DE2643336C3 - Manufacture of solid glycidyl ethers of polyhydric phenols - Google Patents

Description

The invention relates to a method for producing solid glycidyl ethers of phenols more less with a melting point of at least 50 ⁰ C, measured according to DUi * rans (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 Regei liquid, its polymeric glycidyl ethers are mostly solid.

For the production of liquid glycidyl ethers you can according to the information in DE-AS 10 16 273 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 preparation of solid glycidyl ethers of bisphenol A with a melting point of 27 ⁰ C and 43 ° C described by first dissolving the bisphenol A in aqueous alkali hydroxide, and then the epichlorohydrin was added. This sequence is often adhered to for the production in the one-step process, since the reaction product is then obtained in a form that can be freed from the alkali metal halide by washing out. However, solid glycidyl ethers produced in this way always have a strongly fluctuating molecular weight distribution, which greatly reduces the possible applications.

In DE-AS 1131413 is a method for continuous production of solid glycidyl ethers of polyhydric phenols described, the polyvalent Phenol and epihalohydrin are mixed with a ketone and add this mixture before entering the required amount of aqueous sodium hydroxide solution is added all at once into the reaction vessel. the Addition of the ketone allows a continuous production of the glycidyl ethers in a prolonged manner Reaction zone, e.g. B. a reaction tube; however, this method does not give any improvement in the molecular weight distribution in the reaction product.

In US-PS 28 79 259 a method is described which should lead to products with better color. To do this, bisphenol A is dissolved in aqueous sodium hydroxide solution, which Contains sodium dithionite, after which epichlorohydrin is added.

In this process too, solid glycidyl ethers are obtained which have a strongly fluctuating molecular weight distribution exhibit.

In DE-AS 12 82 653 is another method for Production of solid glycidyl ethers described. This process for the production of solid glycidyl

J5 ether with a melting point of at least 50 ⁰ C, measured according to D urra η s, by reacting polyhydric phenols with not more than 1.75 mol of epihalohydrin per mol of the polyhydric phenol in the presence of water and alkali metal hydroxide and optionally in the presence of voi; Sodium dithionite or in the absence of oxygen is characterized in that the polyhydric phenol is dispersed in water at a temperature of 30 to 60 ° C, then the epihalohydrin is added and finally the aqueous alkali hydroxide solution is gradually added to the mixture at a temperature of 30 to 80 ° C gives.

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 production of solid glycidyl ethers of polyhydric phenols with a melting point of at least 50 ^° C., in which the glycidyl ethers are obtained with good solubility properties in organic solvents and a particularly narrow molecular weight distribution. Such glycidyl ethers are particularly suitable for the production of elastic coatings, the coatings produced with them

bo ge 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 glycidyl ethers of polyhydric phenols having a melting point of at least 50 ⁰ C, as measured by Durran, 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, 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 first stage in the presence of 0 , 1 to 50 mmol, per mole of the polyhydric phenol of the Chlorhydrinäther- formation of specific catalyst at temperatures of 50 to 150 ⁰ C under normal pressure, optionally unier elevated pressure within 30 to 300 min. to 10 to 95 wt .-%, weight based on the epichlorohydrin, is reacted to Chlorhydrinäther and dispersing the reaction mixture into water in a 2nd stage, and finally the aqueous Alkalihydroxydlösiing added gradually at a temperature of 25 to 80 "C to the mixture.

Preferred embodiments are in the 1st stage I to 10 mmol, per mol of the polyhydric phenol of a catalyst specific for chlorohydrin ether formation at temperatures of 90 to 120 ° C under normal pressure, optionally under elevated pressure within 60 to 1 20 min. To 50 to 80% by weight, based on the epichlorohydrin used , converted to chkirhydrin ether

To isolate the solid glycidyl ethers , they are dissolved in a solvent such as toluene, xylene or methyl isobutyl ketone at 80 to 95 ° C. during the subsequent condensation process. The aqueous salt phase is removed. The organic phase is neutralized and adjusted to values in the pH range 7-8.2. After removal of water residues by azeotropic distillation with recycling of the dehydrated solvent phase, traces of salt are removed from the organic phase by filtration. The solvent is then removed in vacuo

The etherification is preferably carried out in the absence of oxygen, for which purpose the reaction vessel with an inert gas, e.g. B. nitrogen, is flushed through and an atmosphere of this inert gas is maintained during the etherification

The process according to the invention is suitable for the preparation of glycidyl ethers of any polyhydric phenols . Examples of these are resorcinol and 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-hydi'oxy-2-methylphenyl) -propane, 2 ^ 2-bis- (2 -hydroxy-4-tert-butylphenyl) -propane, 2,2-bis- (2-hydroxypiienyl) -propane, 2,4'-dihydroxydiphenyldimethylmethane, 2,2-bis- (2-chloro-4-hydroxyphenyl) -pro - pan, 2,2-bis (2-hydroxynaphthyl) pentane, 2,2- (2,5-di bromo-4-hydroxyphenyl) butane, 4,4'-dihydroxybenzophenone, l _r 3-bis ( 4-hydroxyphenyloxy) -2-hydroxypro- pan, 3-hydroxyphenyl salicylate as well as complex polyhydric phenols, eg. B. novolak resins, which are obtained by acid-catalyzed condensation of phenol, p-cresol or other substituted phenols with aldehydes, e.g. B. formaldehyde, acetaldehyde, crotonaldehyde , and also condensates of phenols with cardanol, aliphatic diols or unsaturated fatty oils. The polyhydric phenols contain an average of two or more phenolic hydroxyl groups in their molecule and are free of other functional groups which would have an adverse effect on the formation of the desired glycidyl ether. A chlorine derivative is preferably used as the epihalohydrin. In the first stage, the reaction between the epichlorohydrin and the polyhydric phenol takes place in the presence of a catalyst, which can be a tertiary amine, a tertiary phosphine, a phosphorus, an organic sulfide and preferably an onium compound, for example a quaternary ammonium or phosphonium compound or one

ι «sulfonium compound. Examples of suitable catalysts are trimethylamine, triethylamine, triethanolamine, Triphenylphosphine, tributylphosphine, diisopropyl sulfide. Tetramethylammonium chloride and trimethylsulfonium iodide. Quaternary ammonium compounds are preferred

Ii including in particular those with aliphatic groups, each containing no more than two carbon atoms bonded to the nitrogen atom. Excellent results have been achieved with tetramethylammonium chloride and tetramethylammonium bromide

2i) hold.

As further specific catalysts for the formation of chichydrin ether from pherioiischr'üi hydroxyl and epichlorohydrin can be used:
Choline, choline chloride, choline citrate, choline hydrogen

2i 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.

j (i See -i as an example of phosphonium compounds called compounds with the formula

in which X is a halogen atom, such as chlorine, bromine or Jo 1. Ri.

Rj and Rj are the same or different monovalent Hydrocarbon radicals and R4 is a monovalent hydrocarbon radical means that also through a carbonyl. Carboxy ester, nitrile or carbonamide group substituted can be.

Ri, Rj and Rj are preferably alkyl, cycloalkyl. Aryl, alkaryl or arylalkyl groups with not more than 25 carbon atoms each, preferably with I to 18 Carbon atoms, e.g. B. phenyl, butyl, octyl, lauryl. Hexadecyl or cyclohexyl groups. R4 is preferably

-, 0 se an alkyl group having 1 to 10 carbon atoms, such as a methyl, ethyl, propyl, η-butyl, sec-butyl and n-decyl group.

Examples of phosphonium halides that are useful as catalysts are methyl triphenyl

-, -, phosphonium iodide, ethyl triphenylphosphonium iodide. Propyl triphenylphosphonium iodide, η-butyl iriphenyiphosphonium iodide, n-decyl-triphenylphosphonium iodide, methyl-tributylphosphonium iodide, ethyl-triphenylphosphonium chloride, n- butyl triphenylphosphonium

_b o chloride and ethyl tri ^ henylphosphoniium bromide. Preferred phosphonium halides are triphenylalkylphosphonium halides.

As examples of the compounds from the class of phosphoranes, alkylenephosphoranes of the general

_h 5 my formula

R'jP = CR "R '"
where R 'is aromatic hydrocarbon radicals with (·. to

12 carbon atoms and K "and K" water oiler hydrocarbon residues up to / u 20 carbon mean atoms which; iuch by carbonyl, (aibow ester groups or carbonamide groups or which can also be closed to form a ring, called:

Ph) P = C (CHOi-Ph ₁ P = CHCH ₂ CH-CH,. Ph ₁ P = CH-COOR ₁ Ph ₁ P = CH-CONH _2. PhiP = CH - CO - CH j. Ph ₁ P = ClI - CO - Ph.

Ph ₁ P = CH-CO-C H ₂ Ph.

Ph ₂ P = C (CH i) -CO -Ph.

Ph ₁ P = C (CH ₁ ) -CO-Cl I ₂ Ph.

Ph ₁ P = C (ClIi) -CO- C ₁ Hr.

Ph ₁ P = C (Ph) -CO-l'h.

Λ nhydro-siiccinyliden-1 ripl'.enyl-phosphorus ;! n.

Benzoehinonvliden inphenylphosphoran.

lliilyroliiclnnylidi'ii Irinlu η 'nhosphoran. A list of the phosphine alkylenes known from the literature can be found in IJ. S c h ö 11 head, Applied Chemistry 71.273 (1959). Alkylphosphorane. carry the cmu; i carbonyl group, are characterized by particular stability and are preferably used z. B.

Ph ₁ P = CH-CO Ph. Ph ₁ P = C (C'M ₁ ) - CO- l'h.

Ph: P = C (Ph) -CO-Ph.Ph, P = CH - CO-CH-Ph.

Ph ₁ P = CH-COOCH ₁ OdCr

Ph ₁ P = CH-CO-CH ₁ .

The catalyst is used in amounts from 0.1 to V> in mol. preferably 1 to 10 mmoles per mole of the Mehrweni ;. et Phenol used.

The following examples explain the process in more detail.

Example I.

rnOg bisphenol A (2.85 mol). 403 g F. pichlorohydrin (4, jb mol). 4.2 g of a 7OgCw ₁ - ¹ MiJgCn. aqueous choline diloride solution were heated to 95 ° C. with stirring and left at this temperature for 2 hours . 0.65 g of tin dichloride and 880 g of water were added and the mixture was cooled to about 30 ° C. In 30 to 45 minutes, 413 g of a 45% by weight aqueous sodium hydroxide solution were added dropwise evenly and the temperature was increased evenly to 80 ° C. Thereafter, it was heated to 95 ° C. and 465 g of xylene in about 60 minutes gradually added dropwise. Thereafter, a separation of the organic and aqueous phase was carried out by standing for I to 2 hours. The aqueous phase was separated 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 di \ n h line azeotropic distillation with recycling of dewatered solvent from Wasscrivston exploiting eil and filtered. It was then concentrated under reduced pressure of approx. 15 Hg at 100 to 150 ° C.

The advantageous properties of the obtained Product are from Table I and the comparison 1 can be seen.

Example 2

Example! 1 was repeated instead of 403 g if only 387 g epichlorohydrin (4.22 mol) eiiiL'esel / t.

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 Kpiehlorhydrin (4.1 mol) were used. The advantageous properties of the product obtained are shown in Table I.

Table I.

Bisphenol Λ / HCH *) KV **) Viscosity mPa
75 wt .- "nig
in xylene • s 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 M IXII = ■
"ι IV ^ i: Hpichlorohydrin.
poxide equivalent.

Determination of the cloud point

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

15 g of the solid glycidyl ether and! 5 g of xylene will be weighed in a 100 ml Erlenmeyer flask and while stirring on the reflux condenser 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 temperature 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

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

The catalyst solution of 4.2 g of choline chloride (70 wt% in water, 21.1 m mol) was, however, at 95 ° C. added to the mixture in approx. 30 min. While stirring. 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-

at 95 C ⁿ in about 30 min., where linchlorid (m mol 70gcw.% in water, 10.6) with stirring to the batch. The advantageous properties of the product obtained are shown in Table II.

Example 6

Example I was repeated, but instead of 403 g, only 387 g of epichlorohydrin (4.22 mol) used. The catalyst solution used was 1.05 g of choline chloride (70% by weight in Wiisser, "), 3 tu mol) at 9TC in Approx. JO min. given with stirring / to batch. The advantageous properties of the product obtained are shown in Table II.

Example 7

Example I was repeated, but instead of 403 g, only 387 g of epichlorohydrin (4.22 mol)) were used. As the catalyst solution 8.4 g of choline chloride were added at 95 ^C C in 30 min., With stirring, to the mixture (70 wt .-% strength 42.2 m mole in water). The advantageous properties of the product obtained are shown in Table II. The molecular weight distribution of the glycidyl ether obtained above, determined by thin layer chromatography, is given in Cig. 1 shown. For comparison, the molecular structure of a known glyeidyl acid is also shown (Example I of DT-AS 12 82 653).

Table Il mmol cat /
Moles of bisphenol A. % of the bisphenol
Turnover *) Viscosity mPas
75% by weight
in xylene IiV Cloud point example 7.4
3.7
1.85
14.8 57.8
50.7
23.4
71.9 5390
5700
6030
5290 452
449
470
456 30.5 C
30.0 C
33.5 C
31 C 4th
5
6th
7th

*) Based on the hypichlorohydrin that is available for the formation of chlorohydrate ether.

Example 8

697.5 g of bisphenol A and 50 g of a pharmaceutical novolak. 490 g of epichlorohydrin and 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 "C chilled. In 30 to 45 minutes, 556 g of a 45% by weight aqueous sodium hydroxide solution were uniformly added dropwise to the batch with uniform heating up to 80 ° C. The mixture was heated to 95 ° C. and 722 g of methyl isobutyl octone 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 aqueous sodium dihydrotephosphate 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 ether with a Epoxidäquivalem 415, a melting point of 60 to durra η ⁰ C and a viscosity, 80wt .-% strength measured in methyl ethyl ketone of 420OmPa · s obtained.

Example 9

480 g of bisphenol A and 335 g of tetrabromobisphenol, 55 g of a phenol novolak, 465 g of epichlorohydrin, 4.5 g of a 70% strength by weight aqueous choline chloride solution were heated to 95 ° C. with stirring and left at this temperature for 3 hours. 0.65 g of tin (II) chloride and 1000 g of water were added and the mixture was cooled to about 30.degree. In 30 to 45 min. Was 520 g of a 45gew.- ° / o aqueous sodium hydroxide solution uniformly with uniform heating to 80 "C are added dropwise to the mixture. It was heated to 95 C and ⁿ in about 60 min. 550 g of methyl isobutyl ketone added slowly, followed by a separation of the organic and

i) aqueous phase made by standing. The aqueous phase was separated off and discarded. The organic phase was washed with dilute sodium dihydrogen phosphate solution adjusted to a pH of 7.0 to 8.0. The solution was azeotroped Removed water residues by distillation with recycling of the solvent freed from the water. After filtration of the resulting solution was under reduced pressure of about 15 mm Hg at 100 to 150 "C concentrated to the solid resin.

■ Ti It became a solid glycidyl ether with a Epoxy equivalents of 420, a melting point according to D u r r a η of 68 ° C and a viscosity. 80% by weight in Measured methyl ethyl ketone, obtained from 2300 mPas.

so The Phenolnovohk 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% strength by weight formaldehyde solution. 5 g of oxalic acid are added at 70 ° C. 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 under gentle heating for 2 'Ii hours at 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.

Under the same conditions, 25 g of deionized water are added dropwise over a period of 30 minutes, with at the same time a mixture of phenol and water is collected in the template. (This procedure is

repeated until the free phenol content is <0.5% amounts to).

A phenol novolak is obtained with a free phenol content of 0.1%, a capillary melt / point of 91-110 "C and a hydroxyl number of 524. The average value of the degree of condensation ρ is 2.2.

Comparative investigation I to prove the
technical progress achieved

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

To a mixture of 1100 g of bisphenol A, 700 g of F.pichlorohydrin and 2080 g of water are added over the course of of 15 minutes 1384 g of 25% by weight sodium hydroxide solution, the still contains 0.10 g of sodium dithionite (Na2S2O4) in one The reaction vessel was added continuously with stirring in a nitrogen atmosphere. The temperature of the mixture before adding the sodium hydroxide solution 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 ⁰ C for 2 hours, and the resin slurry is then vacuum dried at elevated temperature (drying time 2 hours).

The resulting solid Polyglycidyläthcr 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 50gew.- ° / o solution in xylene of this solid glycidyl ether was 40.5 ⁰ C.

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

Comparative investigation 2 to prove the
technical progress achieved

In the figure are the results of gel chromatogram studies the solid glycidyl ether according to Example 1 of the invention and Example 1 according to the DE-AS 12 82 653 shown. In the case of the solid glycidyl ether according to the invention is clearly a The condensation products predominate in the middle

Table IH

Molecular range (η = 1, MG = 624, η = 2, MG = 454) compared to the lower degrees of condensation (n = 0, MG = 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 bisphenol A (2.85 mol), 403 g epichlorohydrin (4.1 g mol), 4.1 g benzyltriphenylphosphonium chloride were heated to approx "C was added 0.65 g of stannous chloride and 880 g of water and cooled to about 30 to C ^n. In 30 to 45 minutes, 413 g of a 45% by weight aqueous sodium hydroxide solution were added dropwise evenly and the temperature was evenly

2i) increased to 80 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 watery one

2 ", phase was separated off and discarded. The organic Phase was with 10% by weight aqueous sodium dihydrogen phosphate solution to a pH of 7.0 to 8.0 set. The solution was freed from water by azeotropic distillation under reflux

freed from residual water in solvent and filtered.

Thereafter, under reduced pressure of approx.

15 mm Hg concentrated to solid resin at 100 to 150 ° C.

The advantageous properties of the obtained

Product can be seen from Table 111.

^r> B eis ρ ie I 11

Example 10 was repeated. The reaction mixture was however heated for 2 hours with stirring at 120 ⁰ C under a reflux condenser. The advantageous properties of the product obtained are shown in Table III.

Example 12

Example 10 was repeated. Instead of 4.1 g of 4-, benzyltriphenylphosphonium chloride, 3.6 g of triphenylphosphine benzoylmethylene were used

(Ph ₃ P = CH-CO-Ph)

used.

The beneficial properties of the
-, 0 product can be seen from Table III.

received

Bisphenol A / ECH EV

Viscosity mPa
75% by weight
in xylene

M.p.
Durrans

Cloud point

Example 10 1: 1.53 440 3540 63 ° C 25 ° C Example 11 1: 1.53 447 3280 62.5 ° C 25 "C Example 12 1: 1.53 453 4750 64 ° C 27 ° C

Comparative examination 3 to prove the
technical progress achieved

1.) From 40 parts by weight of the approx. 75 Gew .- ^ 'oigen epoxy resin solution according to Example 10 of the present invention, 36 parts by weight of butanol, 14 parts by weight of xylene and 10 parts by weight of dipropylenetriamine is a hardening component Epoxy resin-amine adduct produced, which is ready for use ^{after storage at 20 0 C for one day}

Ii

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

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

Table IV

Example I of DE-AS 12 82 653 an epoxy resin / amine adduct according to I) 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 Steel sheets:

characteristic

lirichscntiefunt
Buchholzharte
Mandrel bending test
Cross-cut

Test standard

DIN 53156
DIN 53 153
DIN 53 152

DIN 53 151
(on steel)

Clear lacquer using the epoxy resin solution according to
Example IO of the invention Example I, I) T-AS 1282 653

approx 7-X mm

mm mandrel without crack formation

III

3 mm mandrel without crack formation

CM 2

Example IJ

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

It became a solid glycidyl ether with an epoxy equivalent of 425, a melting point after Durra η of 69'C, a viscosity, 75gcw .-% ig in Xylene, obtained from 4300 mPas and a cloud point of 26 C.

Example 14

Example 1 was repeated, instead of 4.2 g of the Aqueous choline chloride solutions were found to be anhydrosuccinylidin-triphenylphosphorus used.

It became a solid GkcidvHither with a Epoxy equivalent of 435th a melting point Durra η of 64.5 C of a viscosity. 75% by weight in Xylene, of 4550 mPas and a cloud point of Won 28 C.

1 sheet of drawings

Claims (2)

Claims; 1. A process for the preparation of solid Glyeidyläthern polyhydric phenols having a melting point of at least 50 ⁰ C, measured according to durra · ns, 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 mol of epichlorohydrin per mol 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 specific catalyst for chlorohydrin ether formation at temperatures of 50 to 150 ⁰ C under normal pressure, optionally under elevated pressure within 30 to 300 Mir * to 10 to 95 wt .-%, based on the epichlorohydrin used, converted to chlorohydrin ether and, in a 2nd stage, the reaction mixture is dispersed in water and finally at a temperature v on 25 to 80 ⁰ C the aqueous alkali hydroxide solution gradually adds to the mixture. 2. Use of the solid glycidyl ethers which can be prepared according to claim 1 as paint and coating agent components.