evaluated on the basis of the magnitude of grandmere (ISO 1524).

To obtain a varnish (varnish coating) components 9 - 12 then add in the sequence (table 9). The application produces traditional spray. Depending on the desired viscosity of the finished paint can be diluted by adding butyldiglycol/deionized water (1:1 g/g).

The lacquer as described in Example 17, to produce steel sheets type Bonder (cold rolling, whether steel, manufacturer: Chemetall, Frankfurt/main) layer thickness, which after drying is 100 μm (drying conditions; 14 days at room temperature).

Exercise testing in salt spray (168 hours) and the determination of the coefficients of corrosion protection CPF produce analogous to Example 17. The results are summarized in Table 10. The larger the number, the better protection against corrosion.

1. Salts of alkaline earth metals, salts of transition metals or transition metal complexes of compounds of the formula I

< / BR>
where R1represents hydrogen;

R2, Ralkyl;

n denotes 2,

excluding the calcium salt of 3-(3-chloro-4-isopropylbenzyl) propionic acid.

2. Connection on p. 1, where at least two of the residues R1-R5represent hydrogen.

3. Connection on p. 1, where the metals are calcium, titanium, manganese, iron, cobalt, zinc, yttrium, zirconium, lanthanum or cerium.

4. Connection on p. 1, where the metal is zirconium.

5. Connection on p. 1, where R1, R2, R4and R5denote hydrogen, R3represents hydrogen, C1-C4-alkyl or chlorine, n is 2 and the metals are calcium, titanium, manganese, iron, cobalt, zinc, yttrium, zirconium, lanthanum or cerium.

6. Composition for coating containing (a) an organic film-forming binder and (b) corrosion inhibitor, characterized in that as the corrosion inhibitor contains a corrosion inhibitor, representing at least salts of alkaline earth metals, salts of transition metals or transition metal complexes of compounds of the formula I under item 1

< / BR>
where R1represents hydrogen;

R2, R3, R4and R5independently from the others is in p. 6, where the composition for the coating is the tool for coating.

8. The composition according to p. 6, where he is a water tool coatings.

9. The composition according to p. 6, where component a) is an epoxy resin, polyurethane resin, polyester resin, acrylic resin, crisoprodol resin, polyvinyl resin, phenolic resin, alkyd resin or mixture of such resins.

10. The composition according to p. 6, additionally containing one or more components from the group of pigments, dyes, fillers, controls fluidity, dispersant, means thixotropy, medium adhesion, antioxidants, light stabilizers or catalysts for curing.

11. The composition according to p. 6, where component b) is in an amount of 0.01 - 20%, calculated on the total weight of the composition for coating.

12. The way to protect corroding metal substrate, providing a coating on the substrate composition for coating, characterized in that, as a composition for coating using the composition according to p. 6 and then it is dried and/or utverjdayut.

13. The method of obtaining salts of alkaline earth metals, transition metal salts or transition metal complexes of compounds of the formula I according to the action with the connection alkaline earth metal or transition metal compound.

14. The method according to p. 13, characterized in that compounds of the alkali earth metal or transition metal used salt, ORGANOMETALLIC compound or inorganic metal base.

15. The method according to p. 13, characterized in that the molar ratio ketocarboxylic acids of the formula I to the compound of the transition metal is from 20 : 1 to 1 : 10.

16. The method according to p. 13, characterized in that the transition metal compound is a compound of zirconium or titanium.

 

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