DE1494459A1 - Thermosetting molding and coating compounds containing nitrogen-containing polycondensates - Google Patents

Description

Heat-curable molding and coating compositions containing sticky-stick Pelykendensate The present invention relates to thermosetting Ferm and coating compositions containing nitrogen-containing polycondensates, these in Ragen of solutions in organic solvents. Such forms and masses are suitable besenders only production of temperature-resistant plastic moldings and coatings Metals, for example, for the purpose of corrosion protection or for the purpose of directing rice clation. In the case of the manufacture of coatings, the metals are mixed with the Ferm and coating compounds coated and heated to elevated temperatures, the solvent evaporates and @ aring occurs.

For example, polyester @ us in particular have a sheet metal insulation material Tersphthalic acid, glycerine and glycels gained technical importance; however suffice Such coatings do not meet the higher requirements in terms of temperature resistance, as they are placed on insulated wires in electrical machine construction today. That is true in the same way for insulating coatings based on pelyesteranides, the are obtained because # Dicarboxylic acids, especially tersphthalic acid, The main amount is glyserine and glycols and a limited proportion is aminoalkcheles and / or diamines are reacted, whereby polycondensates are formed, which are predominantly Have ester bonds and additional amide bonds.

An improvement in the temperature resistance of polyesters and polyester amides was achieved because the melecules of these resins were modified in such a way that imide groups (English patent specification 973 377 and German patent application H 56 189 IVb / 75 @) of the general formula and / or benzimidazole groups (German patent application H 56 506 IVc / 39b) of the general Fermel: installed.

The increase in temperature resistance is to be attributed to since # the imide or benzimidazole groups are thermal extraordinary are stable and, moreover, a chain-stiffening and thus thermoplasticity cause the opposite effect. As expected, the temperature resistance increases itt because proportion of these thermostable and chain-stiffening groups.

Surprisingly, it has been found that curable, nitrogen-containing pelycondensates with neutral properties are obtained from their solutions in organic solvents, for example after stoving metals coated with their solutions at elevated temperatures, and can be produced in a simple manner by esterifying benzoxazel-forming starting compounds , unesterified, amidated, transamidated, imidated and / or bensimidazolated, so that # ii polycondensate benzexazole groups of the general Fermel As is known, bensoxazel groups are formed from o-aminophenols and carboxylic acids biv. their esters. Proof of the presence of Bensexasel groups can be provided by infrared spectroscopy.

The 2-position of the Benzoxszelgruppe can be substituted. The 4-, 5-, 6- and / or 7-position can also be optionally substituted one or more benzene aromatic, heteroaromatic and / or alicyclic rings present condensed. Both the 4-, 5-, 6- and / or 7-position and / or at least one of the aforementioned substituents in the 4-, 5-, 6- and / or 7-position as well the substituent in the 2-position must be at least before the conversion to the polycondensate one on ester, given @@ ls also on benzimidazole formation, and / or on the amide or functional group capable of imide formation. 2 Amine groups in ob position and / or an amine and hydroxyl group in each case in o-position be present as benzimidazole or benzoxazole-forming functional groups of the invention are dezag-ÄS heat-curable Ferm and coating compositions containing nitrogenous Polycondensates, which contain residues in the molecule in two and at least in part mchr as compounds containing two-functional carboxyl and hydroxyl and / or amine groups contain, these residues in Polykendensat via ester, amide, imide and / or Benzimidazole groups are linked to one another, characterized in that ii Melekül of the polykendensate, benzoxazole groups are also present, webei a) the 2-position the Benzeexasel group may be substituted b) the 4,5-, 6- and / or 7-position of the benzoxazole group can be substituted, o) the benzoxazole group as well as in the 4-, 5-, 6- and / or 7-position and / or by at least one of the substituents in the 4, 5-, 6- and / or 7-8solution as well as in the 2-position or through the substituent in the 2-position via ester, amide, imide, benzimidazole and / or benzoxazole groups ii pely condensate are installed.

Those contained in the Ferm and coating compositions according to the invention Polycondensates containing nitrogen can be produced by forming benzoxazole Starting compounds and / or their reaction products with carbexyl, ester, anhydride, Monovalent ones containing amines, amides, hydroxyls, lactene and / or lactam groups Starting compounds and / or their reaction products reacts, A @ s bensexasel-forming Starting compounds are: 1. Aliphatic and arematic carboxylic acids or Carboxylic acid esters which contain at least one carboxyl group or eater group and more at least one for ester formation, possibly also for bensimidazole formation, and / or have functional groups capable of amide or imide formation, i.e. they can Pelycarbene acids, Gxycarbene acids, Amincoarbene acids, their liter, Ralbester, anhydrides, Amides, hemiamides, lactones and lactams are used; be used in advance aronatic Carboxylic acids with at least one carboxyl or ester group, in particular thorn phenyl and kremyl ester.

2. o-aminophenels, which each have at least one amine and one hydroxyl group in ortho position and, if only one each. Amino and Je one. Hydroxyl group in ortho position present, in addition at least one sur ester, possibly also for the 3rd nzimidazole formation, and / or have functional groups capable of amide or imide formation, i.e. it can trivalent and polyvalent o-aminophenols, o-aminophenoloarboxylic acids, o-aminophenol alcohols, whose esters, half-esters, amides, half-amides, Laotons and lactams are used @ 3-Amino-4-hydroxybenzoic acid is preferred because of its ready availability.

For the production of the benzexazcl-containing polycondensates, the the already mentioned benzoxasol-forming starting compounds for production of known polycondenes @ at @@ with ester, amide, imide and / or bengimidase groups used polycarboxylic acids, o @ ycarboxylic acids, nchrivalent alkchels, polybasic Phenols and for ester, possibly also for Bensizid @ zolbildung, and / eder for Amide or imide formation capable of amine compounds @ ing @ sets, so that # only creation the polykendensates containing @@ nsoxazel groups include, for example, the following Connections are @ ignored a) The polyearbene acids: terephthalic acid, Isophthalic acid, 4,4'-dicarboxydiphenyldimethylmethane, naphthalene-2,6-dioarboxylic acid, naphthalene-1,6-dicarboxylic acid, diphenyl-1,8-dioarboxylic acid, tetrachloroterephthalic acid, 5-chloroisophthalic acid, pyridine-3,5-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, Cyclohexane-1,4-dicarboxylic acid, succinic acid, adipic acid, trimesic acid, trimellitic acid, Pyromellitic acid, naphthalene-1,4,5,8-tetracarboxylic acid, hemimellitic acid, prchnitic acid, Mellephanic acid, mellitic acid and perylene-3,4,9,10-tetracarboxylic acid bsw. their derivative such as anhydrides, esters, half esters, amides and half amides; b) the oxyoarboxylic acids: m-oxybenzoic acid, , p-Oxybenzoic acid, 5-Oxyisophthalic acid, Oxyterephthalic acid, 5-Oxynaphthoic acid, Phloretinic acid, p- (2-hydroxyethyl) benzoic acid, 4-oxyphthalic acid, glycolic acid, tartaric acid, 2,2-bis (hydrexy methyl) propionic acid and @ -oxypropienoic acid or their derivatives such as Esters, Anides and Laotons; o) dio amineoarboxylic acids are the following under the aning compounds listed; a) the polyvalent alkchels: ethylene glycol, diethylene glycol, propylene glycol, 2,2-dimethyl-1,3-propanediol, 4,4'-di (exyäthexy) diphenyldimethylmethane, 4,4'-di (oxyäthexy) diphenyldimethylmethane, , 4'-di (oxyprepoxy) diphenyldimethylmethane, 1,4-dimethylelcyolchexane, 4,4'-diexydioyolehexyldimethylmethane, Glycerine, trimethylelpropene and pentaerythritol in their old age with volatile monocarboxylic acids; e) the monohydric phenols e: 4,4'-dioxydiphenyldimethylmethane, 3,5,3 ', 5'-tetrachloro-4,4'-dioxydiphenyldimethylmethane Hydrechinen, resorcinol, phloroglucinol, 4,4'-dihydroxydiphenylsulfone, 2,7-dihydroxynaphthalene and phenolphthalein or their esters with volatile ionocarboxylic acids; r) the for Amide or imide formation, possibly at the same time for ester formation, possibly also for Amino compounds capable of forming benzimidazel: 4,4'-diaminodiphenylmethane, 4,4'-diaminediphenyldimethylmethane, 4,4'-bis (methylamine) diphenylmethane, 4,4'-dis (ethylamino) diphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-Diaminodiphenylsulfon, 4,4'-Diaminodiphenyaulfoxyd, 4,4'-Diaminodiphenyl, 4,4'-Diaminodibenzyl, 4,4'-diamino-3,3'-dimethyldiphenyl, 4,4'-diamino-2,6,2 ', 6'-tetramethyldiphenylmethane, 2,4,4'-triaminediphenylmethane, 2,4,2 ', 4'-tetraaminediphenyl, 2,4,2', 4'-tetraaminodiphenylmethane, Ethylene glycol bis (4-aminophenyl ether), 3,5-diaminobenzoic acid, benzidine-2,2'-dicarboxylic acid, 4,4'-diaminodiphenyl-3,3'-diexyacetic acid, p-xylylendinmin, ethylenediamine, tetramethylenediamine, Hexamethylenediamine, piperazine, benzidine, N, N'-di-secondary butyl-p-phenylenediamine, p-phenylenediamine, m-phenylenediamine, m-tolylenediaxnine, p-tolylenediamine, m-aminobenzoic acid, p-aminobenzic acid, 5-amineisophthalic acid, m-aminophenel, p-aminophenol, 4,4'-diaminodioyclehexylmethane, Ethanolamine, 3-aminepropanol, amine acetic acid, α-aminopropionic acid, ß-aminoprepienoic acid, # -Aminecaprenic acid, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol and tris (hydroxymethyl) aminoethane biw. their derivatives such as esters, amides with volatile Carboxylic acids, laotons and lastanes; g) those for the formation of benzimidaseoles, if appropriate at the same time for ister and / or amid bsw. Amivo compounds capable of forming imides; 2, , 2,4-Triaminebenzel, 1,2,3-Triaminobensol, 3,4-Disminebenzoic acid, 3,4-Diaminophenel, 1, 2,4,5-Tetraaminebenzel, 3,3'-Diaminobensidin, 3,4,3 ', 4'-Tetrsaminodiphenylmethane, 3,4,3 ', 4'-tetraaminodiphenylethane, 3,4,3', 4'-tetraamine diphenylpropane, 3,4,3 ', 4'-tetraaminodiphenylsulfone and 7,8-diamine-2-exynaphthalene or their derivatives such as liter, Altde, Lactene and Laotam; h) the siar Benzexaselbildung, possibly at the same time only Kster-, possibly also for benzimidase gel formation, and / or for amide or imide formation o-amine phenels: 3-amine-4-hydroxybeneic acid, 4-amine-3-hydroxybenzeic acid, 3-amine-4-hydroxybenzylalkchel, 3-Amine-4-hydrexyhydrosimtsäure, 2,4-Diaminephcnol, 2,5-Diaminephenel, 3,3'-Dihydroxybensidin, 3,3'-diamine-4,4'-dihydroxybiphenyl bsw. their derivatives Die liter, Altde, Laetene and lactans.

The production of the Pelykendensate containing benzexasel groups , indening, for example, first the bensexasel-forming starting compounds, i.e. a carboxylic acid after 1. and an o-aminophenol after 2. given also fall a mixture of two or more of these carboxylic acids and / or o-aminophenols, - the connections in question are in sections a) and h), some these carboxylic acids are also listed in sections b), f) and g) - at low temperatures between 100 and 300 ° C in a suitable solvent while distilling off the resulting water, optionally also alkchols or phenols to the benzoxazole derivative implemented and then the remaining functional groups of the resulting Benzoxazole compound, if appropriate after removing the solvent, preferably with the addition of a catalyst, sit the functional groups of the suver mentioned converts polyfunctional compounds, i.e. with molecular enlargement into ester, Amide, imide and / or benzimideszene groups transferred.

Examples of suitable solvents are cresols and xylenelines strongly polar. Solvents such as dizethylfermamide, dimethylacetamide, dimethyl sulfoxide or N-methyl pyrrolides. It is advantageous to use predominantly the solvent or only those required for the subsequent esterification of each transesterification Mchrvaligen Alkchels or a mixture of different Mchrwertiger Alkchels, if necessary with the addition of ferrous phenols, the latter also contributing to esterification those. Instead of the dihydric alcohols or phenols can be used as solvents far ai. benzoxazole-forming Starting compounds or for their Umse @ zungsproduk @ also advantageously prefabricated1 known ones melting below 200 ° C Polycondensates with ester, amide, imide and / or benzimidazole groups or mixtures use the same.

The way in which the benzoxazole-forming starting compounds are added kloan can be varied widely.

The easiest way is to add an unchanged composition Mixture of these compounds.

But you can also use the proportion of portion to portion change. The benzoxazole-forming starting compounds can be separated alternately Finally, sugeben and nan can determine the sequence of addition of ester, amide, imide, benzimidazole and / or benzoxazole-forming starting compounds as desired or also in a and combine the same addition; for example, aan can be used as benzimidazole-benzoxazole-forming Mixture 1 mol of diphenyl terephthalate, 1 mol of 3,4-diaminobenzic acid and 1 nel 3-amine-4-hydroxybenzcesäure or as an imide-benzoxazole-forming mixture two moles Trimellitic acid, 1 mole of 4,4'-diaminodiphenylmethane and 2 moles of 3-amino-4-hydroxybenzeic acid use.

In the production of the benzoxazole group-containing polykendensates the temperature of the reaction mixture is, if appropriate with the introduction of inert gas in there ma # e increased to a maximum of about 300 ° C than for distilling off the water formed and, if applicable, the monovalent alkchel formed, Phenels, amines or a meneoarboxylic acid and for stirring the in particular against End of the kendensation of viscous, dying melt is necessary. After distilling off the theoretical amount of water or the monovalent alkchel, phenel, Amine of the menecarboxylic acid and optionally its excess in polyvalent ones Alkcholen is given in the old spring hardness, soluble in kreselen and xylenelene Hars, depending on the composition and the amount of distilled off monovalent Alkchols have a viscosity between 1,000 and 50,000 oP, preferably between 2,000 and 10,000 oP, measured in a 33.3% solution in m-cresol at 25 ° C. The Curing catalysts which accelerate the settling process can be known per se Way, either to the Mars buckle or later to the lacquer solution.

To use the Ferm and coating @@ as @ en g @@ ä # of the invention the Pelykendensate dissolved in Laeklöeungsmittel, preferably in selchen, which increase Soldering the well-known tersphthalic acid pelyester can be used. The ones that can be @charted Distance and coating compounds can also be used in a known manner Leveling agent, Contain dyes, pigments and / or fillers. You coat objects, preferably of metals, with the molding and coating compounds according to the invention for the production of leftover can in a known manner by dipping or spraying, optionally in the electrostatic process.

For baking those coated with the porosity and coating material Metals are dependent on the amount and type of curing catalysts used in each case and, depending on the baking time, temperatures between 150 and 65,000 are required. Coating and baking can, if necessary, be carried out several times in succession when increased film thicknesses have been desired.

The following example explains the invention: Composition: Benzexasel- / Benzimidazol- / Imid- / Amih- / Estergru @ en = 1.00 / 1.00 / 2.06 / 2.06 / 15.45; Sticksteffgchalt = approx. 3.1, in one with thermometer, Eührer, Kolcnne and distilling bridge separate three-necked bottles with a capacity of one liter 1.60 mel ethylene glycol, 0.86 mel glycerin and 1.16 1.1 terephthalic acid in Presence of 0.0025 Mel zinc acetate as esterification catalyst and some Rchkrescl as an entrainer at a temperature between 160 and 230 ° C if possible largely implemented with each other. The addition of terephthalic acid to the submitted Alcohols are made in 3 servings that are 75 g, 60 g and 57 g. The first encore happened at 1000C, the further additions at 1600C. In the meantime, the reaction temperature became increased to a maximum of 2300C. Because water formed during the esterification was distilled off over the bridge. 50 ml of distillate gathered in the template.

In this prefabricated polyester, 0.075 mol isophthalic acid diphenyl ester first and 0.150 moles of 3,4-diaminobenzoic acid as a benzimidazole-forming mixture and thereon 0.075 mol of diphenyl terephthalate and 0.150 mol of 3 * amine-4-hydroxybenzoic acid methyl ester added as a benzoxazel-forming mixture at 140.degree. After both encores, the Temperature of the reaction mixture gradually increased to 23500, with a further 16 ml @ distillate were collected.

In these polyesters containing benzimidazole and benzoxazole groups were 0.309 moles of trimellitic anhydride and 0.131 moles of 4,4'-diaminodiphenylmethane added in two portions of the same mixture composition and reduced, the first addition at 150 ° C and the second addition at 16000 and the Reaction temperature was increased to 23090 or to 2400C.

Another 12 ml of distillate, mainly water, collected iider @erlage.

In these containing benzimidazole, benzexazole and imide groups Lastly, polyesters were 0.131 moles of 4,4'-diaminodiphenylmethane for the purpose of amide formation kendensiert. When the reactor temperature had reached 210 ° C, the column removed and with the remaining water and methanol you also formed phenel and you distilled off excess ethylene glycol over the bridge. Total were approx. 62 μl water, 34 μl ethylene glycol, 6 ml methanol, 26 μl phenol and 10 ml Rchkrezel.

The Polykendensat was hard and brittle in the cold Resin, which was easily soluble in cresols and Äylenelen. The viscosity of a 33.3% solution of b m-krenol at 25 ° C was 2,700 oP.

Claiml

Claims (1)

Claim Thermosetting @ erm- and coating masses contain @ nd sti @@ - steffhaltige Pelyk @@ den @ ate, which in Melekäl remains of two and at least @ ns partly mchr as Zweifunkti @@ all @@ Garbexyl- sewie Mydr @ xyl- and / @ the amine groups indicating compounds contains, which residues in Felykendensat via ester, amide, imide and / or Emzimidasel groups are connected to each other, thereby gek @@@@ eishnet, da # in Melekül the Pelyk @@@ ensate additionally @@@ sex assel groups are entangled, w @ with a) the 2-delivery the Benzer @@ elgruppe substitutes his k @ nn, b) the 4,5,6, and / eder 7-position of the Bensexaselgruppe substitutes @ein kännen, c) the @enze @@@ elgruppe sewehl in 4,5,6 and / or 7-position and / or by at least one of the substituents in 4,5,6 and / or 7-position than after in 2- @ position eder by the substitute @@@ ten in 2-position Ester, amide, imide, @enzinidazel and / or benserazole groups in polycendensate are encased.