DE1745052A1 - Process for the production of condensation products - Google Patents

Description

"Process for the preparation of condensation products." lifach the The present invention provides a process for the preparation of condensation products made available by (I) methylol ether from urea or aminotriazine-formaldehyde condensates and monohydric alcohols with 1 to @ carbon atoms in the molecule, (II) compounds, which contains two more non-phenolic hydroxyl groups in the molecule and / or Polyhydroxyl compounds with a hydroxyl content of at least 1%, and (III) cyclic ones polyfunctional @@ carboxylic acids with or without the presence of solvents, e.g. B. toluene, Xylene, are reacted with one another at temperatures above 40 ° C.

It is advantageous to proceed in such a way that the number of cyclic Dolyfunctional carboxylic acids (III) used to neutralize the hydroxyl groups the hydroxyl-containing compounds and the polyhydroxyl compounds (II) required theoretical amount, calculated as equivalents, exceeds the methylol ethers (I) with the compounds containing hydroxyl groups (II) via the carboxyl groups of the Polycarboxylic acids (III) are linked to one another.

Instead of the methylol ethers (I), the reaction products can also be used this with cyclic carboxylic acids or the tmsetw @ products of hexamethylolmelamine or their derivatives, e.g. B, hexamethoxymethylmelamine, with cyclic carboxylic acids, z. B.

Phthalic acid. Hexahydrophthalic anhydride, benzoic acid, ve @ applies will.

A special variant of the invention is also available. aie implementations only partially, e.g. B. up to acid numbers of 40 and higher, execute and the obtained Condensation product for the purpose of good solubility in water with amines in a cave put that an alkaline reaction of the watery solution of the condensate ti @ nd @ rodaktes conditional.

Of the ethylol ethers in question is hexamethoxymethylmelamine because of its good heat resistance and that of other methylol ethers reduced tendency to self-cor. densation best suited.

Of the compounds that have two or more non-phenolic hydroxyl groups Entalten in the molecule, especially polyhydric alcohols, z. B. ethylene glycol, Diet ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, Polyglycols, 1, 1 'isopropylidene-bis- (p-phenyleneoxy-) di-2-propanol, glycerine, trimethylolproane, Pentaerythritol, cyclohexanediol, phthalyl alcohol, trishydroxyethyl isocyanurate, nempentyl glycol, into consideration.

Particularly suitable polyhydroxyl compounds are those with a Hydroxyl content above 4%, preferably above 8%, the hydroxyl content in more usual Way was calculated based on the OHZ number. Alkyd resins on the basis of two or more polyhydric alcohols, aliphatic and / or cyclic polycarboxylic acids and Monocarboxylic acids, e.g. B. fatty acids, cyclic monocarboxylic acids such as benzoic acid or their derivatives, e.g. B. p-tert-butylbenzoic acid, abietic acid or other cyclic Natural resin acids are very suitable.

The use of fatty acid-free products is particularly advantageous Alkyd resins based on dihydric and polyhydric alcohols, e.g. B. propylene glycol, Glycerol, aromatic dicprboxylic acids or their anhydrides, e.g. B. phthalic anhydride, and / or saturated aliphatic dicarboxylic acids with at least two methylene groups in the molecule, e.g. B. succinic acid, adipic acid sebacic acid, as polyhydroxyl compounds with a hydroxyl content of at least 4, preferably over 8%.

Fatty acids containing hydroxyl groups, e.g. B. castor oil fatty acid, nydroxylruppennaltigefettede, z. B. Iticine oil, blown fatty oils, e.g. B. blown rapeseed oil, and biono or Diglycerides e vox fatty acids or fatty oils, e.g. B. Linseed oil fatty acid monoglyecride, can also be used as hydroxyl-containing Veroinduiigun for the purposes of the invention can be used, although the use of alkyd resins leads to higher quality condensation products leads, especially with regard to heat and light resistance of the condensation products.

Excellent heat resistance of the condensation products by using hydroxyl-containing reaction products of cyclic Polycarboxylic acids, e.g. B. Benzoltricanb @ näure, benzene tetracarboxylic acid, pyridinetricarboxylic acid, Tris-carboxy-ethyl isocyanurate, or derivatives thereof, e.g. B.

Isophthalic acid, terephthalic acid dimethyl ester, benzenetricarboxylic acid anhydride, Benzene tetracarboxylic dianhydride, with dihydric alcohols or glycols, e.g. B. ethylene glycol achieved. These conversion products are particularly suitable polyhydroxyl compounds within the meaning of the invention.

The cyclic polyfunctional carboxylic acids include aromatic and / or heterocyclic polycarboxylic acids with at least two carboxyl groups z. B. phthalic anhydride. Isophthalic acid, hexahydrophthalic anhydride, terephthalic acid or dimethyl terephthalate, pyridinedicarboxylic acid, in addition to cyclic polyfunctional carboxylic acids. z. B. cyclobutane tricarboxylic acid into consideration. Aromatic or heterocyclic polyfunctional carboxylic acids with more than zv. ei carboxyl groups in the molecule or their anhydrides, e.g. B. benzene tricarboxylic acid.

Benzene tetracarboxylic dianhydride, tris-carboxy ethyl isocyanurate. Pyridine tricarboxylic acid.

Furthermore, the condensation products can after application to a Underlay of further condensation in the film by adding hardener, e.g. B. hydrochloric acid, p-toluenesulfonic acid, or by thermal aftertreatment, e.g. B. above 120 ° C, are subjected, if necessary in the presence of other known paint raw materials, z. B. acrylic resins, epoxy resins, epoxy resin esters, urea or. sminotriazine formaldehyde resins, Phenoplasts, polyesters containing terephthalic acid.

The new condensation products are particularly suitable for solvent-free and solvent-based coating agents, which are prepared by the usual methods, for. B. painting, spraying, electrostatic, electrophoretic, whirl sintering, other powder coatings, z. B. electrostatic, pour, can be applied. A special application is that in an aqueous medium or as wire enamel on wire enamelling machines.

The new condensation products for laminates, for Impregnation of paper, fabrics or other substrates, or as adhesives be used.

The following examples are only illustrative of the procedure without claiming to be complete.

Example 1: 60 parts of hexamethoxymethylmelamine and 30 parts of one fatty acid-free alkyd resin based on polypropylene glycol and aromatic and aliphatic saturated dicarboxylic acids, viscosity approx. 5 poises / 25 ° 0, hydroxyl content approx. 1, 7, a, are mixed and azeotroped with 10 parts in the presence of xylene Phthalic anhydride at 80-max. 120 ° C implemented to the acid number below 20 and as Coating agent used for fabric. Drying at 120 ° C.

Example 2: 50 parts of a reaction product from 100 parts Hexamethoxymethylmelamine and 16 parts of phthalic anhydride acid number 12, viscosity approx. 30 poises / 25 ° C, are mixed with 45 parts of a polyester or an alkyd resin, the preparation of which is described below under "B", mixed and azeotropic in the presence of toluene with 5 parts of pyromellitic dianhydride from 40 ° C to a maximum of 110 implemented until the acid number is below 20 The condensation product is considered to be solvent-free Baked enamel used or used as an electrical impregnating resin.

Manufacture of the fatty acid-free alkyd resin "B"; 184 parts glycerine, 76 parts of 1,2 propylene glycol, 100 parts of phthalic anhydride, 100 parts of adipic acid and 120 parts of benzoic acid are azeotroped in the presence of xylene and with 1 part Zinc octoate, 8, 4 Zn, and 1 part lithium naphtenate, 1.5% Li, up to a maximum of 220 ° 0 during about 30 hours until the acid number 15 reacted. Hydroxyl content above 8%.

Example 3: Instead of the benzoic acid in the alkyd resin "B" from example 2 the equivalent amount of phthalic anhydride is used and the rest accordingly Proceed to example 2. The result is a higher viscosity and faster drying Condensation product.

Example 4: 780 parts of hexamethoxymethylmelamine are mixed with 31 parts Ethylene glycol and 200 parts of hexahydrophthalic anhyaride azeotropically in the presence of xylene and under vacuum until the acid number is below 20. The condensation product is used on its own or in combination with other paint raw materials known per se used.

Example 5: 60 parts of hexamethoxymethylmelamine are mixed with 30 parts a fatty acid-free alkyd resin based on glycerine, 1,2-propylene glycol, Phthalic anhydride and adipic acid, viscosity 70sec./DIN 4mm / 20 ° C, 75% in ethanol, Acid number 14, OHN 516, VZ 363, mixed and azeotroped with in the presence of xylene 20 parts of phthalic anhydride at 80 ° -max.

120 ° C implemented up to the acid number 70 and the xylene was distilled off under vacuum.

Now 10% butyl glycol, based on the condensation product, 20% isopropanol, based on the condensation product, added. After that is adjusted to a pH of 9.2 with triattylamine and with desalted Water on a solid body. lt diluted by 50%.

The aqueous solution of the condensation product thus obtained can by Immersion. or electrophoretically on substrates, e.g. B.

Sheet steel, to be applied and is baked.

Claims (27)

P a. tentanspruche 1. Process for the production of condensation products, characterized in that # (I) methylol ether from urea or. Aminotriazine-formaldehyde condensates and e nivalent alcohols with 1 to 4 carbon atoms in the molecule, (II) compounds, which contain two or more non-phenolic hydroxyl groups in the molecule and / or Polyhydroxyl compounds with a hydroxyl level of at least 1 *, and (III) cyclic polyfunctional carboxylic acids with or without the presence of solvents at temperatures above 40 ° C un. be set. 2. The method according to claim 1, characterized in that the amount of the cyclic polyfunctional carboxylic acids (III) for the neutralization of the hydroxyl groups the compounds containing hydroxyl groups and the polyhydroxyl compounds (II) required theoretical amount calculated as equivalents. exceeds. 3. The method according to claims 1 and 2, characterized by Oeketlnzeich, that as (I) methylol ether of an aminotriazine-formaldehyde condensate of ethanol ether of hexamethylolmelamine = hexamethoxymethylmelamine is used. 4. The method in modification of claims 1 to 3, characterized in that since # instead of the methylol ether from urea or. Aminotriazine-formaldehyde condensates and monohydric alcohols with one to four carbon atoms in the molecule now the Reaction products of hexamethylolmelamine or its derivatives with cyclic carboxylic acids be used. 5. The method according to claim 4, characterized in that dalz as a derivative of hexamethylolmelamine, the hexamethoxymethylmelamine is used. 6. The method according to claims 1 to 5, characterized in that that the reactions are only partially up to an acid number of the condensation product of at least 40 or higher and the obtained condensation product then, for the purpose of good solubility in water, amines are added at the same height that an alkaline reaction of the aqueous solution of the condensation product conditional. 7. The method according to claims 1 to 6, characterized in that that as compounds that contain two or more non-phenolic hydroxyl groups in the molecule contain polyhydric alcohols. 8. The method according to claim 7, characterized in that bivalent Alcohols or glycols can be used. 9. The method according to claim 8, characterized in that ethylene glycol or propylene glycols can be used. 10. The method according to claim 7, characterized in that heterocyclic Alcohols are used. 11. The method according to claim 10, characterized in that trishydroxyethyl isocyanurate is used. 12. The method according to claims 1 to 6, characterized in that da # uses polyhydroxyl compounds with a hydroxyl content of at least 4 * will. 13. The method according to claims 1 to 6, characterized in that because # polyhydroxyl compounds with a hydroxyl content above 8% are used. 14. The method according to claims 1 to 6, 12 and 13, characterized in that that, as polyhydroxyl compounds, alkyd resins based on di- and / or polyvalent Alcohols, aliphatic and / or cyclic polycarboxylic acids and monooarboxylic acids be used. 15. The method according to claim 14, characterized in that daM alkyd resins based on di- and trihydric alcohols, saturated aliphatic and aromatic polycarboxylic acids and monocarboxylic acids can be used. 16. The method according to claim 15, characterized in that da3 as monocarboxylic acids Fatty acids and / or cyclic monocarboxylic acids can be used. 17. The method according to claim 16, characterized gekennzeicXlet, daw as cyclic Monooarboxylic acid benzoic acid or its derivatives containing carboxyl groups are used will. 18. The method according to claims 1 to 6, 12 and 13, characterized in that that as polyhydroxyl compounds fatty acid-free alkyd resins based on two and polyhydric alcohols, aromatic dicarboxylic acids and or aliphatic saturated Dicarboxylic acids with at least two methylene groups in the molecule can be used. 19. The method according to claims 1 to 6, 12 and 13, characterized in that that as compounds that contain two or more non-phenolic hydroxyl groups in the molecule contain or, as polyhydroxyl compounds, fatty acids containing hydroxyl groups or fatty oils containing hydroxyl groups can be used. 20. The method according to claim 19, characterized in that castor oil fatty acid, Castor oil, blown fatty oils or mono- and / or diglycerides of fatty acids are used will. 21. The method according to claims 1 to 6, 12 and 13, characterized in that daM, as polyhydroxyl compounds, the reaction products containing hydroxyl groups used by cyclic polycarboxylic acids and dihydric alcohols or glycols will. 22. The method according to claim 21, characterized in that there are: 5 aromatic or heterocyclic polycarboxylic acids with more than two carboxyl groups are used will. 23. The method according to claim 22, characterized in that benzene tri- or Benzene tetracarboxylic acids or pyridine tricarboxylic acid or tris-carboxy-ethyl isocyanurate be used. 24. The method according to claims 1 to 7, 12, 13, 14, 18, 19 and 21, characterized in that the cyclic polyfunctional carboxylic acids (III) aromatic and / or heterocyclic polycarboxylic acids with two or more carboxyl groups be used. 25. The method according to claim 24, characterized in that cyclic Polycarboxylic acids with at least three carboxyl groups can be used. 26. The method according to claims 1 to 25, characterized in that that the condensation products are subject to further condensation after they have been applied to a substrate be subjected in the film by addition of hardener or thermal aftertreatment, if necessary in the presence of other known paint raw materials. 27. The method according to claim 26, characterized in that the further condensation in the film in the presence of acrylic resins, alkyd resins, epoxy resins, epoxy resin esters, Urea or Aminotriazine aldehyde resins, phenoplasts or terephthalic iurehaltigen Polyester takes place.