DE1133735B - Process for the production of glycidyl ethers of monohydric phenols - Google Patents

Description

Process for the production of glycidyl ethers of monohydric phenols It is known to produce glycidyl ethers of monohydric phenols by the phenols in aqueous or alcoholic solution in the presence of alkali with a Haloepoxyalkane, e.g. B.

Epichlorohydrin, or with a suitable dihalo compound, e.g. B. Dichforhydnn, implements. One already has monohydric phenols with epichlorohydrin converted to the corresponding chlorohydrin ethers and these then by splitting off hydrogen halide converted into glycidyl ether with alkali.

It has now been found that one can use glycidyl ethers of monohydric phenols in a particularly simple way and without the simultaneous formation of inorganic salts, which complicate the work-up of the reaction mixture, and with good yields can thereby be prepared by optionally containing alkyl groups or halogen atoms substituted monohydric phenols with more than 2 moles, especially 5 to 40 moles, each Mole of phenol of a haloepoxyalkane, which has a halogen atom in the vicinity to the epoxy group contains, especially epichlorohydrin, in the presence of high molecular weight organic, insoluble in the reaction mixture catalysts, which either a) salt-like groups or b) groups which under the reaction conditions in salt-like Groups can pass over, or c) contain acid amide groups at elevated temperature reacted and then, after the catalyst had been separated off, excess haloepoxyalkane and volatile by-products formed are distilled off from the reaction mixture.

As starting materials for the method of the invention, for. B. phenol, a- or fl-naphthol, also the different ones by alkyl groups or halogen atoms substituted phenols are used.

Halogenepoxyalkanes, which have a halogen atom adjacent to the Containing epoxy group and obtained by the process of the invention with monohydric phenols are implemented, for example, epichlorohydrin, epibromohydrin, 1, 2-epoxy-3-chlorobutane, I-chloro-2,3-epoxybutane and l-chloro-2,3-epoxy-5-methoxypentane. Used preferably one epichlorohydrin. The commercially available technical epichlorohydrin with a water content 0.1% oil can be used without cleaning or drying. It is beneficial the haloepoxyalkane in a much larger excess, e.g. B.

5 to 40 moles and more per mole of phenol to be used.

The unreacted haloepoxyalkane is at implementation does not changed and can easily be recovered and reused.

Cation exchange resins, which contain acidic groups, z. B. sulfonic acid groups, carboxyl groups, phosphoric acid groups and others can, for the process of the invention in the form of their salts, especially in the form of Alkali, ammonium or amine salts can be used. Anion exchange resins, d. H.

Ion exchangers with basic groups, e.g. B.

Amino groups, quaternary ammonium or phosphonium groups and ternary groups Sulphonium groups are in the form of their salts, e.g. B. in the form of chlorides or sulfates used.

Another group of suitable catalysts are those of high molecular weight Compounds containing reactive groups, which among the applied Conditions can change into salt-like groups. Such connections are for example high molecular weight organic bases, e.g. B. Anion exchangers in the form of the free bases, Also other resins which contain tertiary nitrogen are known to contain epihalohydrins can pass into quaternary compounds are suitable, for. B. melamine resins or epoxy resins hardened with organic amines.

Finally, such compounds come into consideration as catalysts, which contain acid amide groups, e.g. B. polyamides, also the known urea resins.

The catalysts mentioned are used for the process of the invention expediently used in granular form. Fine powdery fractions are advantageous previously separated by sieving and / or washing out. Achieved this way one that the separation of the catalyst from the Reaction mixture, z. B. by centrifuging, decanting or filtering, is extremely smooth. Coarse filters are sufficient for the filtration. It is advantageous to use close-meshed wire screens for this purpose.

In general, the catalysts can be used as often as desired, since, apart from a small amount of mechanical wear, they do not wear out.

Should their activity decrease after repeated use, so can they are easily regenerated. The type of regeneration is of that chemical constitution of the catalyst in question. In many cases washing out and swelling with water is sufficient. In other cases, the Catalysts by treatment with salt solutions or with dilute acids or

Bases regenerated. A certain water content of the catalytic converters is annoying the reaction according to the invention generally does not.

The amount of catalyst can vary within wide limits. the optimal amount depends on the constitution of the catalyst and may from case can easily be determined by preliminary tests.

The method of the invention is carried out in such a way that the mentioned starting materials and the catalyst are heated for a few hours.

In some cases it is useful to give the reaction mixture an inert one add organic solvent. If you use what is particularly useful, Epichlorohydrin as a haloepoxyalkane, in a larger excess, is recommended it is necessary to heat the reaction mixture to the boil under reflux. Afterward the catalyst is separated off by z. B. the mixture through a fine sieve made of V4A wire. The separation of the catalyst goes extremely well in this way smooth and swift. After that, the excess haloepoxyalkane will be light as well volatile reaction products, e.g. B. dichlorohydrin, distilled off, preferably at reduced pressure.

Small amounts of water when using hydrous catalysts or technical epichlorohydrin may be present in the reaction mixture removed with this so that the residue is anhydrous. The halogenepoxyalkane distilled off can, if necessary after appropriate cleaning, be used for further approaches will.

Dihalohydrin formed can easily be converted into in a known manner Convert epihalohydrin.

The glycidyl ethers obtained as a residue in this way are for many uses pure enough. You can use distillation at reduced Pressure can be cleaned further. Those resulting from fractionation are higher than the glycidyl ether boiling components mostly consist of the corresponding chlorohydrin ethers These can be added to further batches, which increases the yield of glycidyl ethers can improve.

The products made by the process of the invention can with advantage as a reactive thinner for epoxy resins and as heat stabilizers for Halogen-containing high polymers can be used.

Example I 94 g of phenol, 3700 g of technical epichlorohydrin with a Water content of about 0.1% and 80g a commercially available water-containing anion exchanger were heated under reflux with stirring for 5 hours. Then the Mixture 'filtered off from the catalyst. The filtrate was then at a pressure of about 40 mm of mercury freed from excess epichlorohydrin. The residue was fractionated with a small packed column. There were 138 g of pure distilled Phenyl glycidyl ether obtained, boiling point 4 = 97 to 100 ° C.

The anion exchanger used was a commercial product "Dowex I X 10".

According to the supplier, this represents a strongly basic anion exchanger based on polystyrene, which contains quaternary benzylammonium groups. This Ion exchanger has been used with equal success in the form of the free base and in the form of hydrochloric acid salt used.

Example 2 206 g of technical octylphenol, 3700 g of epichlorohydrin and 100 g of a commercially available anion exchanger were stirred for 7 hours on The reflux condenser was then heated to that in the example 1 described manner worked up. 232 g of octylphenyl glycidyl ether were obtained, Kps, os = 120 120 to 138 ° C.

The anion exchanger used was a commercial product "Lewatit MN", which was used in the form of the free base.

This anion exchanger makes according to the information of the supplier is a strongly basic polycondensate which contains R3 + N groups.

The experiment was repeated, with the ion exchanger in the form both the hydrous sulfuric acid and the hydrochloric acid salt are used became. Practically the same result was obtained.

Example 3 220 g of technical nonylphenol, boiling point lo = 140 to 1720 C, 3700 g epichlorohydrin and 100 g of a commercially available water-containing anion exchanger, known under the trade name "LewatitMN", 6112 hours were stirred heated on the reflux condenser. The reaction mixture was as described above Way worked up. 251 g of nonylphenyl glycidyl ether were obtained, boiling point 0.05 = 131 to 158 ° C.

The ion exchanger was used in the form of the sulfuric acid salt.

Example 4 144 g of fl-naphthol, 3700 g of technical grade epichlorohydrin and 80 g of an anion exchanger known under the trade name "Dowex 1 X 10" were refluxed with stirring for 7 hours. The water-containing anion exchanger was used in the form of the free base. The reaction mixture was in the example 1 described manner worked up. 164 g of ß-naphthyl glycidyl ether were obtained, Kp.o, l = 161 to 1660 C.

Example 5 108 g of p-cresol, 3700 g of technical grade epichlorohydrin and 80 g of an anion exchanger known under the trade name "Dowex 1 X 10" in the form of the water-containing free base were under Stir for 7 hours heated on the reflux condenser. The reaction mixture was made in the manner described worked up. 133 g of p-cresyl glycidyl ether were obtained, b.p. 1 = 90 to 92 " C.

Example 6 108 g of o-cresol, 3700 g of technical grade epichlorohydrin and 100 g of a water-containing one known under the trade name "Dowex 1 X 8" Anion exchanger were heated at the reflux condenser with stirring for 6 hours. Of the Ion exchanger was used in the form of the hydrochloric acid salt. The reaction mixture was worked up in the manner described above. There were 126 g of o-cresyl glycidyl ether obtained, Kp.o, l = 80 to 82 "C.

Example 7 128.5 g of p-chlorophenol. 3700 g of technical grade epichlorohydrin and 150 g of an anion exchanger known under the trade name »Lewatit MN«, which was in the form of the hydrobromic acid salt, were stirred for 6 hours heated on the reflux condenser. The reaction mixture was made in the manner described worked up.

136 g of p-chlorophenyl glycidyl ether were obtained, boiling point 0.2 = 92 to 93 "C.

Example 8 61 g of p-xylenol, 1850 g of technical grade epichlorohydrin with a water content of about 0.1010 and 100g of a commercially available water-containing Anion exchanger, which is known under the trade name "Lewatit MN" and in the form of the sulfuric acid salt were 6 hours with stirring on the reflux condenser heated. The catalyst was then removed by filtration. From the filtrate the excess epichlorohydrin was then at a pressure of about 40 mm of mercury distilled off. The residue now became mercury at a pressure of about 0.1 subjected to fractional distillation. Here, 87 g of a 90 to 92 ° C and 0.1 now mercury-boiling liquid obtained from pure p-xylenylglycidyl ether duration.

Example 9 2000 g of epichlorohydrin were in a distillation apparatus with 100 g of water-containing anion exchanger, which is available under the trade name "Lewatit MN" is known and was in the form of the free base, heated until no more water could be detected in the distillate that was passing over.

About 70 g of distillate passed over here. To the anhydrous residue 75 g thymol were given.

The mixture was then refluxed for 6 hours with stirring heated. The reaction mixture was worked up in the manner described in Example 8. 82 g of pure thymyl glycidyl ether boiling at 94 to 97 ° C./0.2 mm were obtained.

Example 10 47g phenol, 1300g epibromohydrin and 150g "nylon" in the form small cube sold under the trade name "Zytel" from DuPont were supplied, were refluxed with stirring for 8 hours. The reaction mixture was in the manner described in Example 1 worked up. It became 54 g purer Phenyl glycidyl ether obtained. Example 11 54 g of technical grade cresol, 1850 g of epichlorohydrin and 100 g of a commercially available melamine resin were stirred for 7 hours on a reflux condenser heated. The melamine resin was prepared according to example 4 of British patent specification 877 670, then comminuted after the roller treatment described there and hardened for 4 hours at 130 ° C. The reaction mixture was in the im Example 8 described manner worked up. There were 62 g of cresyl glycidyl ether obtained, bp 0.15 = 74 to 82 "C.

Example 12 94 g of phenol, 3700 g of technical epichlorohydrin and 80 g of a cured epoxy resin were stirred for 7 hours on the reflux condenser heated.

The epoxy resin was made according to Example 3 of that published on May 24, 1956 German patent application H 13747 IVb / 12 o, in a weight ratio of 10 : 4 smeared with benzidine, hardened for 6 hours at 1400 C and then crushed. The reaction mixture was then worked up in the manner described in Example 1.

136 g of phenyl glycidyl ether were obtained.

Example 13 72 grams of fl-naphthol, 1850 grams of epichlorohydrin, and 100 grams of one commercially available water-containing cation exchanger, which is available under the trade name "Lewatit S 100" is known and was in the form of the ammonium salt, were 7 hours heated with stirring on the reflux condenser. The reaction mixture was in the example 8 described manner worked up. 81 g of ß-naphthyl glycidyl ether were obtained, Kp.o, l = 156 to 161 "C.

The cation exchanger »Lewatit S« is a styrene resin, which - contains SO3H groups on the core and is strongly acidic.

The above experiment was repeated twice, using the ion exchanger used once in the form of the sodium salt and once in the form of the potassium salt became. The results were practically the same as when using the ammonium salt.

Claims (2)

PATENT CLAIMS: 1. Process for the production of glycidyl ethers monohydric phenols by reacting monohydric phenols with a haloepoxyalkane, characterized in that the optionally substituted by alkyl groups or halogen atoms substituted monohydric phenols with more than 2 moles, especially 5 to 40 moles, each Mole of phenol of a haloepoxyalkane, which has a halogen atom in the vicinity to the epoxy group contains, especially epichlorohydrin, in the presence of high molecular weight organic, insoluble in the reaction mixture catalysts, which either a) salt-like groups or b) groups which under the reaction conditions in salt-like Groups can pass over, or c) acid amide groups included in Reacts elevated temperature and then after the catalyst has been separated off Excess haloepoxyalkane and volatile by-products formed from the Reaction mixture distilled off. 2. The method according to claim 1, characterized in that as high molecular weight organic catalysts, which are insoluble in the reaction mixture, cation exchangers in the form of their salts, preferably their alkali, ammonium and amine salts, or anion exchangers in Form of the free base or in the form of salts or aminoplasts, especially melamine or urea resins, or linear polyamides are used. Considered publications: German patent application K 10079 IVc / 39c (published July 1, 1954); U.S. Patent Nos. 2221 771, 2221818; Deutsche Apotheker-Zeitung, Vol. 96, 1956, pp. 433 to 437, 752 to 754, 1222 to 1226 and 1246 to 1248.