DE19922032A1 - Preparation of modified cycloaliphatic epoxy resins involves reacting cycloaliphatic polyepoxides, cyclic mono- and hydroxy-carboxylic acids and/or semi-esters of dicarboxylic with (poly)glycol monoalkyl ethers and/or fatty alcohols - Google Patents

Abstract

Preparation of storage stable, meltable, dissolvable and/or dispersible modified cycloaliphatic epoxy resins that are solid at room temperature involves replacing the cyclic hydroxycarboxylic acids can be partially or wholly replaced by semi-esters of dicarboxylic acids, their anhydrides and/or diols, the semi-esters having at least one cyclic ring structure. Preparation is claimed of storage stable, meltable, dissolvable and/or dispersible modified cycloaliphatic epoxy resins that are solid at room temperature and have more than one epoxide group per average molecular weight and optionally a fluorine content of 0.01-2 wt.%. Liquid cycloaliphatic polyepoxide compounds and cyclic monocarboxylic acids and/or cyclic hydroxycarboxylic acids and/or semi-esters of dicarboxylic acids, their anhydrides and monovalent alcohols, glycol monoalkyl ethers, polyglycol monoalkyl ethers or fatty alcohols are reacted at above 60 deg C. Reaction is optionally in the presence of organic solvent and/or catalysts for the epoxy-carboxy reaction and optionally with the use of mixtures of fluorine-free carboxyl group-containing fluorine containing carboxylic acids, their anhydrides and/or dicarboxylic acid semi-esters of fluorinated monovalent alcohols and dicarboxylic acids or their anhydrides and/or perfluorocarboxylic acids of formula F-(CF2)n-COOH (n = 5-21). 0.1-0.49 mol. carboxyl group-containing compounds is used per epoxide end group and the amount of fluorinated compounds is less than 0.1 mol. per epoxide group. The cyclic hydroxycarboxylic acids can be partially or wholly replaced by semi-esters of dicarboxylic acids, their anhydrides and/or diols, the semi-esters having at least one cyclic ring structure.

Description

The invention relates to the further development of the patent application 199 01 118.4 according to the explanations and claims below.

For the selection of raw materials, e.g. B. polyepoxide compounds, procedural characteristics and for using the modifi produced according to the invention decorated cycloaliphatic epoxy resins, reference is made to the main application, which is an integral part of the present application.

In addition to this, the following statements are made.

Instead of cyclic hydroxycarboxylic acids the main application is now all or part of half esters of dicarboxylic acids or their anhydrides or their derivatives, in particular those in the main application p. 13, paragraph 1 be wrote, and diols, especially those from the literature on polyester production, for example Stoye / Feitag, lacquer resins, Carl Hanser Verlag, Munich / Vienna, 1996, p. 49 and pp. 83-84, known diols used.

Half-esters of cyclic dicarboxylic acids or their compounds are preferred hydrides, in particular phthalic anhydride, tetrahydrophthalic anhydride, Hexahydrophthalic anhydride, camphoric anhydride, 5-norbonen-2,3-dicarbon acid anhydride, and diols with neo structure, e.g. B. Neopentyl glycol, hydroxy pivalic acid neopentyl glycol ester, 2-methyl-2-ethyl-1,3-propanediol, 2-butyl 2-ethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, or from Cyclopenta dien or dicyclopentadiene derived diols, e.g. B. tricyclodecanedimethanol, or based on lactones, e.g. B. commercially available diols based of caprolactone, or cyclic diols, e.g. B. 1,2- or 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, bisphenol A-bis-hydroxyethyl ether, 1,1'-isopropylidene-bis- (p-phenyleneoxy -) - di-2-propanol, or polyalkylene glycols, preferably with molecular weights of about 250 up to 3000, e.g. B. Polyethylene glycol 300, polyethylene glycol 3000, polypropylene glycol 250 used.

By using or using half-esters from dicarboxylic acids or their Anyhdride and polyalkylene glycols can be according to the invention produce water-dilutable modified cycloaliphatic epoxy resins, the term "water-dilutable" in the sense of the invention both water solution ability as well as aqueous dispersions or emulsions.  

Half-esters of short-chain saturated or are very particularly preferred unsaturated dicarboxylic acids or their anhydrides, especially amber acid anhydride, glutaric anhydride, citraconic anhydride, maleic anhydride; Itaconic anhydride, or cycloaliphatic dicarboxylic acids or their An hydrides, especially tetrahydrophthalic anhydride, hexahydrophthalic acid anhydride, camphoric anhydride, or of cyclopentadiene or dicyclopentadiene derived dicarboxylic acids or their anhydrides, especially 5-norbornene 2,3-dicarboxylic anhydride (3,6-endomethylene-1,2,3,6-tetrahydrophthalic acid anhydride or nadic anhydride), and cycloaliphatic diols, in particular 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, from Cyclopentadiene or dicyclopentadiene or cyclotrimerized butadiene derived diols, preferably tricyclodecanedimethanol, or with diols two cyclic ring structures, in which the individual ring structures in para position are connected by a bridge link and the two phenolic hydroxyl groups capable of esterification, preferably in the para position, included, and in the literature, for example A.M. Paquin, epoxy compound dung and epoxy resins, Springer-Verlag, Berlin / Göttingen / Heidelberg, 1958, P. 260 from multinuclear polyphenols to p. 275, are described in particular Bisphenol A. bisphenol B, bisphenol F, hydrogenated bisphenol A, of which Bisphenol A and perhydrogenated bisphenol A are especially preferred.

The production of half-esters is known in the art and not Subject of the invention. The production of half-esters can be in substance or in the melt, optionally in the presence of inert organic Solvents, e.g. B. xylene, butylgylcol tert-butyl ether, and / or Ver esterification catalysts, e.g. B. p-toluenesulfonic acid. With advantage are used for half-ester production in a known manner dicarboxylic anhydrides used.

Mixtures of the claimed half esters are preferably used. Purpose these mixtures are moderately and advantageously from the start the use of various dicarboxylic acids, especially dicarboxylic acid anhydrides, and / or various diols, in the manufacture of the half esters produced, in particular of eutectic mixtures of the components that compared to the component with the highest melting point a clearly low lower mixed melting point and / or dissolving power for the others Components have, whereby the manufacturing conditions, e.g. B. Time / Temperature curve for which half-esters can easily be optimally adjusted.

It has also been shown that the implementation in the half-ester production of dicarboxylic acids or their anhydrides and diols are not necessarily quantitative or must be carried out until 100% conversion and it is advantageous is when the half esters have unreacted or excess amounts of Dicar bonic acids or their anhydrides and / or the diols homogeneous, especially in dissolved form, because both dicarboxylic acids and their anhydrides as also diols with the polyepoxide compounds at elevated temperature, e.g. B. 60-170 ° C, especially 90 to 160 ° C. react.  

The half esters preferably contain 0 to 20 mol percent, in particular 5 up to 15 mole percent, very particularly preferably 5 to 10 mole percent, based to the stoichiometric amounts required for the half-ester production Dicarboxylic acids or their anhydrides and diols as 100 mole percent in each case, unreacted or excess amounts of dicarboxylic acids or their Anhydrides and / or diols in solution or solid solution or in homogeneous Form in the half-star. The degree of implementation in the half-ester production leaves differs in the usual way by the difference between the theoretical acid number and / or calculate the hydroxyl number (100% conversion) from the determined values.

Since according to the main application for an epoxy group 0.1 to 0.49 mol of the bean Wanted carboxyl group-containing compounds can be used (see An pronoun 12) and the preferred amount of cyclic hydroxycarboxylic acids for example 4-hydroxycarboxylic acid, according to the main application 0.01 to 0.11 mol, is very particularly preferably 0.04 to 0.08 mol (cf. main application p. 14, Paragraph 2 or line 6-21, especially line 16), this means that on a Epoxy group at most about up to 0.1 mol of dicarboxylic acids or their anhydrides and / or at most about up to 0.1 mol of diols and their amounts generally only about 0.02 moles per epoxy group.

To determine the optimal amount of the half-esters claimed by empi trials is analogous to the process engineering versions in the main application, in particular pp. 14-15, pointed out that the amount of the claimed half esters, especially in the case of partial use place the carboxyl group-containing Ver described in the main application bonds, optionally less than 0.1 mol, for example 0.01 to 0.08 mol, per epoxy group.

According to the method according to the invention, modified cycloaliphatic Epoxy resins according to claims 1 to 11 and the description of the main message created.

The use of the modifi produced by the inventive method Ornamental cycloaliphatic epoxy resins is identical to the main application as already mentioned at the beginning.

The following examples serve to supplement the description and claims play to further explain the invention without claiming full to raise consistency. The parts specified are parts by weight.  

example 1

In a conventional apparatus 80 parts of the main one in Example 1 used cycloaliphatic diepoxide heated to 110 ° C and gradually in portions (approx. 2 h approx.) taking into account a slightly exothermic Reaction 42 parts of the half ester of bisphenol A and hexahydrophthalic acid anhydride, the 2.6 parts of excess or unreacted bisphenol A and contains 1.1 parts dissolved hexahydrophthalic anhydride, and reacted at 108-112 ° C to an acid number of about 21 (guide value about 2 h). Then the temperature is increased to 127 ° C and reacted until the melt point of the colorless solid resin in a thin layer is 47 ° C, one Acid number of 14.22 was determined.

Example 2

In a conventional apparatus, 80 parts of the cycloaliphatic diepoxide 30 parts of the half according to Example 1 over a period of about 2 hours at 108-112 ° C esters of hexahydrophthalic anhydride and neopentyl glycol are added and reacted at this temperature up to an acid number of 5.9. The end product is a clear, slightly yellowish that is no longer flowable at room temperature Solid resin that has a light adhesive at room temperature (20 ° C) (sub jective test by thumb pressure).

Example 3

The solid resin from Example 3 is in a layer thickness of 3-5 mm in one the usual bottle press-in lid (diameter approx. 83 mm) and at a set temperature of 165 ° C in a laboratory drying oven Subsequent temperature treatment until the melting point is 45 ° C (dir worth about 2 h).

Example 4

In a conventional apparatus, 80 parts of the cycloaliphatic diepoxide according to Example 1 are metered in over the course of about 2.5 hours at 108-112 ° C., 50 parts of the half ester of hexahydrophthalic anhydride and polyethylene glycol 300 (by average molecular weight 285-315) and at this temperature implemented up to the acid number of 18. Then 40 parts of p-tert-butylbenzoic acid are gradually added at this temperature in the course of about 3 h and reacted to an acid number of 40. Now the temperature is slowly increased to 128 ° C until the melting point of the clear, slightly yellowish, thin, colorless solid resin is 42 ° C, an acid number of 29 being determined.
Annotation:
If significant unreacted portions of the half esters in the end products, e.g. B. remain at a higher acid number of the latter, these half esters act as latent hardener, which at a higher temperature, for. B. 130-180 ° C, the curing of the modified cycloaliphatic epoxy resins according to the invention can effect, for. B. when baking a coating.

Claims (13)

1. Process for the production of storage-stable, meltable and / or soluble and / or dispersible, modified at room temperature, modified cycloaliphatic epoxy resins with more than one epoxy group per average molecular weight, optionally with a fluorine content of 0.01 to 2% by weight, in the case of the cycloaliphatic polyepoxide compounds which are liquid at room temperature and cyclic monocarboxylic acids and / or cyclic hydroxycarboxylic acids and / or half esters from dicarboxylic acids or their anhydrides and a valuable alcohol, glycol monoalkyl ether, polyglycol monoalkyl ether or fatty alcohol, the half esters having at least one cyclic ring structure, optionally with a concomitant use of minor amounts, based on the above fluorine-free compounds containing fluorine carboxylic acids or their anhydrides and / or dicarboxylic acid half-esters of fluorine-containing monohydric alcohols and dicarboxylic acids or their anhydrides ride and / or perfluorocarboxylic acids of the general formula F- (CF ₂ ) _n -COOH with n as an integer from 5 to 21, at temperatures above 60 ° C., optionally in the presence of organic solvents and / or catalysts for the epoxy / carboxy Reaction, are implemented, using 0.1 to 0.49 mole of the carboxyl group-containing compounds on an epoxy group and the amount of optionally used carboxyl group-containing fluorine compounds is less than 0.1 mole per epoxy group, according to patent application 199 01 118.4, characterized that instead of the cyclic hydroxycarboxylic acids wholly or partly half esters of dicarboxylic acids or their anhydrides and diols, the half esters having at least one cyclic ring structure, are used. 2. The method according to claim 1, characterized in that the half esters 0 to 20 mole percent, especially 5 to 15 mole percent, especially before adds 5 to 10 mole percent, based on that for the preparation of the half esters set or stoichiometric amounts of the dicarboxylic acids or their An hydride and the diols as 100 mole percent, unreacted or over shot amounts of dicarboxylic acids or their anhydrides and / or diols contained in solution or solid solution or in homogeneous form. 3. The method according to claims 1 and 2, characterized in that half esters of cyclic dicarboxylic acids or their anhydrides and diols are used become. 4. The method according to claims 1 and 2, characterized in that half esters of dicarboxylic acids or their anhydrides and cyclic diols used become.   5. The method according to claims 1 to 4, characterized in that half esters of cyclic dicarboxylic acids or their anhydrides and cyclic Diols are used. 6. The method according to claim 5, characterized in that half esters cycloaliphatic dicarboxylic acids or their anhydrides and cyclic diols be used. 7. The method according to claim 6, characterized in that half-esters cycloaliphatic dicarboxylic acids or their anhydrides and cycloaliphatic Diols are used. 8. The method according to claims 1 to 7, characterized in that half esters of dicarboxylic acids or their anhydrides and bisphenol A and / or hydrogenated bisphenol A and / or 1,4-cyclohexanedimethanol and / or 1,4-cyclo hexanediol and / or diols derived from cyclopentadiene or dicyclopentadiene and / or diols with a neo structure and / or polyalkylene glycols can be used. 9. The method according to claims 1 to 8, characterized in that Ge Mix of half-stars can be used. 10. Use of the modifi manufactured according to the preceding claims graced cycloaliphatic epoxy resins for the production of fatty acid modifi graced epoxy resins or epoxy resin esters. 11. Use of the modified according to claims 1 to 9 cycloaliphatic epoxy resins or of epoxy resin esters according to claim 10 as a binder component for the production of solvent-free, solvent medium-containing or water-dilutable coating agents. 12. Use of the modified according to claims 1 to 9 Cycloaliphatic epoxy resins as a binder component for the production of powdered coating agents, optionally in aqueous Dispersion. 13. Use according to claim 12 as a binder component for the production pigmented or transparent powder topcoats, especially powders clear varnish for automotive serial multi-layer painting or for automotive or motor vehicle parts.