Crystalline complex compounds derivatives of the research with carbon keto acid as corrosion inhibitors, method for their preparation and composition for coating and method of protection against corrosion

 

(57) Abstract:

Proposed crystalline complex compounds of formula I, where R1, R2, R3, R4, R5independently of one another represent hydrogen, halogen, C1-C15-alkyl or C6-C10-aryl, and at least one of the radicals R1-R5denotes hydrogen, halogen or1-C15-alkyl, R10is1-C15-alkyl, a m represents the integer 2, which can be used as corrosion inhibitors in compositions for coating metal surfaces. Also disclosed are a composition for coating, method for protecting a metal substrate from corrosion and method of producing compounds. The invention can be applied in coatings to protect metal surfaces. 5 C. and 10 C.p. f-crystals, 11 PL.

This invention relates to complexes of derivatives research with ketocarboxylic acids, compositions for coatings containing organic film-forming binder, preferably, the means for covering, and a new corrosion inhibitors, and their use in coatings to protect metal surfaces.

The use of alkaline, the local and described, for example, in US - A - 4909987, US - A - 5128396 or EP - A - 496555.

From EP - A - 300325, example 7, as a result of the exchange reaction of equivalent 3-benzoylpropionic acid with equivalent research in ethanol formed crystalline salt, which, as expected, is one part acid and one part of the grounds.

It was found that the passage of the exchange reaction ketocarboxylic acid derivatives of the research without solvent or in the presence of protopage solvent formed of crystalline complexes, the composition of which consists of two parts acid and only one part of the Foundation. These crystalline complex compounds most suitable as corrosion inhibitors in coating compositions for protecting metallic surfaces, as well as for pre-treatment of metal substrates. Crystalline complex compounds do not affect the lacquer system, in particular, water lacquer system and in coating compositions differ exceptionally good stability during storage. They are suitable both for temporary and for permanent protection against corrosion. In addition, these lacquer systems are extremely vlagoperenosu.

2, R3, R4and R5independently of one another represent hydrogen, halogen, nitro, cyano, CF3C1-C15-alkyl, C5-C12-cycloalkyl, C2-C15alkenyl, C1-C12-halogenated, C1-C12-alkoxy, C1-C12-alkylthio, unsubstituted or substituted C1-C4-alkyl, C6-C10-aryl; unsubstituted or substituted C1-C4-alkyl, C6-C10-aryloxy; unsubstituted or substituted on the aryl residue 1 to 3 C1-C4-alkyl, C7-C12-arylalkyl;

- CO2R6, - COR6or with at least one of the residues R1to R5means hydrogen, halogen or C1-C15-alkyl; residues R1and R2, R2and R3, R3and R4or R4and R5together with the carbon atoms to which they are linked, form a benzo - or cyclohexadiene ring, R6means C1-C20- alkyl interrupted by oxygen, sulfur or C2-C20- alkyl; unsubstituted or substituted on the aryl residue 1 to 3 C1-C4- alkyl, C7-C12- arylalkyl, R7and R8independently of one another represent hydrogen, C1-C24- alkyl or n is Il, R10represents C1-C15- alkyl interrupted by oxygen, sulfur or C2-C20- alkyl, C5-C12- cycloalkyl, C2-C15alkenyl, C1-C12- alkoxy, C1-C12- alkylthio, unsubstituted or substituted C1-C4- alkyl, C6-C10- aryl; unsubstituted or substituted C1-C4- alkyl, C6-C10- aryloxy; unsubstituted or substituted on the aryl residue 1 to 3 C1-C4- alkyl, C7-C12- arylalkyl, and m means an integer from 2 to 5.

Halogen means, for example, fluorine, chlorine, bromine or iodine. Preferred are fluorine, chlorine or bromine, in particular chlorine or bromine.

Alkyl with up to 24 carbon atoms means a branched or non-branched residue, such as methyl, ethyl, propyl, isopropyl, n - butyl, dibutil, isobutyl, tert-butyl, 2-ethylbutyl, n - pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n - hexyl, 1-etylhexyl, n-heptyl, isoheptyl, 1,1,3,3-TETRAMETHYLBUTYL, 1-methylheptan, 3-methylheptan, n - octyl, 2-ethylhexyl, 1,1,3-trimethylpentyl, 1,1,3,3-TETRAMETHYLBUTYL, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylene, tridecyl, tetradecyl, pentadecyl, hexade carbon atoms. The preferred value of R3is C1-C4- alkyl, in particular methyl. The preferred value of R10is C1-C4- alkyl, in particular ethyl.

C5-C12- cycloalkyl means, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl or cyclododecyl. Preferred is cyclohexyl.

Alkenyl from 2 to 15 carbon atoms means a branched or non-branched residue, for example, vinyl, 2-propenyl (alkyl), 2-butenyl, 3-butenyl, Isobutanol, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl or ISO-dodecenyl. Preferred is alkenyl from 3 to 12, especially 3 to 8, for example, from 3 to 6, especially 3 to 4 carbon atoms.

Halogenated with a content of up to 12 carbon atoms means a branched or non-branched residue, such as, for example, chloromethyl, methyl bromide, forproper, chloropentyl, chlorhex, character, hardell or hardtail. It is preferable to halogenate from 3 to 8, in particular from 3 to 6 carbon atoms.

Alkoxy with up to 12 carbon atoms means a branched or non-branched residue, such as, for example, methoxy, ethoxy, propoxy, isopropoxy, who is alkoxy with 1 to 8, in particular, from 1 to 4 carbon atoms.

Alkylthio with a content of up to 12 carbon atoms means a branched or non-branched residue, such as, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutyric, pentylthio, isopentyl, hexylthio, Reptilia, octylthio, decillia or dodecylthio. Preferred is alkylthio from 1 to 8, especially 1 to 4, carbon atoms.

Unsubstituted or substituted C1-C4-alkyl, C6-C10-aryl, which is mostly from 1 to 3, especially 1 or 2 alkyl groups, means, for example, phenyl, naphthyl, o-, m - or n-were, 2,3-dimetilfenil, 2,4-dimetilfenil, 2,5-dimetilfenil, 2,6-dimetilfenil, 3,4-dimetilfenil, 3, 5dimethylphenyl, 2-methyl-6-ethylphenyl, 4-tert-butylphenyl, 2-ethylphenyl, 2,6-diethylphenyl, 2-methylnaphtho, 1-methylnaphtho, 4-methylnaphtho, 2-eternity or 2,6-diacylates.

Unsubstituted or substituted C1-C4-alkyl, C6-C10-aryloxy, which contains mostly from 1 to 3, in particular 1 or 2 alkyl groups, means, for example, phenoxy, naphthoxy, o-, m - or n-methylphenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2,5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenol the 4-maternotoxic, 2 etraftaki or 2,6-diethylketone.

Unsubstituted or substituted on the aryl residue 1 to 3 C1-C4-alkyl, C7-C12-aryl-alkyl means, for example, phenyl-C1-C6-alkyl or naphthyl-C1-C2-alkyl, such as benzyl, 4-methylbenzyl, 4-tert-butylbenzoyl, 2,4-dimethylbenzyl - methylbenzyl, ,- -dimethylbenzyl, 2-phenylethyl, 2-naphthylmethyl, 1-naphthylmethyl, 1-naphtalate or 2-naphtalate. Preferred is benzyl.

Interrupted by oxygen, sulfur or alkyl with 2 to 24 carbon atoms means, for example, CH3-O-CH2-CH3-S-CH2-, CH3-NH-CH2-, CH3-N(CH3)-CH2-CH3-O-CH2CH2-O-CH2-, CH3-(O-CH2CH2-)2O-CH2-,

CH3-(O-CH2CH2-)3O-CH2or CH3-(O-CH2CH2-)4O-CH2-.

Preferred are crystalline complex compounds of formula I where at least two of the residues R1to R5are hydrogen.

m in the formula I means preferably from 2 to 4, in particular 2.

Particularly preferred are crystalline complex compounds of formula I, where R1means is on, cyano, CF3C1-C8- alkyl, C5- C7-cycloalkyl, C3- C8alkenyl, C1- C8-alkoxy, C1-C8-alkylthio, phenyl, phenoxy, benzyl, -CO2R6, -COR6or R6means C1-C12-alkyl interrupted by oxygen C2-C12-alkyl, or benzyl, and R7and R8independently of one another represent hydrogen, C1-C8-alkyl or interrupted by oxygen C2-C12-alkyl.

Also particularly preferred are crystalline complex compounds of formula I, where R10C1- C8- alkyl means interrupted by oxygen or sulfur C3-C12-alkyl, C5-C7-cycloalkyl, C3-C8alkenyl, C1-C8-alkoxy, C1-C8-alkylthio, phenyl, phenoxy or benzyl.

Also particularly preferred are crystalline complex compounds of formula I, where R1, R2and R4mean hydrogen, R3and R5independently of one another represent hydrogen, chlorine, bromine, CF3C1-C8-alkyl, cyclohexyl, C1-C8-alkoxy, phenyl, -CO2R6, -COR6or R6means C1-C8-alkyl, R7and R8UB>8-alkyl, cyclohexyl, phenyl or benzyl, and m means an integer from 2 to 4.

Of particular interest are the crystalline complex compounds of formula I, where R1, R2, R4and R5mean hydrogen and m is 2.

Of specific interest are the crystalline complex compounds of formula I, where R10means C1-C4-alkyl.

Also interesting crystalline complex compounds of formula I, where R1, R2, R4and R5are hydrogen; R3means hydrogen, C1-C4-alkyl, phenyl or chlorine; R10represents C1-C4-alkyl and m is 2.

Most preferred is a crystalline 2:1 complex of 3-(4-methylbenzoyl)propionic acid with N-ethylmorpholine /connection (101)/.

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Was carried out x-ray structural analysis of this complex compounds (101) (example 1). Shows the packing of the crystals, the numbering of the atoms in the complex compound (101). Experimental data of the crystals are given in example 1.

Packing of crystals of complex compounds (101).

The numbering of the atoms in the complex compound (101).

Table 1 shows zrenija crystalline complex compounds of formula I, according to the invention.

Therefore, another object of the invention is a new method of obtaining crystalline complex compounds of formula I, wherein the ketocarboxylic acid of the formula II

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where the General symbols are defined as in formula I, is administered in cooperation with morpholine-derived formula III

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where R10defined as in formula I, without solvent or in the presence of an aprotic solvent.

For this method unsuitable proton solvents, such as alcohols, e.g. methanol or ethanol.

The preferred reaction conditions of the method according to the invention are as follows.

Preferably the mixture ketocarboxylic acids of the formula II is heated with morpholine-derived formula III to obtain a homogeneous and transparent melt. After cooling to room temperature is the crystallization of the complex compounds of the formula I. they are Then filtered off and washed with the appropriate solvent. After drying, the precipitate formed crystalline complex compounds of formula I, according to the invention, pure for analysis.

As can be seen from examples 1, 2 and 3, in the exercise of this sposobnoe the research of the formula III. In any case, have the same crystalline complex is 2:1 formula I.

However, preferred is a method, wherein the molar ratio of ketocarboxylic acids of the formula II relative to the derivative of the research of the formula III is 4:1 to 1:4, in particular 2:1 to 1:2, for example, 1:1.

The conversion of both components is preferably in an atmosphere of inert gas such as nitrogen or argon.

The reaction temperature or melting point in the method according to the invention, depends on the physical properties used ketocarboxylic acids of the formula II and derived the research of the formula III. The preferred melting point of from 40 to 130oC, in particular from 50 to 120oC. Particularly preferred melting point for the most preferred crystalline complex compounds of formula I is 60 - 80oC.

Once the reaction mixture reaches the melting temperature and the melt is homogeneous and transparent, at this temperature, produce stirring, preferably by cooling, for 1 to 20 minutes, in particular from 1 to 10 minutes.

Precipitated crystalline complain of a number of hydrocarbons, such as naphtha, pentane, hexane, hexane - faction or gasoline. Particularly preferred is hexane.

The compounds of formula I, according to the invention is stable at room temperature and can be dried under normal pressure or high vacuum. Particularly preferably, if the crystalline complex compounds of formula I are dried in a drying Cabinet with a water-jet vacuum at a temperature of from 20 to 30oC.

If crystalline complex compounds according to the invention, dried under more severe conditions, such as elevated temperature, the derivative of the research of the formula III partially evaporates, and the complex is 2:1, according to the invention, partially destroyed. The dried product contains, as before, the semi-crystalline compound of the formula I according to the invention, but is very dirty free ketocarboxylic acid of the formula II.

The reaction ketocarboxylic acids of the formula II derived from the research of the formula III can be carried out in the presence of an aprotic solvent. Suitable for this are the same as those aprotic solvents, which are used for washing products. Preferred rustle gasoline. Most preferred are aliphatic hydrocarbons such as hexane. As the aprotic solvent can also be used an excess of the compounds of formula III.

The preferred reaction temperature in the process according to the invention with a solvent, for example, from a number of hydrocarbons, is the boiling point of the solvent.

The invention also applies to products obtained by the reaction of exchange ketocarboxylic acids of the formula II derived from the research of the formula III without solvent or in the presence of an aprotic solvent.

Ketocarboxylic acids of the formula II are known and part of them can be purchased or made, as described in Houben-vail in the "Methods of organic chemistry", T. VIII, pages 381-382 (1952), and so E5, pages 398-399 (1985). So, in the acylation according to the method of Friedel-substituted aromatic hydrocarbons (derivatives of benzene and naphthalene) with cyclic anhydrides obtain the compounds of formula II with a beautiful exit.

Derivatives of the research of the formula III are known and part of them can be purchased or made, as described in Houben-vail in the "Methods of organic chemistry", I. XI/I, page 815 (1957).

The next subject of the invention are compositions for coatings containing: a) an organic film-forming binder and (b) as corrosion inhibitor, at least one crystalline compound of formula I.

Particularly preferred is an aqueous coating. Coatings are, for example, varnishes, paints or Alif. They always contain an organic film-forming binder along with other optional components.

As the organic film-forming binder composition for coating suitable all the usual binders for aqueous spray compositions containing a solvent or not containing it. Examples of such binders are epoxy resins, polyurethane resins, resins or their mixtures, of a basic aqueous dispersion or solution of an acidic resin.

Preferred organic film-forming binders are epoxy resins, polyurethane resins, polyester resins, acrylic resins and copolymer resins, polyvinyl resins, phenolic resins, alkyd resins or mixtures of such smo is for example, alkyd resins; acrylic resins; 2-component epoxy resins; polyurethane resins; polyester resins that are formulated in the usual way; water-soluble phenolic resins or derivatives of the dispersion, water-soluble urea-formaldehyde resin; resin based on vinyl/crisoprodol.

Considered more specific alkyd resin can be applied in the form of water-soluble systems, you can use an air-dry or in the form of hot drying in combination with water-soluble melamine resins; we can talk about regarding drying, air-drying or hot drying systems that choice used in combination with the aqueous dispersions based on acrylic resins or copolymers, with vinylacetate etc., Acrylic resins can be pure acrylic resins, copolymers of esters of acrylic acid, a combination of vinyl resins or copolymers with vinyl monomers as vinyl acetate, styrene or phenylbutazone. These systems can be systems with air drying or hot drying systems.

Water-soluble epoxy resins possess in combination with the relevant polyaminoamide means the ability to education is possible to dispense additives of organic solvents to aqueous systems. When using solid resins or dispersions, solid resins usually requires the addition of small amounts of solvent, in order to improve film formation.

Preferred epoxy resins are resins based on aromatic polyhydric alcohols, in particular, on the basis of bisphenol. Epoxy resins are used in combination with means forming a cross connection. Regarding the latter, it could be, in particular, amino - or hydroxyquinoline compounds, acid, acid anhydride or acid levy. Examples for this are polyamine, polyaminoamide, polymers based on polysulfides, polyphenols, boron fluoride, and their complex compounds, polycarboxylic acid, 1,2-dicarboxylate anhydrides or Diametric pyromellitic acid.

Polyurethane resins are derived from polyesters and polybutadienes with terminal hydroxyl groups, on the one hand and aliphatic or aromatic polyisocyanates on the other hand.

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

Suitable phenolic resins are artificial starcinema formaldehyde resin, alkylphenolate resins and condensation products of phenols with acetaldehyde, furfural, acrolein or other aldehydes. Interest is also modified phenolic resin.

The coating compounds may optionally contain one or more components from the group of pigments, dyes, fillers, means for controlling the fluidity, dispersively funds, thixotropic means, means for improving adhesion, antioxidants, light stabilizers or catalysts for curing. They can also contain other known means of protection against corrosion, for example, corrosion-protective pigments, such as phosphate or brutalny pigments or metallocene pigments, or other organic or inorganic corrosion inhibitors, for example, salts nitroisophthalic acid, phosphoric ester, technical amines or substituted benzotriazole.

The additional examples of pigments are titanium dioxide, iron oxide, aluminum bronze or phthalocyanine blue.

Examples of additional fillers are talc, alumina, aluminium silicate, barytes, mica or silicon dioxide.

Means of controlling the fluidity and the Yu, based on the modified silanes.

Another advantage is the addition of basic fillers or pigments, which in certain resin systems have Energeticheskiy effect on corrosion inhibition. Examples of such basic fillers and pigments are calcium carbonate or magnesium, zinc oxide, zinc carbonate, zinc phosphate, magnesium oxide, aluminum oxide, aluminum phosphate, or mixtures thereof.

The main examples of organic pigments are pigments based on aminoanthraquinone.

Corrosion inhibitors according to the invention, can be added to the tool for coating during the manufacture of the latter, for example, during the distribution of pigment in the grinding or during the extrusion process in the case of powder varnishes, or the inhibitor is dissolved in a solvent and then introduced into the composition for cover.

Crystalline complex compounds of formula I are useful in amounts from 0.02 to 20 wt.%, mainly from 0.1 to 10 wt.%, in terms of the weight of the whole solid surface.

Coatings can be applied by conventional means to the substrate, for example, by spraying, dipping, painted inhibitors are added, first of all, in the core layer, as they primarily operate on the boundary of the metal-coating. They can also be added to the intermediate or outer layer of the coating.

Depending on whether the binder is physically, chemically or oxidative drying resin or thermosetting resin, or a resin that hardens when exposed, is the hardening of the coating at room temperature or by heating (scalding), or radiation.

Primarily the means for covering is a basic coating for metal surfaces such as iron, steel, copper, zinc or aluminum, and their alloys.

In addition to the corrosion action of the crystalline complex compounds of formula I, according to the invention have the advantage that they have a positive effect on the adhesion of the coating to the metal and do not adversely affect the storage stability of the coating compounds according to the invention.

The preferred form of the present invention is the use of crystalline complex compounds of formula I as corrosion inhibitors in compositions for okrzei metal surface, which differs in that it applied intermediate composition, which contains: a) an organic film-forming binder and (b) as corrosion inhibitor at least one crystalline compound of formula I, after applying the composition dries and/or hardens.

The following examples explain in more detail the invention. The data specified in parts or percentages relate to weight.

Example 1. Obtaining the crystalline complex of 3-(4-methylbenzoyl)propionic acid with excess N-ethylmorpholine /connection (101)/.

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11,5 g (0.10 mol) of N-ethylmorpholine and 9.60 g (0.05 mol) of 3-(4-methylbenzoyl)propionic acid are heated under nitrogen atmosphere to 60oC. Homogeneous transparent reaction solution is stirred for 10 minutes at a temperature of 60oC, and then with stirring, cooled to room temperature. The precipitate is filtered off, well washed repeatedly with hexane and dried in a vacuum Cabinet at a temperature of 30oC. eventually get 11,8 connection (101), in the form of white crystals, melting point - 66-68oC. Elemental analysis corresponds to the composition of C11H12O30.5 C6H13NO. The analysis was based on the calculation: C 67,3 texts (101): crystalline compound (101) is melted at a temperature of 60-68oC. the Crystals are large and often grow together. They have kind of plastinates, color "milk glass". More subtle instances are more transparent. For measuring larger crystal is separated optically perfect part with razor blades and with Araldit Rapid (Ciba Geigy) is bonded to steklokapet MARK. Part of the crystal is covered with the same glue. Pictures taken with a Polaroid show on the precession of the goniometer is for a single crystal with the same low melting point, good quality reflection and normal ability distribution. Unit cell, crystal system and space group are determined on a diffractometer. During the 9-day period of measurement the crystal until the end remains in good stable condition.

The value of one piece of crystal (mm): 0,90 x 0,72 x 0,20.

Crystal system: monoclinic space group: P21/n (symmetrically to the center)

a = 28,466 ; b = 9,623 ; c = 31,246 ;

= 111,73;

Z = 4;

volume = 7950,9 ; density = 1,252 n/cm3.

The measurements were performed on the diffractometer Philips PW 1100 with MoKa radiation1( = 0,70926 ):

latitude reflection: 1,4o;

time ismeri;

scale: measurement result 3 refl., after hours;

measuring range: in the range 2 6o-44owas measured 10750 of refl. From them it was possible to observe 3482 (1 > 2 (1)).

Example 2. Obtaining the crystalline complex of 3-(4-methylbenzoyl)propionic acid with excess N-ethylmorpholine /connection (101)/.

2,88 g (0,025 mol) N-ethylmorpholine and 9.60 g (0.05 mol) of 3-(4-methylbenzoyl)propionic acid is heated in a nitrogen atmosphere up to 70-75oC. once formed a clear melt, conduct cooling to room temperature. The solid reaction mass is stirred with hexane, filtered, washed with hexane and dried in a vacuum Cabinet at a temperature of 30oC. is Obtained 12.2 g of compound (101) in the form of light brown crystals, melting point - 65-67oC.

Elemental analysis corresponds to the composition of C11H12O30.5 C6H13NO. The analysis was based on the calculation: C 67,31; H 7,47; N 2,80%. Found: C 67,35; H 7,38; N 2,47%.

Example 3. Obtaining the crystalline complex of 3-(4-methylbenzoyl)propionic acid with excess N-ethylmorpholine in the presence of hexane as a solvent /compound (101)/.

5,76 g (0.05 mol) of N-ethylmorpholine and 4.8 g (0,025 mol) 3-( After 30 minutes while stirring is cooled to room temperature. The precipitate is filtered off, washed with hexane and dried in a vacuum Cabinet at a temperature of 30oC. is Obtained 5.9 g of the compound (101) in the form of white crystals, melting point - 66-68oC.

Elemental analysis corresponds to the composition of C11H12O30.5 C6H13NO. The analysis is based on the calculation: C 67,31; H 7,47; N 2,80%. Found: C 67,45; H 7,42; N 2,58%.

Example 4. Obtaining the crystalline complex of 3-(4-methylbenzoyl)propionic acid with N-methylmorpholine /connection (102)/.

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of 5.05 g (0.05 mol) of N-methylmorpholine and 9.60 g (0.05 mol) of 3-(4-methylbenzoyl)propionic acid are heated to 70oC in nitrogen atmosphere. Once formed a clear melt, produce cooling to room temperature. The solid reaction mass is stirred with hexane, filtered, washed with hexane and dried in a vacuum Cabinet at a temperature of 20oC. is Formed of 8.5 g of compound (102) in the form of beige crystals, melting point - 67-68oC. Elemental analysis corresponds to the composition of C11H12O30.5 C5H11NO. The analysis was based on the calculation: C 66,79; H 7,27; N is 2.88%. Found: C 66,54; H 7,30; N Is 2.88%.

Example 5. The manufacture of the crystalline complex of 3-(4-methylbenzamide and 9.60 g (0.05 mol) of 3-(4-methylbenzoyl)propionic acid are heated to 60oC in nitrogen atmosphere. Homogeneous transparent reaction solution is stirred for 10 minutes at a temperature of 60oC, and then with stirring, cooled to room temperature. The precipitate is filtered off, well washed repeatedly with hexane and dried in a vacuum Cabinet at a temperature of 20oC. is Formed 12.8 g of the compound (103) in the form of yellow crystals pink color, melting point - 69-71oC. Elemental analysis corresponds to the composition of C11H12O30.5 C8H17NO. The analysis is based on the calculation: C 68,29; H 7,83; N to 2.65%. Found: C 68,28; H 7,81; N 2,55%.

Example 6. Obtaining the crystalline complex of 3-(4-methylbenzoyl)propionic acid with N-n-butalbitalnop /connection (104)/.

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7,16 g (0.05 mol) of N-n-butylboron and 4,80 g (0,025 mol) 3-(4-methylbenzoyl)propionic acid are heated to a temperature of 60oC in nitrogen atmosphere. Homogeneous transparent reaction solution is stirred for 30 minutes at a temperature of 60oC, and then cooled with stirring to room temperature. The precipitate is filtered off, well washed repeatedly with hexane and dried in a vacuum Cabinet at a temperature of 20oC. is Formed of 5.6 g of compound (104) in the form of beige crystals, precise>7NO. The analysis was based on the calculation: C 68,29; H 7,83; N to 2.65%. Found: C 67,58; H Of 7.82; N 2,78%.

Example 7. Obtaining the crystalline complex of 3-(4-chlorobenzoyl)propionic acid with N-ethylmorpholine /connection (105)/.

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2,90 g (0,025 mol) N-ethylmorpholine and 5.30 g (0,025 mol) 3-(4-chlorobenzoyl)propionic acid are heated to 70oC in nitrogen atmosphere. Homogeneous transparent reaction solution is stirred for 10 minutes at a temperature of 60oC, and then with stirring, cooled to room temperature. The precipitate is filtered off, well washed repeatedly with hexane and dried in a vacuum Cabinet at a temperature of 20oC. is Formed of 6.0 g of compound (105) in the form of white crystals, melting point - 77-79oC. Elemental analysis corresponds to the composition of C10H9O3Cl 0.5 C6H13NO. The analysis was based on the calculation: C 57,78; H 5,78; N 2,59; Cl 13,12%. Found: C 57,88; H Of 5.75; N Of 2.51; Cl 13,22%.

Example 8. Obtaining the crystalline complex of 3-(4-phenylbenzyl)propionic acid with N-ethylmorpholine /connection (106)/.

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2,90 g (0,025 mol) N-ethylmorpholine and 3,20 g (0,025 mol) 3-(4-phenylbenzyl) propionic acid are heated to a temperature of 120oC in nitrogen atmosphere. Homogeneous transparent reaktsiooniajas. The solid reaction mixture is stirred with hexane, filtered, washed with hexane and dried in a vacuum Cabinet Pori temperature of 20oC. is Formed of 3.8 g of compound (106) in the form of white crystals, melting point - 105-107oC. Elemental analysis corresponds to the composition of C16H14O30.5 C6H13NO. The analysis was based on the calculation: C 73,17; H 6,63; N of 2.25%. Found: C 73,00; H Of 6.68; N 2,24%.

Example 9. Check crystalline complex of 3-(4-methylbenzoyl)propionic acid with N-ethylmorpholine /connection (101)/ water-soluble corrosion-protective coating of 2K-epoxy resin-based bekopaka EP 384 W /bekopaka EP 075/ bekopaka EH 623 W as a corrosion inhibitor.

For the manufacture of a composition for coating on the basis of bekopaka EP 384 W /bekopaka EP 0,75 /bekopaka EH 623 W are the components 1 - 8 (without additives) or the components 1 to 9 (with additives) in the sequence (component A, cf. table 2).

The resulting component A (composition with and without corrosion inhibitor) was dispersed using a horizontal ball mill to a fineness of <15 m. The resulting dispersion is evaluated by setting the measured value (iso 1524) using the green is (with the addition of corrosion-protective agent, example 9b) is mixed with 66,7 g of component B. To establish the desired viscosity for spraying lacquer is diluted with demineralized water. Applique is performed on a steel sheet (h,5 cm) of the Bonder type (cold rolling, whether steel; manufacturer: Chemetall, Frankfurt am main /Germany) thickness, which after drying is 60 m. (drying conditions: 10 days at room temperature).

Before testing for atmospheric corrosion on "lacquer films using cross cutting tool of the Bonder type (Mod. 205; manufacturer /sales: Firm Lau, Helger/ Germany) done some damage in the form of a parallel incision (i.e., parallel to the longest edge of the sheet). Edge protect sheet by applying protective coatings ( Jcpsit 255; manufacturer: Inertol Joint stock company. Winterthur, Switzerland).

Then the sample is subjected to istropolitana testing for atmospheric corrosion in salt spray (DiN 50 021 SS) for 190 hours, or when moisture condensation (ASTM D 4585-87) for 168 hours. The results are given in tables 3 and 4. Evaluation results carried out on the basis of the relevant standards according to DiN code estimates by specifying corrosion values CPF (factt maximum 12 points. Individual maximum values for coatings (films) and steel amounted to 6 points. The larger the number, the better the corrosion protection.

Example 10. Check crystalline complex of 3-(4-methylbenzoyl)propionic acid with N-ethylmorpholine /connection (101)/ water dispersion based on a copolymer ether /styrene acrylic acid (acronal S 760) as a corrosion inhibitor.

To obtain a composition for coating on the basis of acronal S 760 parts 1 - 5 pre-mix, then add components 6 and 7 (part no. corrosion inhibitor) or 6 - 8 (composition with corrosion inhibitor, the compound (101), example 1) in the sequence (EUR.table. 5).

The obtained pigment paste was dispersed using a horizontal ball mill or similar device to a fineness of <15 m. Fine grain appreciate by setting the measured value (iso 1524). For the manufacture of varnish adds the components 9 to 12 in the sequence (table 5). The application is carried out using conventional spraying. Depending on the desired viscosity of the finished paint can be diluted by adding butyldiglycol/deion. water (1:1 g/g).

The application l 100 m (drying conditions: 14 days at room temperature).

Before testing for atmospheric corrosion on "lacquer films using cross cutting tool of the Bonder type (Mod. 205; manufacturer/sales: firm Lau, Hemer/Germany) do some damage in the form of a parallel incision (i.e., parallel to the longest edge of the sheet). Edge protect sheet by applying protective coatings ( Jcosit 255; manufacturer: Jnertol A. G., Winterthur, Switzerland).

Then the sample is subjected to istropolitana testing for atmospheric corrosion in salt spray (DiN 50 021 SS) for 168 hours. The results are given in table 6. Evaluation results carried out on the basis of the relevant standards according to DiN code estimates by specifying corrosion values CPF (factor corrosion protection). CPF is determined by summing the estimates of the coating (film) and evaluation of steel: it is a maximum of 12 points. Individual maximum values for coatings (films) and steel amounted to 6 points. The larger the number, the better the corrosion protection.

Example 11. Check crystalline complex of 3-(4-methylbenzoyl)propionic acid with N-ethylmorpholine /connection (101)/ water acrylic dispersion (Maincote HG-54) as a corrosion inhibitor.

Components 1-8 or 1-9 dispersed with rapid stirring with 3000 equipment. /min, up to a fineness of < 15 m. The result of the dispersion thus obtained pigment paste estimate by setting the measured value (iso 1524). The quantity used of the corrosion inhibitors according to the invention, refers to the entire solid body without additives (all solid body: 47%). As a consequence, the additive, for example, 1% corrosion inhibitor in 100 g of a dispersion means an amount equal to 0.47,

To obtain a composition for coating add components 10-16 according to table 7 at a lower speed stirring (1000 Rev/minutes) in a specified sequence. Immediately after controlling the pH value to the application, in this case we are talking about ammonia solution (25%), set the pH from 8 to 8.5.

Applique composition for coating can be carried out without dilution by airless spraying, smearing, rolling or after dilution by conventional spraying.

Dilution to the desired viscosity is due to the addition of butylglycol/water (1 : 1 g/g). In the tion of the composition is carried out on steel plates (19 x 10.5 cm) type Bonder (cold rolling, defatted steel; manufacturer: Chemetall, Frankfurt am main, Germany) with a layer thickness, which after drying is 50-55 m (drying conditions: 10 days at room temperature).

Before testing for atmospheric corrosion on "lacquer films using cross cutting tool of the Bonder type (mod. 205; manufacturer/sales: Firm Lau, 5870 Hemer/Germany) do some damage in the form of a parallel incision (i.e., parallel to the longest edge of the sheet). Edges protect by applying protective coatings (Jcosit 255; manufacturer: Jnertol A. G., Winterthur, Switzerland). Immediately after this, the samples are subjected to accelerated testing for atmospheric corrosion in salt spray (DiN 50 021SS) for 168 hours and tested for corrosion by condensation of moisture (ASTM 4585-87) for 330 hours. The results are summarized in tables 8 and 9. Evaluation results carried out on the basis of the relevant DiN standards according to the estimated code by specifying the values of the corrosion protection CPF (factor corrosion protection). CPF is obtained by summing the estimates of the coating (film) and evaluation of steel: he maximum is 12 points. Individual maximum values for coatings (films) and steel make up 6 points. What b is benzoyl)propionic acid with N-ethylmorpholine/ connection (101) /water-soluble Alcide/urethane-based coatings Resydrol AZ 436 W/Daotan VTW1237 as a corrosion inhibitor.

To obtain a composition for coating based on Resydrol AZ 436 W/Daotan VTW 1237 use components 1-12 in the sequence (EUR. table 10).

To obtain a composition for coating based on Resydol'a AZ 436 W/Daotan VTW 1237 first Resydol AZ 436 W (component 1) with ammonia solution (component 2) installed at pH = 8,5. Immediately after this, the component 3 is well dispersed. Daotan VTW 1237 (component 4) is mixed with components 1-3, the pH value is controlled in this case by using ammonia solution set to a value of pH = 8,5. Then add components 5-12 in the specified sequence, and the lacquer only dispersed (so-called Andissolvern). The composition is left on the night and afterwards the dispersion to the fineness of < 15 m. The resulting fine grain determined using grindometer (iso 1524). The original amount of the corrosion inhibitors according to the invention applies to the entire solid composition without corrosion inhibitors (all solid body: 51%). According to this adding, for example, 1% corrosion inhibitor to 100 g of the coating means the quantity of 0.51 g

For conventional spraying lacquer with deionized water set on the desired viscosity of an oil-free steel; manufacturer: Chemetall, Frankfurt am main /Germany) with layer thickness, which after drying is 50-55 m (drying conditions: 14 days at room temperature).

Before testing for atmospheric corrosion on "lacquer films with the use of cross cutting tool of the Bonder type (Mod. 205; manufacturer/sales: Company law, Hemer/ Germany) do some damage in the form of a parallel incision (e.g., parallel to the longest edge of the sheet). Edge protect sheet by applying protective coatings ( Jcosit 255; manufacturer: Jnertol AG, Winterthur, Switzerland).

After that, the samples are subjected to accelerated testing for atmospheric corrosion in salt spray (DiN 50 021 SS) for 120 hours. The determination of the values of corrosion protection CPF carried out as described in example 11. The results of the summation in table 11. The larger the number, the better the corrosion protection.

1. Crystalline complex compounds derivatives of the research with carbon keto acid of the formula I

< / BR>
where R1, R2, R3, R5, R4independently of one another represent hydrogen, halogen, C1- C15-alkyl or C6- C10-aryl, and lower R10is1- C15-alkyl, and m denotes an integer of 2.

2. Crystalline complex compounds under item 1, in which at least two radicals of R1- R5are hydrogen.

3. Crystalline complex compounds under item 1, in which R1, R2, R4and R5denote hydrogen.

4. Crystalline complex compounds under item 1, in which R10stands WITH1- C4-alkyl.

5. Crystalline complex compounds under item 1, in which R1, R2, R4and R5are hydrogen; R3denotes hydrogen, C1- C4-alkyl, phenyl or chlorine; R10represents a C1- C4-alkyl, and m denotes the number 2.

6. Composition for coating containing (a) an organic film-forming binder and b) as corrosion inhibitor, at least one crystalline compound of formula I under item 1.

7. Composition for coating on p. 6, and as a composition for coating is house paint.

8. Composition for coating on p. 6, and as a composition for coating is water house paint.

9. Composition for covered the market of acrylic resins, polyvinyl, phenolic, alkyd resin or their mixture.

10. Composition for coating on p. 6, additionally containing one or more components from the group of pigments, dyes, fillers, viscosity stabilizers, dispersants, thixotropic substances, means of improving adresi, antioxidants, light stabilizers or curing agents.

11. Composition for coating on p. 6, in which component b) is contained in an amount of from 0.02 to 20.0% in recalculation on weight of total solids of the composition for a covering.

12. Crystalline complex compounds derivatives of the research with carbon keto-acid of formula I under item 1 as corrosion inhibitors in compositions for coating metal surfaces.

13. Method for protecting a metal substrate from corrosion, characterized in that it is applied composition for coating on p. 9, and then dried and/or utverjdayut.

14. A method of obtaining a crystalline complex compounds of formula I on p. 1, characterized in that the carboxylic ketoacid of formula II.

< / BR>
in which the General symbols have the meanings specified in paragraph 1, is reacted with a derivative of the research of the formula III

< / BR>
in which R10Imaam on p. 14, characterized in that the molar ratio of carbon of the keto-acid of formula II and derived the research of the formula III is 4 : 1 to 1 : 4.

 

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39 cl, 7 tbl

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8 ex

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