DE2643336B2 - MANUFACTURE OF SOLID GLYCIDYLAETHERS OF HIGH VALUE PHENOLS - Google Patents

Description

The invention relates to a process for the production of solid glycidyl ethers containing polyhydric phenols a melting point of at least 50 ° C, measured according to Durrans (Gardner and Sward, »Paint Testing Manual "12th edition, 1962, p. 367).

It is known that glycidyl ethers of polyhydric phenols, especially bisphenol A, are reacted of polyhydric phenol with epihalohydrin in the presence of alkali hydroxide. Ever according to the molar ratio of the epihalohydrin and the polyhydric phenol one can glycidyl ether of low molecular weight (so-called monomers) or of higher molecular weight (so-called Polymers).

When using an excess of 2 or more moles of epihalohydrin per mole of the polyvalent Phenols are mainly obtained as monomeric glycidyl ethers; with less than 2, preferably less than 1.75 Polymeric glycidyl ethers are obtained up to 1 mole of epihalohydrin per mole of the polyhydric phenol. at Room temperature are the low molecular weight glycidyl ethers z. B. the most commonly used bisphenol A in the Usually liquid, its polymeric glycidyl ethers, on the other hand, are mostly solid.

For the production of liquid glycidyl ethers, according to the information in DT-AS 1016 273 and the US-PS 24 67 171 dissolve the polyhydric phenol in an excess of epichlorohydrin and this solution Add aqueous sodium hydroxide solution. Since the reaction product is liquid, it can be formed as a by-product Sodium chloride can be removed from the main product without difficulty. With decreasing amount of epichlorohydrin the glycidyl ether becomes more viscous.

In US-PS 25 28 932 a process for the production of solid glycidyl ethers of bisphenol A is with melting points of 27 ° C and 43 ° C, the bisphenol A first in aqueous alkali hydroxide dissolved and then the epichlorohydrin is added. This order is common for the Production in the one-step process complied with, since the reaction product is then obtained in a form that can be used can be freed from the alkali halide by washing out. However, so produced have solid glycidyl ethers

ίο always a strongly fluctuating molecular weight distribution, which greatly reduces the application possibilities.

DT-AS 1131413 describes a process for the continuous production of solid glycidyl ethers of polyhydric phenols, the polyhydric phenol and epihalohydrin being mixed with a ketone and the required amount of aqueous sodium hydroxide solution being added all at once to this mixture before entering the reaction vessel. The addition of the ketone allows the glycidyl ethers to be produced continuously in an extended reaction zone, e.g. B. a reaction tube; however, this method does not provide any improvement in the molecular weight distribution in the reaction product.
In US-PS 28 79 259 a process is described which is said to lead to products with better color. To do this, bisphenol A is dissolved in aqueous sodium hydroxide solution containing sodium dithionite, after which epichlorohydrin is added.
In this process too, solid glycidyl ethers are obtained which have a strongly fluctuating molecular weight distribution.

DT-AS 12 82 653 describes another process for the production of solid glycidyl ethers. This process for the production of solid glycidyl ethers with a melting point of at least 50 ° C, measured according to Durrans, by repositioning polyhydric phenols with no more than 1.75 moles of epihalohydrin per mole of the polyhydric phenol in Presence of water and alkali hydroxide and optionally in the presence of sodium dithionite or in the absence of oxygen is characterized in that the polyhydric phenol is used a temperature of 30 to 60 ° C dispersed in water, then admixed the epihalohydrin and finally the aqueous alkali hydroxide solution is gradually added to the mixture at a temperature of 30 to 80 ° C.

This process also gives solid glycidyl ethers which have a fluctuating molecular weight distribution and thus have unsatisfactory solubility properties.

The object of the present invention is to provide a process for the preparation of solid polyvalent glycidyl ethers To provide phenols with a melting point of at least 50 ° C, at which the Glycidyl ether with good solubility properties in organic solvents and particularly narrow Molecular weight distribution arise. Such glycidyl ethers are particularly suitable for the production of elastic coatings, the coatings produced with them do not tend to become brittle because the low molecular weight Proportion in the molecular spectrum is reduced.

The invention relates to a process for the preparation of solid polyvalent glycidyl ethers Phenols with a melting point of at least 50 ° C,

b5 measured according to major ran, by repositioning polyhydric phenols with no more than 1.75 moles of epihalohydrin per mole of the polyhydric phenol in Presence of water and alkali hydroxide and

optionally in the presence of tin (II) salts or in the absence of oxygen, which is characterized in that the polyhydric phenol is dissolved in not more than 1.75 moles of epichlorohydrin per mole of the polyhydric phenol in a 1st stage in the presence from 0.1 to 50 mmol, per mole of the polyhydric phenol of a catalyst specific for the formation of chlorohydrin ether at temperatures from 50 to 150 ° C under normal pressure, given under increased pressure within 30 to 300 min. at 10 to 95% by weight o, based on the epichlorohydrin used, converted to chlorohydrin ether and in a 2nd stage the reaction mixture was dispersed in water and finally the aqueous alkali metal hydroxide solution was gradually added to the mixture ^{at a temperature of 25 to 80 ° C.}

Preferred embodiments are in the 1st stage, 1 to 10 mmol, per mole of the polyhydric phenol of a specific for the Chlorhydrinätherbildung catalyst at Temperaluren of 90 to 120 ⁰ C under atmospheric pressure, optionally under elevated pressure within 60 to 120 min. 50 to 80 % By weight, based on the epichlorohydrin used, converted to chlorohydrin ether.

To isolate the solid glycidyl ethers, they are heated to 80 to 95 ° C during the final phase Dissolved condensation process in a solvent such as toluene, xylene or methyl isobutyl ketone. the aqueous salt phase is removed. The organic phase is neutralized and thereby reduced to values in Adjusted pH range 7-8.2. After removing water residues by azeotropic distillation under Recirculation of the dehydrated solvent phase, traces of salt are removed by filtration from the organic Phase removed. The solvent is then removed in vacuo.

The etherification is preferably carried out in the absence of oxygen, for which purpose it is expedient to do so Beginning of the etherification the reaction vessel with an inert gas, e.g. B. nitrogen, is flushed and an atmosphere of this inert gas is retained during the etherification.

The inventive method is for the preparation of glycidyl ethers of any polyhydric phenols suitable. Examples are resorcinol, hydroquinone, methylresorcinol, phloroglucinol, 1,5-dihydroxynaphthalene, 4,4'-dihydroxydiphenyl, bis- (4-hydroxyphenyl) -methane, 1,1-bis- (4-hydroxyphenyl) -ethane, 1,1-bis- (4-hydroxyphenyl) -isobutane, 2,2-bis (4-hydroxyphenyl) propane, hereinafter referred to as "bisphenol A", 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis- (4-hydroxy-2-methylphenyl) -propane, 2,2-bis- (2-hydroxy-4-tert-butylphenyl) -propane, 2,2-bis- (2-hydroxyphenyl) -propane, 2,4'-dihydroxydiphenyldimethylmethane, 2,2-bis- (2-chloro-4-hydroxyphenyl) propane, 2,2-bis (2-hydroxynaphthyl) pentane, 2,2- (2,5-dibromo- 4-hydroxyphenyl) butane, 4,4'-dihydroxybenzophenone, 1,3-bis (4-hydroxyphenyloxy) -2-hydroxypropane, 3-hydroxyphenyl isalicylate as well as complexes polyhydric phenols, e.g. B. novolak resins obtained by acid catalyzed condensation of Phenol, p-cresol or other substituted phenols with aldehydes, e.g. B. formaldehyde, acetaldehyde, crctonaldehyde, and also condensates of phenols with cardanol, aliphatic diols or unsaturated ones fatty oils. The polyhydric phenols contain an average of two or more in their molecule phenolic hydroxyl groups and are free of other functional groups involved in the formation of the the desired glycidyl ether would have an adverse effect. The chlorine derivative is preferably used as the epihalohydrin used. In the first stage, the reaction between the epichlorohydrin and the polyvalent takes place Phenol in the presence of a catalyst that contains a tertiary amine, a tertiary phosphine, a phosphorane, an organic sulfide and preferably an onium compound, for example a quaternary Ammonium or phosphonium compound or a

IU sulfonium compound. Examples of suitable catalysts are trimethylamine, triethylamine, triethanolamine, triphenylphosphine, tributylphosphine, diisopropyl sulfide, Tetramethylammonium chloride and trimethylsulfonium iodide. Queter ammonium compounds are preferred, especially those with eliphatic groups each having no more than two carbon atoms which are bonded to the nitrogen atom. Excellent results have been obtained with tetramethylammonium chloride and tetramethylammonium bromide.

As further specific catalysts for the formation of chlorohydrin ether from phenolic hydroxyl and epichlorohydrin can be used:

Choline, choline chloride, choline citrate, choline hydrogen citrate, choline hydrogen tartrate or other choline salts in solid or dissolved form or mixed with inorganic or organic substrates.

Choline or choline chloride are preferably used.

Examples of phosphonium compounds are compounds having the formula

R ₄

in which X is a halogen atom such as chlorine, bromine or iodine, Ri, R2 and Rj are identical or different monovalent hydrocarbon radicals and R4 is a monovalent hydrocarbon radical which can also be substituted by a carbonyl, carboxy ester, nitrile or carbonamide group.

R |, R2 and Rj are preferably alkyl, cycloalkyl, aryl, alkaryl or arylalkyl groups with not more than 25 carbon atoms each, preferably with 1 to 18 carbon atoms, e.g. B. phenyl, butyl, octyl, lauryl, hexadecyl or cyclohexyl groups. R ₄ is preferably an alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, η-butyl, sec-butyl and n-decyl groups.

Examples of phosphonium halides that are useful as catalysts are methyl triphenylphosphonium iodide, Ethyl triphenylphosphonium iodide, propyl triphenylphosphorium iodide, n-butyl triphenylphosphonium iodide, n-decyl triphenylphosphonium iodide, methyl tributylphosphonium iodide, ethyl triphenylphosphonium chloride, n-Butyl-triphenylphosphonium - (, 0 chloride and ethyl triphenylphosphonium bromide. Preferred Phosphonium halides are triphenylalkylphosphonium halides.

As examples of the compounds from the class of the pi.osphoranes, alkylenephosphoranes of the general _b 5 are my formula

wherein R 'aromatic hydrocarbon radicals with 6 to

12 carbon atoms and R "and R '" are hydrogen or hydrocarbon radicals with up to 20 carbon atoms mean which are also substituted by carbonyl, carboxy ester groups or carbonamide groups or which can also be closed to form a ring, called:

Ph ₃ P = CH ₂ , Ph ₃ P = CHCH ₃ , Ph ₃ P = CHPh,
Ph ₃ P = C (CH ₃ J ₂ , Ph ₃ P = CHCH ₂ CH ₂ CH ₃ ,
Ph ₃ P = CH-COOR-Ph ₃ P = CH-CONH ₂ ,
Ph ₃ P = CH-CO-CH ₃₁ Ph ₃ P = CH-CO-Ph, ι ο

Ph ₃ P = CH-CO-CH ₂ Ph,
Ph ₂ P = C (CHj) -CO-Ph,
Ph ₃ P = C (CH ₃ ) - CO - CH ₂ Ph,
Ph ₃ P = C (CH ₃ J-CO-C ₃ H ₇ ,

Ph ₃ P = C (Ph) -CO-Ph, ι ₅

Anhydro-succinylidene-triphenyl-phosphorane,
Benzoquinonylidene-triphenyl-phosphorane,
Butyrolactonylidene-triphenyl-phosphorane.
A compilation of the phosphine alkylenes known from the literature can be found in U. S chö 11kopf, Angew. Chemistry 71.273 (1959). Alkylenephosphoranes, which carry a ^ carbonyl group, are characterized by particular stability and are preferably used z. B.

Ph ₃ P = CH-CO-Ph, Ph ₃ P = C (CH ₃ ) -CO-Ph, Ph ₃ P = C (Ph) - CO - Ph, Ph ₃ P = CH - CO - CH ₂ Ph, Ph ₃ P = CH-COOCH ₃ or
Ph ₃ P = CH-CO-CH ₃ .

The catalyst is used in amounts of 0.1 to 50 mmoles, preferably 1 to 10 mmoles, per mole of the polyhydric phenol.
The following examples explain the process in more detail.

example 1

650 g of bisphenol A (2.85 mol), 403 g of epichlorohydrin (4.36 mol), 4.2 g of a 70% by weight aqueous choline chloride solution were heated to 95 ° C. with stirring and at this for 2 hours Leave the temperature. There was added 0.65 g of tin (II) chloride and 880g of water was added to and cooled to about 30 ⁰ C. In 30 to 45 min. Was uniformly added dropwise 413 g of a 45gew.- ° / o aqueous sodium hydroxide solution while the temperature was increased uniformly to 8O ⁰ C. The mixture was then heated to 95 ° C. and 465 g of xylene were gradually added dropwise over about 60 minutes. The organic and aqueous phases were then separated by allowing them to stand for 1 to 2 hours. The aqueous phase was separated off and discarded. The organic phase was adjusted to a pH of 7.0 to 8.0 with 10% by weight aqueous sodium dihydrogen phosphate solution. The solution was freed from water residues by an azeotropic distillation with recycling of the solvent freed from the water and filtered. It was then concentrated under reduced pressure of approx. 15 mm Hg at 100 to 150 ° C. to give the solid resin.

The advantageous properties of the product obtained are shown in Table I and the comparative study 1 can be seen.

Example 2

Example 1 was repeated, but instead of 403 g, only 387 g of epichlorohydrin (4.22 mol) used.

The advantageous properties of the product obtained are shown in Table I.

Example 3

Example 1 was repeated, but instead of 403 g, only 379 g of epichlorohydrin (4.1 mol) used. The advantageous properties of the product obtained are shown in Table I.

Table I. Bisphenol A / ECH *) EV **) Viscosity mPas
75% by weight
in xylene M.p. Durrans Cloud point Example 1 1: 1.53 420 4200 61'C 25 "C Example 2 1: 1.48 449 5600 64 C 29 "C Example 3 1: 1.44 470 6200 68 C 31.5 "C *) ECIl = epichlorohydrin.
**) F ^: .V = epoxy equivalent.

Determination of the turbidity peak

The cloud point of the solid glycidyl ether is determined in 50% strength by weight xylene solution.

15 g of the solid glycidyl oil and 15 g of xylene are used weighed in a 100 ml Erlenmeyer flask and while stirring at the reflux cooler with a thermometer on a sand bath with careful stirring dissolved until a clear solution is obtained. Then the mixture is stirred at decreasing temperature until the solution is cloudy will.

The Tcmpcnilur read off shows the cloud point and is a criterion for the solubility in organic solvents and for the molecular weight distribution of the tested polyglycidyl ether.

Example 4

repeated, instead of 403 g only 387 g epichlorohydrin (4.22 mol]

Example 1 was
were however
used.

The catalyst solution of 4.2 g of choline chloricl (70gcw .-% in water, 21.1 mol) was, however, at 95 ° C. added to the batch with stirring in about 30 minutes. The advantageous properties of the product obtained are shown in Table II.

Example 5

Example 1 was repeated, but instead of 403 g, only 387 g of epichlorohydrin (4.22 mol] used. 2.1 g of Cho-

linchloride (70% by weight in water, 10.6 m mol) at 95 ° C added to the batch in approx. 30 min. while stirring. The advantageous properties of the product obtained are shown in Table II.

Example 6

Example 1 was repeated, but instead of 403 g, only 387 g of epichlorohydrin (4.22 mol) used. As a catalyst solution, 1.05 g of choline chloride (70 wt .-% in water, 5.3 m mol) at 95 ° C in added for approx. 30 min. while stirring. The advantageous properties of the product obtained are shown in Table II.

Table II Example 7

Example 1 was repeated, but instead of 403 g, only 387 g of epichlorohydrin (4.22 mol) used. 8.4 g of choline chloride (70% strength by weight in water, 42.2 m mol) at 95 ° C. were used as the catalyst solution added to the batch in approx. 30 min. while stirring. The advantageous properties of the product obtained emerge from tables. The by thin layer chromatography The determined molecular weight distribution of the glycidyl ether obtained above is in F i g. 1 shown. For comparison, the molecular weight distribution of a known glycidyl ether is shown with shown (example 1 of DT-AS 12 82 653).

example

mmol cat /
Moles of bisphenol A.

% of the bisphenol
Turnover *)

Viscosity mPa
75% by weight
in xylene

EV

Cloud point

4th 7.4 57.8 5390 452 30.5 ^° C 5 3.7 50.7 5700 449 30.0 ⁰ C 6th 1.85 23.4 6030 470 33.5 ° C 7th 14.8 71.9 5290 456 31 ⁰ C

*) Based on the epichlorohydrin that is available for the formation of chlorohydrin ether.

Example 8

697.5 g of bisphenol A and 50 g of a phenol novolak, 490 g of epichlorohydrin, 5.1 g of a 70% by weight aqueous choline chloride solution were heated to 95 ° C. with stirring and left at this temperature for 2.5 hours. There was added 0.65 g of tin (II) chloride and 1000 g of water was added to and cooled to about 30 ⁰ C. In 30 to 45 min. Was added dropwise to the mixture 556 g of a 45gew.- ° / o aqueous sodium hydroxide solution uniformly with uniform heating to 80 ⁰ C. It was heated to 95 ° C. and 722 g of methyl isobutyl ketone were slowly added in about 60 minutes. The organic and aqueous phases were then separated by allowing them to stand. The aqueous phase was separated off and discarded. The organic phase was adjusted to a pH of 7.9 to 8.0 with dilute aqueous sodium dihydrogen phosphate solution. The solution was freed from water residues by an azeotropic distillation with recycling of the solvent from which the water had been removed. After filtration of the solution obtained, it was concentrated under reduced pressure of approx. 15 mm Hg at 100 to 150 ^° C. to give a solid resin. There was a solid glycidyl ethers having an epoxy equivalent 415, melting point by Durran of 60 ⁰ C and a viscosity, 80wt .-% strength measured in methyl ethyl ketone, obtained from 4200 mPa · s.

Example 9

480 g of bisphenol A and 335 g of tetrabromobisphenol, 55 g of a phenol novolac, 465 grams of epichlorohydrin, 4.5 g of a 70 .-% aqueous choline chloride solution IGSN ⁰ C were heated under stirring to 95 and maintained for 3 hours at this temperature. There was added 0.65 g of tin (Il) chloride and 1000 g of water was added to and cooled to about 3O ⁰ C. In 30 to 45 min. Was 520 g of a 45 wt .-% aqueous sodium hydroxide solution evenly added dropwise to the mixture with uniform heating to 8O ⁰ C. It was heated to 95 ° C. and 550 g of methyl isobutyl ketone were slowly added in about 60 minutes. The organic and aqueous phases were then separated by allowing them to stand. The aqueous phase was separated off and discarded. The organic phase was adjusted to a pH of 7.0 to 8.0 with dilute sodium dihydrogen phosphate solution. The solution was freed from water residues by an azeotropic distillation with recycling of the solvent freed from the water. After filtration of the solution obtained, it was concentrated under reduced pressure of approx. 15 mm Hg at 100 to 150 ^° C. to give a solid resin.

It became a solid glyddyl ether with an epoxide equivalent of 420, a melting point after Durran of 68 ° C and a viscosity of 80% by weight in Measured methyl ethyl ketone, obtained from 2300 mPas.

so The phenolic novolak used in Examples 8 and 9 has been manufactured as follows:

500 g of phenol are melted and mixed with 143 g of aqueous 44% by weight formaldehyde solution. At 7O ⁰ C 5 g of oxalic acid are added. When the exothermic reaction has ended, the mixture is heated to reflux and a further 143 g of 44% strength by weight aqueous formaldehyde solution are added over the course of 30 minutes. After the addition, the batch is heated with careful warming for a further 272 hours

W) to reflux temperature. Thereafter, largely unconverted phenol and water are distilled off with the inclusion of a receiver up to 140 ^° C. under normal pressure and at this temperature under a reduced pressure of 20 to 40 mm Hg.

b5 Under the same conditions are within of 30 min. 25 g of deionized water were added dropwise, at the same time a mixture of phenol and water in the Template is caught. (This procedure is

10

20th

repeatedly until the free phenol content is <0.5%).

To obtain a phenol having a free phenol content of 0.1%, a capillary of 91-110 ⁰ C and a hydroxyl number of 524. The average value of the degree of condensation ρ is 2.2.

Comparative examination 1 to prove the
technical progress achieved

Example 1 of DT-AS 12 82 653 was repeated, with the approach, as indicated, a molar ratio Bisphenol A to epichlorohydrin = 1: 1.57.

To a mixture of 1100 g bisphenol A, 700 g Epichlorohydrin and 2080 g of water are 1384 g of 25% strength by weight sodium hydroxide solution in the course of 15 minutes still contains 0.10 g of sodium dithionite (Na2S2Ü4) in one The reaction vessel was added continuously with stirring in a nitrogen atmosphere. The temperature of the mixture before adding the caustic soda is 52 ° C.

After the exothermic reaction has ended (1 hour), the temperature ^{rising to 102 °} C., the mother liquor formed, which contains sodium chloride formed and excess sodium hydroxide solution, is siphoned off. The resin slurry is washed with water at temperatures of 75 to 85 ° C. for 2 hours, and the resin slurry is then dried in vacuo at an elevated temperature (drying time 2 hours).

The resulting solid polyglycidyl ethers showed a softening point of 68 ⁰ C after the Durrans mercury method, an epoxy equivalent of 480 for sale.

The cloud point of a 50 .-% solution in xylene of this solid glycidyl ether was 40.5 ⁰ C.

A comparison of the results shows that, despite the low j ^ Epichlorohydrin excess (1: 1.53 to 1.44) significantly lower epoxy equivalents due to the more uniform Molecular weight distribution can be achieved, which is characterized by a lower cloud point and a better solubility of the ^ o expresses solid glycidyl ether in xylene.

Comparative examination 2 to prove the
technical progress achieved

The figure shows the results of gel chromatogram examinations of the solid glycidyl ethers according to Example 1 of the invention and Example 1 according to DT-AS 12 82 653. In the case of the solid glycidyl ether according to the invention, there is a clear predominance of the condensation products in the middle y> molecular range (/ J = I, MG = 624, η = 2, MC = 454) over the lower degrees of condensation (n = 0, MC = 340, η = 3, MG = 1192 etc.).

This different molecular weight distribution translates into improved physical properties the solid glycidyl ether as a paint and coating binder.

Example 10

650 g of bisphenol A (2.85 moles), 403 g of epichlorohydrin (4.36 moles), 4.1 g of benzyltriphenylphosphonium chloride were heated with stirring to about 120 ⁰ C under reflux and maintained for 5 hours at this temperature. After cooling below 100 ⁰ C, 0.65 g of stannous chloride and 880 g of water were added and up to about 30 ⁰ C cooled. In 30 to 45 min. Was uniformly added dropwise 413 g of a 45gew.- ° / o aqueous sodium hydroxide solution while the temperature was increased uniformly to 8O ⁰ C. The mixture was then heated to 95 ° C. and 465 g of xylene were gradually added dropwise over about 60 minutes. The organic and aqueous phases were then separated by allowing them to stand for 1 to 2 hours. The aqueous phase was separated off and discarded. The organic phase was adjusted to a pH of 7.0 to 8.0 with 10% strength by weight aqueous sodium dihydrogen phosphate solution. The solution was freed from water residues by an azeotropic distillation under reflux of the solvent from which the water had been removed and filtered. It was then concentrated under reduced pressure of approx. 15 mm Hg at 100 to 150 ° C. to give the solid resin. The advantageous properties of the product obtained are shown in Table III.

Example 11

Example 10 was repeated. However, the reaction mixture was refluxed at 120 ° C. with stirring Heated for 2 hours. The advantageous properties of the product obtained are off Table III can be seen.

Example 12

Example 10 was repeated. Instead of 4.1 g of benzyl triphenylphosphonium chloride, there was 3.6 g of triphenylphosphine benzoylmethylene

(Ph ₃ P = CH-CO-Ph)
used.

The advantageous properties of the product obtained are shown in Table III.

JO

Table III Bisphenol A / ECH : 1.53
: 1.53
: 1.53 EV Viscosity mPas
75% by weight
in xylene Snip.
Durrans Cloud point 1
1
1 440
447
453 3540
3280
4750 63'C
62.5 ^'1 C
64 ' ¹ C 25'C
25 "C
27 ' ¹ C Example 10
Example 11
Example 12

Comparative investigation 3 to prove the
technical progress achieved

1.) From 40 parts by weight of the approx. 75% strength by weight epoxy resin solution according to Example 10 of the present invention Invention, 36 parts by weight of butanol, 14 parts by weight Xylene and 10 parts by weight of dipropylenetriamine is an epoxy resin-amine adduct as the curing component which is ready for use after it has been stored at 20 ° C for 1 day.

2) From 22 parts by weight of solution 1), 40 parts by weight of the approx. 75% strength by weight epoxy resin solution according to Example 10 of the present invention, 14 parts by weight n-butanol, 9 parts by weight of xylene and 15 parts by weight Methyl i-butyl ketone, a clear coat was made.

In the same way, using a 75% by weight xylene solution of the epoxy resin according to

Table IV

Example 1 of DT-AS 12 82 653 produced an epoxy resin-amine adduct according to 1) and a clear lacquer according to 2).

The investigation of the clearcoats showed after curing for 7 days at room temperature at one Layer thickness of approx. 30 μ has the following properties on sheet steel:

Eigenschart I'rüfnorm clear lacquer using the epoxy resin solution according to

Example 10 of the invention Example 1, DT-AS 1282653

Erichsen depression
Buchholz hardness
Mandrel bending test
Cross-cut

DIN 53156
DIN 53 153
DIN 53 152

DIN 53 151
(on steel)

approx. 7-8 mm

mm mandrel without crack formation

Gt 3

9-10

111

3 mm mandrel without cracking

Gt 2

Example 13

Example 1 was repeated, instead of 4.2 g of the aqueous choline chloride solution, 4 g of tetramethylammonium bromide were used used.

It became a solid glycidyl ether with an epoxy equivalent of 425, a melting point after Dur ran of 69 ° C, a viscosity of 75% by weight in xylene, of 4300 mPas and a cloud point of Gained at 26 ° C.

Example 14

Example 1 was repeated, instead of 4.2 g of the aqueous choline chloride solution, 6 g of anhydrosuccinylidene-triphenyl-phosphorane were used used.

It became a solid glycidyl ether with a

Epoxy equivalent of 435, a Durran melting point of 69.5 ° C., a viscosity of 75% by weight in

jo xylene, of 4550 mPas and a cloud point of 28'C won.

1 sheet of drawings

Claims (2)

Patent claims: 1. Process for the preparation of solid glycidyl ethers of polyhydric phenols with a melting point of at least 50 ° C, measured according to D urra η s, by reacting polyhydric phenols with not more than 1.75 moles of epihalohydrin per mole of the polyhydric phenol in the presence of water and Alkali hydroxide and optionally in the presence of tin (II) salts or in the absence of oxygen, characterized in that the polyhydric phenol is dissolved in not more than 1.75 moles of epichlorohydrin per mole of the polyhydric phenol in a 1st stage in the presence of 0 , 1 to 50 mmol, per mole of the polyhydric phenol of a catalyst specific for the formation of chlorohydrin ether at temperatures of 50 to 150 ° C. under normal pressure, optionally under elevated pressure within 30 to 300 minutes at from 0 to 95 % by weight on the epichlorohydrin used, converted to the chlorohydrin ether and, in a 2nd stage, the reaction mixture is dispersed in water and finally at a temperature v from 25 to 80 ° C gradually adding the aqueous alkali hydroxide solution to the mixture. 2. Use of the solid glycidyl ethers which can be prepared according to claim 1 as a paint and coating agent component.