DE2533505C3 - Process for the production of low viscosity, low molecular weight glycidyl ethers of monohydric or polyhydric phenols - Google Patents

Description

The invention relates to a method for producing low-viscosity, low-molecular glycidyl ethers monohydric or polyhydric phenols with improved properties.

By improved properties it is meant that produced by the process of this invention obtained glycidyl ether have a low viscosity, and after mixing with finely dispersed Fillers and pigments form stable dispersions. Further improved properties of this glycidyl ether prepared according to the invention are lower Chlorine content and a low inherent coloring of the glycidyl ethers, expressed by low values of the

ίο Hazen color number ASTM D 1209/62, Pt / Co standard: Hazen standard [(APHA)].

There are already various processes in the literature for the preparation of diglycidyl ethers of one and polyhydric phenols have become known under Use of suitable catalysts, mainly quaternary ammonium salts, as well as certain sulfonium salts and phosphonium salts, in one In the first process stage, in the absence of alkali, a certain degree of conversion to chlorohydrate make in ether of the phenols.

Mention should be made of DE-PS 21 08 207, which is a method for the production of glycidyl ethers of monohydric and polyhydric phenols by reacting the phenols with 3 to 15 Moles of epichlorohydrin per phenolic hydroxyl group in

Presence of about one equivalent of a solid alkali hydroxide as well as phenolic hydroxyl group 0.05 to 5 percent by weight of a tertiary amine or a quaternary ammonium compound as a catalyst at elevated temperature and subsequent separation tion of the excess epichlorohydrin together describes with the water from the reaction mixture by distillation and recovery of the glycidyl ether formed, characterized in that the Alkali hydroxide for 30 to 300 minutes adds and the reaction in the presence of choline or choline salts or mixtures thereof as a catalyst and in the presence of 2 to 8 percent by weight Water and additionally the water of reaction formed at 50 to 110 ° C with removal of the reaction heat carries out Choline or choline salts are added as catalysts before the addition of alkali

In DE-OS 20 28136 a method is for Production of low molecular weight polyglycidyl ethers by reacting a polyhydric phenol with Epichlorohydrin in an equivalence ratio of at least 14: 1 in the presence of a catalyst in one practically anhydrous, non-alkaline medium, in which to at least »5%. preferably at least 80%, the phenolic hydroxyl groups are etherified, in a first stage, and then Dehydrochlorierii obtained in the first stage in the presence of excess Chlorhydrinäthers Jon epichlorohydrin with an aqueous solution of an alkaline compound described, which is characterized in that the dehydrochlorination with an amount of 0.80 to 0.99 equivalents of the alkaline compound per equivalent of the polyhydric phenol being, during dehydrochlorination first Water is distilled off azeotropically from the mixture, then the remaining epichlorohydrin is distilled off and finally the reaction product of a second Dehydrochlorination with an excess of the alkaline compound with respect to the amount of the easy saponifiable, still present chlorine is subjected.

In the first stage the reaction takes place between the Epichlorohydrin and the polyhydric phenol in

Presence of a catalyst instead of a tertiary Amine, a tertiary phosphine, an organic sulfide and preferably be an onium compound of these substances can, i.e. a quaternary ammonium or phosphonium compound «Who has a sulfonium compound. Examples of suitable catalysts are

Trimethylamine, triethylamine,
Triethanolamine, triphenylphosphine,
Tributylphosphine, diisopropyl sulfide,
Tetramethylammonium chloride,
Methyltriphenylphosphonium bromide and
Trimethylsulfonium iodide.

10

15th

Quaternary ammonium compounds are preferred, especially those with aliphatic groups, the each contain no more than two carbon atoms bonded to the nitrogen atom. Outstanding Results were obtained with tetramethylammonium chloride and tetramethylammonium chloride.

The CH-PS 4 32 544 describes a method for Production of glycidyl ethers of polyhydric phenols, characterized in that polyhydric phenols are mixed with epihalohydrins in the presence of sulfonium salts or sulfur-containing compounds that can react with epihalohydrin to form sulfonium salts, converts to the corresponding halohydrins and that after the excess epihalohydrin has been separated off hydrogen halide is split off from the halohydrins.

The salt-like compounds used as catalysts behave in relation to the finished ones Epoxy resins such as latent hardeners; and since they are obviously not completely during the manufacturing process are removed from the respective glycidyl ether, these have a lower storage stability in particular at higher temperatures, which has considerable disadvantages for many purposes, where the viscosity stability of the resins is important. The use of low-viscosity epoxy resins may be mentioned in the cast resin sector as well as in 2-component injection molding machines in which the resins are used for a longer period of time need to be heated to higher temperatures. Tertiary ammonium salts from tertiary amines and Inorganic acids can dissociate through the action of heat and then through the catalytic action cause an undesirable increase in viscosity. This is due to the fact that ammonium salts are made up tertiary amines and inorganic acids dissociate by the action of heat and then by the catalytic effect of the tertiary amine on the epoxy groups through polymerization

j OH

\ l \ /
CC

R ₃ N * ⁹

C <

O — C —C

OH

\ / C-C

R3N * ⁹

cause a strong increase in viscosity, which can lead to the structure * ', _,. At the start of the polymerization

The small amounts of hydroxyl groups in the

y] epoxy resin are included when opening the

Dissociate epoxide groups with in the same way f \ quaternary salts in the heat, which in any case tertiary

,. "l Amines are generated. The use of betaine as

; <latent hardening agent is in GB-PS 9 61 023

p described.

K The from produced by known processes

ö Glycidyl ethers, fillers and pigments obtained

ß Solvent-based and solvent-free dispersions tend to be

'J often used to separate the two phases. Also the

d The addition of dispersing auxiliaries is of no use

_t ' remedy for this phenomenon.

The chlorine content of the known, commercially available

Polyglycidyl ether comes from three different by-products from:

1. RO-CH ₂ -CH-CH ₂
O Cl

2. R-0 -CH
\

H
CH ₂ Cl

60

65

CH ₂ OH

3. RO-CH ₂ -CH-O-CH ₂ -CH CH ₂

CH ₂ Cl 0

The organically bound chlorine can be removed in different ways by saponification. Just that im normal chlorohydrin ether (1.) existing chlorine is referred to as hydrolyzable chlorine and z. B. after the Method ASTM D 1726-67 recorded

When the glycidyl ethers are hardened with amines or anhydrides, especially when tertiary amines or other compounds are used, which tend to form onium salts as accelerators as a result of reaction with HCl-splitting groups, the total chlorine content, however, has a negative influence on the Course of hardening, as the onium salt formation can disturb the hardening reaction in an irregular manner. In addition, the glycidyl ethers of monohydric or polyhydric phenols have a more or less strong yellow color.

The object of the present invention is to provide a process for the production of such low-viscosity Glycidyl ethers provide monohydric or polyhydric phenols with finely dispersed fillers and pigments form stable dispersions and low levels of organically bound chlorine as well as a have little inherent coloring.

Surprisingly, it has been found that low-viscosity glyeidyl ethers are monovalent and polyvalent Can produce phenols that do not have these disadvantages if you implement the mono- or polyhydric phenols with epichlorohydrin too Carries out chlorohydrin ethers in the presence of catalysts that are very specific for the implementation.

The invention relates to a process for the production of low viscosity, low molecular weight glycidyl ethers by reacting mono- or polyhydric phenols with excess epichlorohydrin, based on the phenolic hydroxyl group, in the presence of a catalyst specific for the formation of chlorohydrin ether, at least 10% by weight, based on the phenolic hydroxyl groups are converted to chlorohydrin ethers and these then with 0.9 to 1.15 of an equivalent of a solid or dissolved alkali metal hydroxyl per phenolic hydroxyl group, optionally in two stages, at temperatures between 50 to 200 ⁰ C and optionally reduced pressure be converted to glycidyl ethers with simultaneous dehydration by azeotropic distillation or by circulating distillation, characterized in that the chlorohydrin ether formation in the presence of 0.01 to 10 mol%, based on the mono- or polyhydric phenols used, of an alkylene phosphorane of the formula

Ph ₃ P = CR "R '

(1)

carried out, where R "and R '" a hydrogen aiom or hydrocarbon radicals with up to 2G carbon atoms, which may be replaced by carbonyl, nitrile, Carboxy ester groups or carbonamide groups or which are also closed to form a ring.

Another embodiment of the method is characterized in that 0.25 to 5 mol%, based on the monohydric or polyhydric phenols used, alkylene phosphorane can be used.

After the formation of the glycidyl ether by adding solid alkali hydroxide or dissolved in water the excess epichlorohydrin is distilled off from the glycidyl ether formed and optionally the obtained glycidyl ether dissolved in an inert solvent and with the help of excess aqueous Alkali hydroxide solution, based on the hydrolyzable chlorine present, is subjected to a further dehydrochlorination.

In this way, very low-viscosity glycidyl ethers are obtained whose chlorine content is below 03 % By weight. The glycidyl ethers produced in an improved manner can therefore be used with particular advantage Production of molding compounds and coatings and embeddings are used in the electrical sector, where epoxy resins with a higher chlorine content especially with the simultaneous presence of heat and Moisture have a lower resistance. In addition, the hardening z. B. when using tertiary amines without interference.

In connection with the low chlorine levels, the level of chlorine is that produced according to the invention Glycidyl ether on hydroxyl groups, expressed by low values of the hydroxyl numbers, very low, which greatly facilitates the formation of stable dispersions with finely dispersed pigments or fillers will.

The achievable resin color numbers of the glycidyl ethers obtained by the process according to the invention are below 100 on this color scale.

With glycidyl ethers of bisphenol A, which have such color numbers, it is possible when using Correspondingly lighter epoxy resin hardener areas of application that were previously used for unsaturated polyesters were reserved for the latter, however, due to their less favorable chemical resistance and mechanical properties, were only suitable to a limited extent. Such uses are, for example, electrical, anatomical and other embeddings Objects, white pigmented layers and lacquer coats.

Another object of the invention is to provide such to provide improved method available that one glycidyl ethers of mono- or polyhydric phenols by reacting the phenolic OH groups with excess epichlorohydrin in the presence of Obtain catalyst groups and alkali in a very pure form with the shortest possible boiler occupancy times can.

It is also possible in this process to remove the epichlorohydrin-De obtained after the condensation stillat after replenishing the smoky parts Epichlorohydrin and the losses by distillation can be used again and again without rectification and without the condensation products being adversely affected. This is a rational production of the Glycidyl ethers are possible in the first place.

The new process is also characterized by the fact that the yield is almost that according to theory The resulting glycidyl ether also corresponds to the secondary epichlorohydrin losses undesirable side reactions, such as. B. the polymerization of epichlorohydrin or ether formation Epichlorohydrin in the presence of alkali, depressed to a minimum.

As examples of the alkylenephosphoranes of the general formula claimed as catalysts for the formation of chlorohydrin ethers

PhjP = CR "R" '

where R "and R '" have the meaning already mentioned, may be mentioned:

Ph ₃ P = CH ₂ , Ph ₃ P = CHCH ₃ , Ph ₃ P = CHPh, Ph ₃ P = C (CHj) ₂ , Ph ₃ P - CHCH ₂ CH ₂ CH ₃ , Ph ₃ P = CH-COOR, Ph ₃ P = CH-CONH ₂ , Ph ₃ P = CHCN, Ph ₃ P - CH-CO-CH ₃ , Ph ₃ P = CH-CO-Ph, Ph ₃ P = CH-CO-CK ₂ Ph, Ph ₃ P = QCHj) -CO-Ph ₁ Ph ₃ P - C (CH ₃ ) -CO-CH ₂ Ph, Ph ₃ P - QCH ₃ J-CO-C ₃ H ₇ , Ph ₃ P = QPh) -CO-Ph, Anhydro-succinylidene-triphenyl-phosphorane, Benzoquinonylidene-triphenyl-phorphoran, Butyrolactonylidene-triphenyl-phosphorane.

A compilation of the phosphine alkylenes known from the literature can be found in U. Schöllkopf, Angew. Chemie 71, 273 (1959).

Alkylenephosphoranes, which carry a / J-carbonyl group, are characterized by particular stability from and are preferably used, for. B.

Ph ₃ P = ClJ -CO-Ph, Ph ₃ P = C (CH ₃ ) - CO -Ph,

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

A particular embodiment of the invention Process is characterized in that the amount of catalyst used is between 0.2 and 1 mole percent. in particular between 0.25 and 0.75 mol%, based on the monohydric or polyhydric phenol.

The following can be used as monohydric or polyhydric phenols: phenol, o-, m- and p-cresol. 1,2,4-, 1,2,6-, 1,2,3-, 1,2,5-, 1,3,4- and! .3.5-xylenol. p-tert-butylphenol, o-, m- and p-phenylphenol, the isomeric amylphenols. Octylphenols and nonylphenols, resorcinol, 2.2'-. 2,4'- and 4,4'-dihydroxydiphenylmethane. individually or in a mixture (also known as bisphenol F), furthermore substituted dihydroxydiphenylmethanes. such as are formed by the acidic condensation of phenols with aldehydes or ketones, in particular 4,4'-dihydroxydiphenyl-2,2-propane, the so-called diphenylolpropane or bisphenol A, and tetrabromobisphenol, which can be prepared from phenol and acetone.

There are also polyhydric phenols, e.g. B. Novolak resins, the acid-catalyzed condensation of phenol, p-cresol or other substituted phenols with aldehydes such as formaldehyde, acetaldehyde, crotonaldehyde, i-butyraldehyde, i-nonylaldehyde, etc. obtained be in question.

The above list of compounds suitable as starting materials is not exhaustive. One detailed compilation of the connections in question is z. B. in the book »Epoxy compounds and Epoxy Resins ”by A. M. Paquin. Springer publishing house. 1958, pages 256-307.

Phenol and p-tert-butylphenol are preferred. Bisphenol A. Bisphenol F and tetrabromobisphenol are used.

In another embodiment, a mixture of 0.60 to 0.99 moles of bisphenol A and 0.40 to 0.01 mol of a diphenol from the group of the compounds listed above, in particular resorcinol. Bisphenol F. Novolak resins, dir by acid catalyzing component, but also as a solvent for the einodcr polyhydric phenols and the chlorohydrin ethers formed. The mono- or polyhydric phenols are mixed with and dissolved in such an amount of epichlorohydrin that on each phenolic Hydroxyl group come at least 1.5, preferably between 2.5 and 10 mol of epichlorohydrin.

The inventive method surprisingly allows the production of resins with low Ratios of epichlorohydrin to mono- or polyhydric phenol which have the same viscosity as such Have products made by the known processes, but with higher ratios of epichlorohydrin and phenol can be used. The reaction mixture can also be inert solvents contain, such as xylene or n-butanol, but this is unnecessary.

You can carry out the reaction in the presence of 3 to 25 percent by weight of a sparingly water-soluble Alcohol, such as n-butanol, i-butanol. sec-butyl alcohol. the various isomer pentanols or hexanols, preferably i-butanol or n-butanol. in fact preferably in an amount of 5 to 10 percent by weight, based on the amount of epichlorohydrin used. carry out.

For the same purpose, it can also be used alone or in addition to the aliphatic , Alcohols) presence of 3 to 25 percent by weight aromatic solvents such as benzene. Toluene, xylene and others, preferably xylene, worked will.

In the first stage the reaction takes place between the Epichlorohydrin and the monohydric or polyhydric phenol in the presence of a phosphorane as a catalyst instead. The reaction in the first stage is allowed to proceed until at least 10, preferably 50 to 90% of the available phenolic hydroxyl groups have been etherified. There is an advantage when at this stage as many phenolic hydroxyl groups as possible, preferably more than 96%, are etherified.

This latter requirement can be met by proper selection of the reaction conditions, such as the reaction time and temperature, and the amount of catalyst

Formaldehyde. Acetaldehyde. Crotonaldehyde. i-butyraldehyde for the production of diglycidyl ether with low viscosity (6000 to 16000 cP / 25 ° C) used to at to prevent these products from crystallizing after prolonged storage in cool rooms.

The monohydric or polyhydric phenols used should have as little inherent color as possible, z. B. the resin color number of a 30 wt .-% solution of bisphenol A in methanol should be below 50.

The alkali hydroxides can be used as 30 to 70% strength by weight aqueous solutions. Further come the solid compounds in granular, flaky or powdered form in question, whereby the Sodium hydroxide is the preferred alkali hydroxide

The addition of the solid alkali metal hydroxides can be carried out by known devices, such as metering screws or Rotary feeders take place, as this z. B. in the book Jan Pinkava "Laboratory technology for continuous chemical processes", Harri Deutsch publishing house, Frankfurt / Main 1962, pages 144-146. Are described above.

1.5 to 15 are preferably used in the reaction 2.5 to 10 mol epichlorohydrin per phenolic OH group.

The epichlorohydrin not only acts as a reaction

see 50 and 200 "C. in particular between 90 and 130 ⁰ C.

For etherification of more than 80%, the reaction time required in the first stage is at least 15 minutes, depending on the temperature used, the reaction time generally being between 20 minutes and 5 hours at reaction temperatures between 90 and 130.degree. For lower etherification values (at least 10%), the first stage can be ^{carried out at temperatures of 20 to 100 °} C. for 5 to 20 minutes.

The pressure in the reactor during the first stage can be selected so that all reaction components stay fluid. However, it may be advantageous to select the pressure so that, for. B. epichlorohydrin am Distilled under reflux. If the reaction mixture contains too much water, the water content can be azeotropic Distillation can be reduced with epichlorohydrin.

After the vapors have condensed and separated into layers, the epichlorohydrin layer be returned to the reactor. This method can e.g. B. then be used when the catalyst is added to the reaction mixture in the form of an aqueous solution.

During the first stage, the reaction medium contains less than 3% by weight of water.

The reaction product from the first stage contains, inter alia, the catalyst, excess epichlorohydrin, dichloropropanol, chlorohydrin ether and glycidyl ether. If the flowability of the mixture is too low, an inert solvent such as xylene can conveniently be added. However, if a revealing, z. D. A five-fold excess of epichlorohydrin is used in the first stage, this is not necessary. In the following stage, the reaction mixture is by reaction with 0.90 to 1.15 equivalents of a solid or dissolved in water alkali metal hydroxide, for. Sodium or potassium hydroxide, per equivalent of phenolic hydroxyl group, which is added in portions or continuously added thereto at 50 to 12O ⁰ C, preferably 50 to 110'C in 30 to 300 minutes, with azeotropic dehydration, or dehydration by azeotropic distillation with recycling of the distilled and dehydrated epichlorohydrin takes place, dehydrohalogenated. It is advantageous to introduce as little water as possible into the reaction mixture through the aqueous solutions of the alkaline compound, which are therefore added in the most concentrated possible form of at least 25% by weight, preferably at least 45% by weight.

By removing the water of reaction by dehydration in the circuit or by azeotropic Distillation shifts the equilibrium to the side of the glycidyl ether and the formation of Glycidyl ethers favored, which are particularly poor in easily saponifiable chlorine:

n ο

Cl

R-O-CH ₂ -CH-CH ₂ + NaOH >

This procedure prevents the formation of higher molecular weight, sparingly soluble phenoxy ethers, which can easily happen if too little reaction /
RO-CH ₂ -CH

CH ₂ + NaCl + H ₂ O

speed of chlorohydrin ether formation at the same time glycidyl ether and phenols in an alkaline medium are present:

// + 2CH ₂ CH-CH ₂ -ORO-CH, CH CH ₂ + «HO - R-OH

H
O

NaOH

CH ₂ CH-CH ₂ -ORO-CH ₂ CH CH ₂ -TOROI ₇ ^ CH ₂ -CH CH ₂ -ORO

CH,

CH

(R = aromatic radical).

This would considerably reduce the yield and the isolation of the glycidyl ether make more difficult. In addition, there is only the monomeric chlorohydrin ether when the alkali metal hydroxide is added from the outset is present, also ensures the formation of a largely monomeric glycidyl ether.

A suitable way of removing water is by distilling off the water as an azeotrope with epichlorohydrin during the dehydrochlorination. If necessary, the azeotrope can be condensed, the epichlorohydrin layer can be separated from the water layer and the epichlorohydrin layer can be returned to the reactor (circulation distillation). Vigorous stirring is carried out during the dehydrochlorination

In general, the dehydrochlorination, which can be carried out at a temperature between 50 and 120 ° C., takes between 30 minutes and 5 hours found that short dehydrochlorination times of between 30 minutes in terms of epichlorohydrin losses and 2 hours are very advantageous. Gradual addition of the alkaline compound over a period of

for example at least 30 minutes, also helps to prevent unnecessary epichlorohydrin losses.
If you put solid alkali hydroxide, z. B. caustic soda,

W is initially given from 10 to 90% by weight, preferably from 15 to 50% by weight, of the solid alkali hydroxide in 18 to 90%, preferably from 15 to 50%, of the total addition time of the solid alkali hydroxide, which is 30 to 300, preferably 90 to 180 minutes, with removal of the heat of reaction by cooling or by distillation under reflux at reduced pressure in the presence of water of reaction and then 90 to 10% by weight, preferably 85 to 50% by weight, of the solid alkali metal hydroxide in 82 to 10%, preferably 85 to 50% of the total addition time of the solid alkali metal hydroxide, with removal of the heat of reaction, of the water of reaction by azeotropic distillation and optionally recycling of the epichlorohydrin-containing phase freed from the water to the reaction mixture.

After addition of the alkali metal hydroxide, preferably sodium hydroxide, is distilled under reduced pressure at a temperature of 60 to 70 ° C a part of the excess epichlorohydrin and optionally of

additional solvent - about 10 to 30 percent by weight of the amount used - then filtered off the metal halide formed in the reaction and concentrated further under vacuum and heating the batch to 120 ^° C. The liquid glycidyl ether can be filtered again to remove minor impurities; or is removed by vacuum at temperatures of 60 ⁰ C initially and finally 1.WC excess epichlorohydrin and optionally the additional limited water-soluble solvent. The reaction product is then taken up in a suitable solvent, such as acetone, methyl isobutyl ketone, benzene, toluene or xylene, and the alkali metal chloride is washed out with water.

After this process stage, the subsequent is dehydrochlorination of the polyglycidyl ether product is carried out with an excess of the alkaline compound, based on the amount of easily saponifiable chlorine still present. This Nachdehydrochiorierung soiiie preferably unier use m a dilute alkaline solution of z. B. between 2 and 20 wt .-% sodium hydroxide between 60 and 120 ⁰ C are carried out. The amount of dilute alkali metal hydroxide for the second dehydrochlorination is preferably a 3 to 15-fold excess, based on the amount of easily saponifiable chlorine that is still present in the polyglycidyl ether.

The salt formed during the first and second dehydrochlorination, which is derived from the Γ. _dukt must be removed can also be removed by centrifugation or filtration. The removal of the Salt can be done in different process steps and can also be done with the help of a combination of Filtration, centrifugation and washing are done. The glycidyl ether solution is, if necessary after a) 5 Neutralization of the solution, e.g. B. with dilute acetic acid or sodium dihydrogen phosphate solution a pH of 6.0 to 8.0 dehydrated by azeotropic distillation and under vacuum to 150 ° C constricted. The liquid glycidyl ether can then still -to be freed from impurities by filtration.

In a particular embodiment, the last residues of organic solvent from the liquid Glycidyläthev by steam distillation at temperatures from 100 to 180 ^e C, preferably 140 to 160 ° C, optionally by means of vacuum, removed.

In another embodiment, from 100 to 180 preferably ⁰ _C1 140 to 160 ° C, heated liquid glycidyl ethers of the volatiles removed in such a way, by adding 10 to 1 wt .-%, preferably as 6-3 wt %, based on the glycidyl ether, aqueous hydrogen peroxide solution (HjOr content: 1 to 20% by weight, preferably 3 to 6% by weight) can flow in with stirring

The individual stages of the process according to the invention are also suitable for continuous implementation.

The following examples explain the process in more detail:

example 1

1341 g epichlorohydrin, 330 g bisphenol A and 1.71 g Triphenylphosphine-benzoyl-methylmethylene

Ph ₃ P = C (CHs) -CO-Ph

was in one with stirrer, thermometer and Flask provided with distillation device for 120 min heated to reflux temperature (about 120 ° C) and then

60 dehydrohalogenated 00 ⁰ C under normal pressure by uniform train "Se of 255 g 44,4gew.- ° / aqueous sodium hydroxide solution cent, the azeotrope was distilled off from epichlorohydrin and water: in a further 120 min at.

After completion of the addition, the residual epichlorohydrin was distilled off, the temperature was raised to 120 ⁰ C. At 12O ⁰ C, the mixture was left for 60 minutes under a vacuum of about 20 mm Hg. To separate the common salt, the glycidyl ether was dissolved in 500 g of xylene and 660 g of water were added. The salt phase was separated, the xylene phase was heated with a mixture of 45 g 44,4gew .-% sodium hydroxide solution and 300 g of water at about 90 ⁰ C for 75 min to convert residual Chlorhydrinäther in glycidyl ethers. The aqueous phase was again separated off. After neutralization of the xylene phase with dilute, aqueous sodium dihydrogen phosphate solution, water residues in the Xy- ιύικίcisiaüi äugcifcifi'ii.

/ \ yiOi wüi'uc üi'itci * vciTim '

dertem pressure of about 20 mm Hg and temperature increase to 120 ⁰ C removed. After a further filtration to remove the salt residue to obtain a bisphenol A-glycidyl ether having an epoxy equivalent of 182, viscosity of 805OcP, measured at 25 ⁰ C, a content of easily hydrolyzable chlorine of 0.12 wt .-%, a Hazen Color number of 60 and a hydroxyl number of 18.

Example 2

The procedure given in Example 1 was followed. However, 1.99 g were used as the catalyst Triphenyl-phosphine-benzoyl-phenylmethylene

Ph ₃ P = QPh) -CO-Ph

used. A bisphenol A glycidyl ether was obtained with an epoxide equivalent of 184, one Viscosity of 790OcP, measured at 25 ° C, a content ar. easily saponifiable chlorine of 0.15% by weight, a Hazen color number of 70 and a hydroxyl number of 21.

Example 3

The procedure given in Example I was followed. The second dehydrohalogenation was made but made with 70 g of 44.4% strength by weight aqueous sodium hydroxide solution and 500 g of water. You got one Bisphenol A glycidyl ether with an epoxy equivalent of 183, a viscosity of 705OcP, measured at 25 ° C, a content of easily saponifiable chlorine of 0.08 wt .-%, a Hazen color number of 60 and one Hydroxyl number of 16.

Example 4

The procedure was as in Example 1. Instead of 330 g of bisphenol A were used but 290 g of bisphenol F (mixture of isomers) were used. A bisphenol F glycidyl ether was obtained with a Epoxy equivalent of 172, a viscosity of 2100 cP, measured at 25 ° C, a content of easily saponifiable Chlorine of 0.15% by weight and a hydroxyl number of 17.

Example 5

The procedure was as in Example 1. Instead of 330 g of bisphenol A were used however 290 g of a phenol novolak was used Production is described below. The sodium hydroxide solution was added at 50 to 60 ° C and 70 to

! 2Cmm Hg and constant circulatory drainage, whereby the epichlorohydrin freed from the water was returned to the batch. You got one Novolsk glycidyl ether with an epoxy equivalent of 177, a viscosity of 21,000 cP, measured at 52 ° C, and a content of easily saponifiable chlorine of 0.17% by weight.

Manufacture of the phenolic novolak used

900 g of phenol was dissolved 9 g of oxalic acid in 18 g of water, and heated to 100 ⁰ C. 369 g of a 37% strength by weight formaldehyde solution were added over the course of 3 hours, with a reflux condenser switched on. ^{The mixture was heated to 120 °} C. without a vacuum, a mainly aqueous distillate being removed with the aid of a separator. ^{The batch was heated to 150 °} C. under reduced pressure of approx. 15 mm Hg and left at these conditions for 30 min, the excess phenol being largely distilled off.

At 150 "C and 40 to 5" Hg, 25 g Deionized water was added dropwise to the batch within 30 min, while at the same time a mixture of Water and phenol was collected in the template. (This procedure is repeated until the content reaches free phenol is <0.5%.)

A phenol novolak is obtained with a free phenol content of <0.1%, a capillary melting point of 42-45 ° C. and a hydroxyl number of 524. The average value of the degree of condensation is 1.6. ie, 3.6 phenolic nuclei and linked to one another via methylene bridges.

Example 6

The procedures in Examples 1 and 3 were followed. However, 1.5 g was used as a catalyst Triphenylphosphine benzoyl methylene

(PhjP = CH-CO-Ph)

used. A bisphenol A glycidyl ether was obtained with an epoxide equivalent of 181, a viscosity of 760 oP ₁ measured at 25 ° C., a content of easily saponifiable chlorine of 0.07% by weight. a Hazen number of 60 and a Hvdrnxvl7ahl of 16.

Example 7

The procedures in Examples 1 and 3 were followed. Instead of 1341 g, 1610 g Epichlorohydrin was used and 1.2 g of triphenylphosphine acetylmethylene were used as the catalyst

(Ph ₃ P = CH-CO-CH ₃ )

used. A bisphenol A-glycidyl ether was obtained having an epoxy equivalent of 177, a viscosity of 630OcP, measured at 25 ° C ₁ a content of easily hydrolyzable chlorine 0.07 wt .-%. a Hazen color number of 60 and a hydroxyl number of 14.

Example 8

The procedures in Examples 1 and 3 were followed. However, 1.2 g were used as a catalyst Triphenylphosphine carbomethoxymethylene

(Ph ₃ P = CH-COOCH ₃ )

used. A bisphenol A glycidyl ether with an epoxide equivalent of 183 was obtained Viscosity of 800OcP, measured at 25 ° C, a Easily hydrolyzed chlorine content of 0.08% by weight, a Hazen color number of 50 and a hydroxyl number from 16.

Example 9

It was according to the details iii Example 1 and 3 worked. The 44.4 wt .-% aqueous sodium hydroxide solution was, however, in approx. 120 min at a batch temperature

ίο door from 110 to 115 ⁰ C and at a BrüdentemperaMir of 104 to 107 ⁰ C evenly added, the water-containing distillate condensed in a receiver being freed from the entrained water of reaction and the organic layer consisting of epichlorohydrin

ι> was constantly returned to the approach, so that the The water content in the reaction mixture was always less than 2% by weight. A bisphenol A glycidyl ether was obtained with an epoxy equivalent of 180, a viscosity of 810OcP, measured at 25 ° C, a

2 »content of easily saponifiable chlorine of 0.06% by weight, a Hazen color number of 70 and a hydroxyl number of 18.

Example JO

: '■■ 330 g bisphenol A, 1610 g epichlorohydrin. 32 g xylene. 48 g of water and 1.5 g of triphenylphosphine-benzoyl-methyl-methylene were heated to 95 ° C. for 2 hours in a three-necked flask. This was followed by evenly distributed over 2 at the same temperature

i "hours the addition of 124 g (solid) caustic soda (Containing at least 98% by weight NaOH), the reaction mixture initially under a reflux condenser was held. 30 min after the start of the addition of caustic soda, the temperature was also below 95.degree

Γι weak vacuum removes the water azeotropically, the epichlorohydrin phase freed from the water being returned to the reaction mixture. To Completion of the caustic addition was epichlorohydrin and solvent under a water pump vacuum from about 15 mm Hg away.

The residue wur'e held under this vacuum for about 1 hour at 120 ⁰ C. The residue was then dissolved in 500 g of xylene. The common salt formed u / iirHf »with fififl σ Waiwr aiKCfPwacrhpn FaIk in the glycidyl ether obtained in eggs , the content of vp soapable chlorine was more than 0.1% by weight, was treated with 115 g of a 10% strength aqueous matron lye for 1 hour at 95 ° C subjected to further dehydrochlorination. The aqueous phase was removed, the xylene solution was neutralized with dilute phosphoric acid, freed from water by azeotropic circulatory distillation, filtered and concentrated under a vacuum of approx Leave C under this vacuum.

A bisphenol A glycidyl ether with an epoxide equivalent of 177 and a viscosity of 808OcP, measured at 25 ° C, a content of easily saponifiable chlorine of 0.04 wt .-% and a Hazen color number of 60.

Example Il

Example 10 was repeated with the modifications that

1. 10 min after the start of the addition of caustic soda with the azeotropic removal of the water and recycling the epichlorohydrin phase freed from water was started to the reaction mixture and

t6

Z waived further dehydrochlorination could be.

A bisphenol A glycidyl ether was obtained with a Epoxy equivalent of 179, a viscosity of 7070 cP, measured at 25 ° C, with a content of easily saponifiable Chlorine of 0.08 wt .-% and a Hazen color number of 60

Example 12

Example 10 was repeated with the modifications that

1. the reaction mixture contained no xylene and

2. Before the start of the caustic soda addition, dfci approach 3 hours. was held at 95 ° C for a long time.

Additional dehydrochlorination was used in the performance of this example. One was obtained Bisphenol A glycidyl ether with an epoxy equivalent of 174, a viscosity of 810 ocP, measured at 25 ° C, a content of easily saponifiable chlorine of less than 0.1% by weight and a Hazen color number of 70.

Example 13

Example 10 was repeated with the modifications that

1. Instead of 32 g of xylene, the reaction mixture contained 32 g of i-butanol and

2. 50 min after the start of the caustic soda addition with the azeotropic removal of the water and recycling of the epichlorohydrin phase freed from the water to the reaction mixture was started.

In the embodiment of this example was carried out with a further dehydrochlorination to obtain a bisphenol A-glycidyl ether having an epoxy equivalent of 178, a viscosity of 7570 cP when measured at 25 ⁰ C, a content of easily hydrolyzable chlorine of 0.07 wt .-% and a Hazen color number of 50.

Example 14

Example 10 was repeated with the modifications that

1. In the 1st hour of the caustic soda addition time Ά of the total amount and in the 2nd hour of the caustic soda addition time V * of the total amount of caustic soda was added evenly and

2. No further dehydrochlorination was carried out.

A bisphenol A glycidyl ether was obtained with a Epoxy equivalent of 180, a viscosity of 7920 cP, measured at 25 ° C, a content of easily saponifiable Chlorine of 0.05% by weight and a Hazen color number of 70.

Example 15

Example 10 was repeated with the modifications that

1. A total of only 119 g of caustic soda (NaOH content at least 98% by weight) was added,

2. In the 1st hour of ^{the caustic soda addition time 3} A of the total amount and in the 2nd hour of the caustic ^{soda addition time 1} A of the total amount of caustic soda was added evenly and

3. during all process steps in which the work was not carried out under vacuum, under one Atmosphere of nitrogen was worked.

Additional dehydrochlorination was employed in carrying out this example. One received a bisphenol A glycidyl ether with an epoxy equivalent of 174, a viscosity of 7670 cP measured at 25 "C, a content of easily saponifiable chlorine of 0.08 wt .-% and a Hazen color number of 50.

Example 16

330 g bisphenol A, 1570 g epichlorohydrin, 25 g xylene,

40 g of water and 1.5 g of triphenylphosphine-benzoyl-methylene were heated to 95 ° C. with stirring and under a nitrogen atmosphere and left at this temperature for 2 hours. Within 2 hours a total of 119 g of caustic soda (content of NaOH at least 98% by weight) was added in such a way that Vi in the 1st hour and the remaining 1/3 of the amount of caustic soda was added uniformly in the 2nd hour.

30 min after the start of the addition of caustic soda, the azeotropic circulatory drainage with return flow tion of the epichlorohydrin freed from the water Reaction start started. After completion of the caustic soda solution, a vacuum of 17 mm Hg and with a temperature increase of up to a maximum of 120 ° C excess epichlorohydrin removed. The residue was dissolved in 500 g of xylene and 660 g of water and 30 g caustic soda (NaOH content at least 98% by weight> subjected to further dehydrochlorination for 1 hour at approx. 95 ° C. in the reflux condenser. the aqueous phase was discarded. The xylene phase on a pH of 6.7 with dilute phosphoric acid adjusted, dehydrated by azeotropic circular distillation, filtered and under vacuum up to one maximum temperature of 120 ° C. freed from xylene. After filtration, a bisphenol A glycidyl was obtained ether with an epoxy equivalent of 182, one Viscosity of 836OcP, measured at 25 ° C, a content of easily saponifiable chlorine of 0.1% by weight and a Hazen color number of 70.

Example 17

1650 g of epichlorohydrin, 50 g of water, 13 g of triphenylphosphine benzoylmethylene and 330 g of bisphenol A were kept at 95 ° C. for 4 hours. Within 16.5 g of caustic soda were obtained at this temperature for 20 minutes (NaOH content at least 98% by weight) with stirring added evenly. Then with simultaneous circulatory drainage and return of the Epichlorohydrin phase freed from water for the reaction mixture at 90 to 95 ° C caustic soda (content of NaOH

so at least 98 wt .-%) with stirring evenly admitted. After the addition of the caustic soda, the pressure was reduced to approx. 20 mm Hg and temperature increase to 120 ° C, the excess epichlorohydrin is distilled off. The back was dissolved in 470 g of xylene The formed Table salt was dissolved out with 660 g of water. The salt phase was discarded. The xylene phase was with a solution of 35 g caustic soda (NaOH content at least 98% by weight) in 330 g water for 2 hours re-dehalogenated at 70 ° C. with vigorous stirring. The aqueous phase was then discarded The xylene phase was adjusted to a pH of 5.5 with dilute, aqueous phosphoric acid. in the Circuit was dehydrated by distillation that Anhydrous solution was filtered and the temperature increased to 120 ° C and under reduced pressure constricted at about 17 mm Hg. Under these conditions approx. 15 g of water were added to the batch in one hour

130 241/258

dropped, the volatile constituents were collected in a template. The residue was left for a further 1/2 hour at 120 ^q C under vacuum of about 17 mm Hg and then filtered through a filter candle to give a bisphenol A diglycidyl ether with a Epoxjdäquivalent of 180, a viscosity of 7980 cP when measured at 25 ⁰ C, a content of easily saponifiable chlorine of 0.07% by weight and a Hazen color number of 60,

Example 18

Example 17 was repeated with the modification that instead of 330 g of bisphenol A, a mixture of 85 g of bisphenol A and 218 g of bisphenol F (mixture of isomers) were used. A bisphenol-diglycidyl ether mixture was obtained with an epoxide equivalent of 172, a viscosity of 280OcP, measured at 25 ° C, a content of easily saponifiable chlorine of 0.05 % By weight and a Hazen color number of 70.

Example 19

Example 17 was repeated with the modification that instead of 330 g of bisphenol A, 88 g of bisphenol F (Mixture of isomers) was used. A bisphenol F diglycidyl ether was obtained with an epoxide equivalent of 169, a viscosity of 1960 cP, measured at 25 ° C, a content of easily saponifiable chlorine of 0.05 wt .-% and a Hazen color number of 90.

Example 20

Example 17 was repeated with the modification that instead of 330 g of bisphenol A, a mixture was now used from 248 g of bisphenol A and 75 g of bisphenol F (mixture of isomers) was used. A bisphenol-diglycidyl ether mixture with one epoxide equivalent was obtained of 178, a viscosity of 596OcP, measured at 25 ° C, a content of easily saponifiable chlorine of 0.08% by weight and a Hazen color number of 60.

Example 21

Example 17 was repeated with the modification that 1070 g of epichlorohydrin were used instead of 1650 g of epichlorohydrin. A bisphenol A-glycidyl ether was obtained having an epoxy equivalent of 186, a viscosity of 990OcP, measured at 25 ⁰ C, a content of easily hydrolyzable chlorine of 0.05 wt .-% and a Hazen color number of 60,

Example 22

985 g of epichlorohydrin, 36 g of i-butanol, 26 g of xylene, 24 g of water, 0.8 g of triphenylphosphine acetylmethylene were in a three-necked flask by introducing N ₂ from

ίο Freed atmospheric oxygen With further supply, 210 g of p-tert-butylphenol were added. While stirring was heated under reflux to 95 ° C. and left at this temperature for 60 minutes. Then the in even portions with a further supply of N2

254 g of caustic soda (content of NaOH at least 98% by weight) were added at approx. 95 ° C. under reflux. Subsequently, a further 30 g of caustic soda were added under normal pressure or a slight vacuum NaOH at least 98% by weight) at approx. 95 ° C during simultaneous circulation drainage and return of the epichlorohydrin phase freed from the water to Approach added evenly. When the caustic soda addition was complete, excess epichlorohydrin became and solvents under a vacuum of approx.

20 mm Hg and increasing temperature up to 120 ° C distilled off. The residue freed from epichlorohydrin was dissolved in 350 g of xylene and mixed with 320 g of water and 15 g of caustic soda (NaOH content at least 98% by weight) are added and the mixture is refluxed for 60 min door warmed. The aqueous phase was removed The xylene phase is adjusted to a pH of approx. 6.5 with dilute phosphoric acid, xylene and water were removed by distillation, the temperature rising to 150 ° C. under a vacuum of approx. 17 mm Hg was increased. After this temperature was maintained for 1 hour, after adding 3 g filtered using a filter aid similar to diatomaceous earth. A p-tert-butylphenyl glycidyl ether was obtained an epoxy equivalent of 215, a viscosity of 16 cP, measured at 25 ° C, a content of light saponifiable chlorine of 0.06% by weight and a Hazen color number of 30.

According to the method according to the invention explained in Examples 1-4 and 5-21 above, the resultant hen to about 90 wt .-% of the diglycidyl ethers Bisphenol A or bisphenol F. The remainder consists essentially of polyglycidyl ethers of the corresponding bisphenols with the general formula

OH

R- <fV-O - CH ₂ -CH-

CH ₂

where the degree of condensation η is 1 to 10 65 characterizing phenol novolaks in more detail.

can have and -R- the groups -C (CH ₃ ) or. In Example 22, about 90% by weight of the

-CH ₂ - can mean. Monoglycidyl ether of p-tert-butylphenol in addition to

In Example 5, a polyglycidyl ether is formed from the by-products that are not identified there.

DE-OS 20 28 136 9300 0% 9 770 DE-PS 21 08 207 8900 0% 9230 invention 7600 0% 7 770

19 20

DE-PS 21 08 207 with a viscosity of

Comparative test for the detection of 890OcP (25 ° C) and an epoxy equivalent of

of the technical progress achieved j 81 _unc j

Was used ³ · ^e 'n bisphenol A Diglycjdyläther according to Example 6

5 of this invention with a viscosity of 7600 cP

1. a bisphenol A diglycidyl ether according to Example 1 (25 ^Q C) and an epoxy equivalent of 181. DE-OS 20 28136 with a viscosity of

9300 cP (25 ° C) and an epoxy equivalent of the bisphenol A diglycidyl ethers were 24, 48 and

187, stored for 72 hours at 120 "C, with the

2. a bisphenol A diglycidyl ether according to Example 2 o viscosity increase at 25 ° C was followed.

Table 1 Resin sample according to viscosity (measured in cP at 25 C)

0 hours 24 hours 48 hours 72 hours

5.1% 10,540 13.3% 11,100 19.4%

9.7% 9,650 8.4% 10 140 13.9%

i Invention 7,600 0% 7,770 2.2% 8010 5.4% 8 200 7.9%

§ As can be seen from Table 1, according to nium salts of the formula

ii the bisphenol A-Di-25 process according to the invention

l | glycidyl ethers are produced, the temperature of which is (Ph ₃ P ■ CHR "R '") ⁺ X ~ (Π)

f | ' compared to the known processes that are listed under

«F Use of quaternary ammonium salts in which R" and R '"have the meaning already mentioned

If chlorohydrin ether formation make about 61 or have and X- a Cl-, Br- or I- anion means the I 40% has been improved 30 basicity of epichlorohydrin is sufficient, by splitting off

% It has been shown (see Chem. Ber. 107, 2050-2078 processing of HX from the phosphonium salt in the sense

% [1974]) that with mild to strongly C — H-acidic phospho the following equation forms the phosphoranes:

I ο xo

1 / \ 11

f. (Ph ₃ P-CHR "R"') ⁺ X ~ + CH ₂ CH-CH ₂ Cl? = »Ph ₃ P = CR" R "' + CH ₂ -CH-CH ₂ Cl (UI)

In such cases it is not necessary for the medium-rich medium in it to run off when the reaction mixture is heated from the corresponding phosphonium salts

Action of alkalis on the latter separately from the phosphonium salts, which are caused by reaction

but you can use the phosphonium salts with epichlorohydrin, the corresponding phosphoranes

as precursors of the phosphoranes in the process of forming, the following may be mentioned, which are them

Instead of the phosphoranes 45 corresponding phosphoranes are compared with the present invention: start, with the formation of phosphorane in the epichlorohydro-

Table 2 Phosphonium Halide Phosphorane

(Ph ₃ P • CH ₂ Ph) ⁺ Cl Ph ₃ P = CHPh

(Ph ₃ P-CH ₂ COOR) ⁺ Br Ph ₃ P = CHCOOR

(Ph ₃ P-CH ₂ -CONH ₂ ) + Cr Ph ₃ P = CHCONH ₂

(Ph ₃ P-CH ₂ COCH ₃ ) + Cl "Ph ₃ P = CHCOCH ₃

(Ph ₃ P • CH ₂ COPh) ⁺ Br- Ph ₃ P = CHCOPh

(Ph ₃ P • CH (CH ₃ ) • COPh) ⁺ Br Ph ₃ P = C (CH ₃ ) • COPh

(Ph ₃ P • CH (Ph) • COPh) ⁺ Br Ph ₃ P = C (Ph) ■ COPh

(Ph ₃ P CH ₂ COPh NO ₂ W) ⁺ Br Ph ₃ P = CH CO Ph NO ₂ W

(Ph ₃ P CH ₂ CO CH ₂ Ph) ⁺ Br Ph ₃ P = CH CO · CH ₂ Ph

(Ph ₃ P- CH (CH ₃ ) - CO CH ₂ Ph) ⁺ Br Ph ₃ P = C (CH ₃ ) - CO · CH ₂ -Ph

(Ph ₃ P-CH ₂ CN) ⁺ Cl- Ph ₁ P = CH CN

continuation

Phosphonium halide

Phosphorane

Ph ₃ P-HC-

-CH ₂

O O O

⁺ cr

Ph ₃ P-HC-

-CH ₂ ^ ⁺ Br "

(Ph ₃ P -CHCH = CH ₂ J ⁺ Cr (Ph ₃ P-CH (CH ₃ ) COOR) ⁺ Br (Ph ₃ PC HPh ₂ ) + Br

Ph = phenyl radical, R- = methyl or ethyl radical

Ph ₃ P = C-

-CH ₂

O O O

Ph ₃ P = C CH ₂

Ph ₃ P = CH · CH = CH ₂ Ph ₃ P = C (CH ₃ ) COOR Ph ₃ P = CPh ₂

The phosphonium salts recognized as precursors for the phosphoranes were used in the following manner Production of glycidyl ethers of bisphenol A used, with, based on 1 mole of bisphenol A, 10 Moles of epichlorohydrin and 5 mmoles of the respective phosphonium salt were used:

1341 g of epichlorohydrin and 7.25 mmol of the respective phosphonium salt were in a stirrer, Flask equipped with a thermometer and distillation device is heated to reflux temperature, the Conversion of the phosphonium salt into the phospho- J5 ran took place. After adding 330 g of bisphenol A. the reaction mixture was kept at reflux temperature for 120 min by means of a rotary valve, in a further 120 min was at 100 ° C. under normal pressure dehydrohalogenated by uniform addition of 259 g of 45% strength by weight aqueous sodium hydroxide solution, the Azeotrope of epichlorohydrin and water was distilled off.

After the addition was complete, the remaining epichlorohydrin was distilled off, the temperature rising to 120 ° C was increased. At 120 ° C was the approach

Table 3

Leave under a vacuum of approximately 20 mm Hg for 60 minutes. To separate the common salt, the Glycidyl ether dissolved in 500 g of xylene and mixed with 600 g of water. The salt phase was separated off Xylene phase was mixed with a mixture of 7Cg 45% by weight sodium hydroxide solution and 300 g water to approx. 95 ° C for 75 min to convert residual chlorohydrin ethers into glycidyl ether. The watery one Phase was again separated off. After neutralization of the xylene phase with dilute, aqueous sodium dihydrogen phosphate solution, water residues were passed through azeotropic distillation and recycling of the dehydrated XyIoIs separated. The xylene was under reduced pressure of about 20 mm Hg and temperature increase to 120 ° C removed after another Filtration to remove the salt residues, the glycidyl ether of bisphenol A was isolated and its Characteristic data determined The results obtained using various phosphonium salts as precursors of the phosphoranes are shown in the summarized in Table 3 below:

Manufactured Used phosphonium salt as Epoxy viscosity Easily llazcn- Hydro Glycidyl ether Phosphorane precursor equivalent to scifable Color number xyl number according to of the glycidyl chlorine example ether cP (25 C) 23 (Ph ₃ P- CH ₂ Ph) ⁺ CP 182 8000 0.15 75 21 24 (PhjP ■ CH ₂ (OOCH ₃ ) J ⁺ Br " 184 8600 0.16 80 22nd 25th (Ph ₃ P-CH ₂ CONHj) ⁺ CI " 185 8700 0.15 70 22nd 26th (Ph ₃ P • CH ₂ COCHj) ⁺ Cr 182 8100 0.13 70 21 27 (Ph ₃ P CH ₂ COPh) ⁺ Br 183 7900 0.15 65 19th 28 (Ph ₁ P CH ₂ CN) ⁺ CI " 185 8600 0.14 70 22nd 29 (Ph ₁ P • CH (CH ₃ ) COOCH ₃ ) ^f Br 183 8200 0.12 60 21 30th (Ph ₁ P • CH (CH ₁ ) COPh) ⁺ Br 181 7800 0.13 70 20th 31 (Ph ₁ P CH (Ph) COPh) ⁺ Br 180 7700 0.14 60 20th 32 JPh ₁ P CH ₂ CO CH ₂ Ph) ^f Br 185 8700 0.12 70 22nd 33 (Ph ₁ P • CH (CH,) COCH ₂ Ph) * Br 186 8750 0.15 75 22nd

In a further embodiment of the method instead of the phosphonium salts, their reaction mixtures, which are obtained by reacting the triphenylphosphine with the respective halide to the phosphonium salt have been prepared in a solvent, in which is the phosphonium salt is used. In such cases it is advisable to use the cheaper one Component, generally the halide (e.g. benzyl chloride, methyl or ethyl bromoacetate, Chloroacetamide, chloroacetone, bromoacetophenone, I-methylbromoacetophenone, 1-phenolbromoacetophenone, p-nitrobromoacetophenone, 1-phenylbromoacetone, 1-phenyl-3-methyl-i-bromoacetone. Chloroacetonitrile. Chlorosuccinic anhydride, bromobutyi 'acetone, allyl chloride, methyl or ethyl Λ-bromopropionate. Di- π phenylmethyl bromide), to be used in excess to bring the equilibrium to the side of the phosphonium salt to move. Here, triphenylphosphine and one of the organic halides mentioned are used together with an inert organic solvent heated for a long time until the conversion to the phosphonium salt has taken place. The reaction mixture obtained is used as a phosphorane precursor without isolating the phosphonium salt.

Inert organic solvents that can be used are methanol, ethanol, propanol, benzene, toluene, xylene, chloroform, carbon tetrachloride, ethyl or methyl acetate. In general, the Reaction batches heated to reflux for 30 minutes to 24 hours.

If an epihalohydrin, for example epichlorohydrin, is used instead of the inert solvent Solvent, occurs through the above-described reaction of the phosphonium salt that is formed with epichlorohydrin to form phosphorane and U-dichloropropanol-2 another shift of the Reaction equilibrium to the phosphoranes.

The following examples explain this embodiment in more detail.

Example 34

2.62 g trinhenylphosphine and 1.265? Benzyl chloride are dissolved in 20 g of epichlorohydrin by refluxing for 60 min. The formation of phosphorus is evident by an intense orange coloration of the solution. The solution is stored with exclusion of moisture.

As already described, bisphenol A and epichlorohydrin are reacted with 17.2 g of this solution to form bisphenol A glycidyl ether.

Example 35

2.62 g triphenylphosphine and 13g benzyl chloride are dissolved in 20 g of epichlorohydrin by refluxing for 60 min. The formation of phosphorus is evident by an intense orange coloration of the solution. The solution is stored with exclusion of moisture.

With 17.5 g of this solution, bisphenol A and t> o Epichlorohydrin, as already described, converted to the glycidyl ether of bisphenol A.

Reacted hours under reflux to the benzyltriphenylphosphonium chloride.

Bisphenol A and epichlorohydrin are reacted with 17.5 g of this solution, as already described, by means of bisphenol A glycidyl ethers.

Example 37

2.62 g triphenylphosphine and 1.97 g phenacryl bromide are in 20 g dry epichlorohydrin through Heating for 3 hours under reflux to give benzoylmethy I triphenylphosphonium bromide.

As already described, bisphenol A and epichlorohydrin are reacted with 17.8 g of this solution to form bisphenol A glycidyl ether.

Example 38

2.62 g of triphenylphosphine and 0.925 g of chloroacetone are carried out in 20 g of dry epichlorohydrin Heating for 3 hours under reflux converted to acetylmethyltriphenylphosphonium chloride.

With 17.1 g of this solution, bisphenol A and epichlorohydrin, as already described, are converted to glycidyl ether..ws bisphenol A.

B e i s ρ i e 1 36

2.62 g triphenyl phosphine and 1.5 g benzyl chloride are in 20 g of absolute ethanol by heating for 8 Example 39

2.62 g of triphenylphosphine and 1.53 g of methyl bromoacetate are dissolved in 20 g of dry epichlorohydrin reacted by refluxing for 3 hours to give acetylmethoxytriphenylphosphonium bromide. With 17.5 g of this solution are bisphenol A and Epichlorohydrin. converted to the glycidyl ether of bisphenol A.

Example 40

2.62 g triphenylphosphine and 0.755 g chloroacetonitrile are in 20 g dry epichlorohydrin through Heating for 9 hours under reflux converted to cyanomethyltriphenylphosphonium chloride. With 16.9 g In this solution, bisphenol A and epichlorohydrin, as already described, become the glycidyl ether of white nols A implemented.

Example 41

2.62 g triphenylphosphine and 0335 g chloroacetamide are reacted in 20 g of dry epichlorohydrin by refluxing for 9 hours to give carbamidomethyltriphenylphosphonium chloride.

With 17.1 g of this solution are bisphenol A and Epichlorohydrin, as already described, converted to the glycidyl ether of bisphenol A.

In the following Table 4 the characteristic data of the glycidyl ethers prepared according to Examples 35 to 41 are summarized.

Table 4

25th

26th

Example solution of the phosphonium salt as an epoxy

Prepare of phosphorane equivalent

viscosity

cP (25 C)

Easily

soapable

chlorine

llazen color number

Hydroxyl number

34 (Ph ₃ P • CHjPh) ⁺ CI 184 8300 0.15 90 20th 35 (Ph ₃ P CHjPh) ⁺ CI 183 8260 0.13 80 21 36 (Ph, p-CH ₂ Ph) 'cr 185 8600 0.16 90 22nd 37 (Ph ₃ P CH ₂ COPh) * Br 182 8180 0.13 75 19th 38 (Ph, P-CH ₃ COCH ₁ ) CI 181 8200 0.14 80 20th 39 (Ph ₁ P CH ₃ COOCH ₁ ) Br 184 8700 0.13 80 21 40 (Ph ₁ P CH ₃ CN) CI 185 8650 0.16 80 22nd 41 (Ph ₁ P CH ₁ CONH ₁ ) CI 185 8500 0.17 75 21

Claims (4)

Claims; 1. Process for the production of low viscosity, low molecular weight glycidyl ethers by reacting mono- or polyhydric phenols with excess epichlorohydrin, based on the phenolic hydroxyl group, in the presence of a specific catalyst for the formation of chlorohydrin ether, at least 10% by weight, based on the phenolic hydroxyl groups are converted to chlorohydrin ethers and these then with 0.9 up to 1.15 of an equivalent of a solid or dissolved alkali metal hydroxide per phenolic Hydroxyl groups (optionally in two stages) at temperatures between 50 and 200 ° C and optionally reduced pressure with simultaneous dehydration by azeotropic distillation or by Distillation can be converted to glycidyl ethers in the circuit, characterized in that that the chlorohydrin ether formation in the presence of 0.01 to 10 mol%, based on the used monohydric or polyhydric phenols, an alkylene phosphorane of the formula Pn ₃ P = CR "R"'(I) carried out, where R "and R '" a hydrogen atom or hydrocarbon radicals with up to 20 Mean carbon atoms which are optionally substituted by carbonyl, nitrile, carboxy ester or carbonamide groups or to form a ring are closed. 2. The method according to claim 1, characterized in that the alkylenephosphorane of the formula (I) in amounts of 0.25 to 5 mol%, based on the mono- or polyhydric phenols used, is used. 3. The method according to claim 1, characterized in that the alkylenephosphorane of the formula (I) in amounts between 0.2 and 1 mol%, in particular between 0.25 and 0.75 mol%, based on the monohydric or polyhydric phenols used. 4. The method according to any one of claims 1 to 3, characterized in that the chlorohydrin ether formation with a) an alkylene phosphorane carries out this first by heating the phosphonium salt of the formula (PhjPCHR "R '") ⁺ X- where R "and R '" have the meaning already mentioned and X- is a Cl--, Br-- or J - anion or of the phosphine and the respective halide has been obtained in epichlorohydrin, and that then the phenol is added to this reaction mixture for reaction with epichlorohydrin, or b) converts the reaction mixture of the conversion of phosphine and halide as a phosphorane precursor with epichlorohydrin and phenol