DE2131115A1 - Monoglycolethers or glycol-semiesters of aromatic cpds - contg hydroxyl gps - by reacting 1,2-epoxides with hydroxyl-aromatic - Google Patents

Abstract

Monoglycol ethers or glycol semiesters of aromatic cpds. contg. hydroxyl-gps. or of carboxylic acids are obtd. by reacting 1,2- epoxides with aromatic cpds. contg. hydroxyl-gps. or carboxylic acids, at elevated temps. in presence of a phosphoric acid triamide, as catalyst, e.g. phenol may be reacted with ethylene oxide in presence of hexamethylphosphoric acid triamide to give phenylmonoglycol ether.

Description

Process for the production of monoglycol ethers or glycol half-esters of aromatic compounds containing hydroxyl groups or of carboxylic acids It is from Houben-Weyl, Methods of Organic Chemistry, Vol. 6/3, 1965, pages 79 and 458 known that monoglycol ethers of phenols can be obtained by reacting phenols with ethylene oxide in the presence of alkaline catalysts such as alkali metals, Alkali hydroxides, alkali carbonates, alcoholates or tertiary amines, also in Presence of acidic catalysts such as sulfuric acid, perchloric acid, tin tetrachloride or aluminum chloride.

When using basic and acidic catalysts, however, occurs a side reaction that leads to the formation of polymeric glycols. These polymers Glycols can then be removed from the desired ones only with difficulty by distillation Separate reaction products. According to Houben-Weyl, op. Cit., There is also the reaction of ß-naphthol with epoxides the possibility that a core substitution occurs, when acidic catalysts are used, they ultimately lead to the formation of dihydrofuran derivatives leads. The catalysts mentioned are also disadvantageous in the conversion of chlorinated ones Phenols, since halogen is often split off in the process.

it has now been found that monoglycol ethers or glycol half esters of Aromatic compounds containing hydroxyl groups or of carboxylic acids Reaction of 1,2-epoxides with aromatic compounds containing hydroxyl groups or carboxylic acids at elevated temperature in the presence of a catalyst, if appropriate in the presence of an inert solvent advantageously obtained when using a phosphoric acid triamide as a catalyst.

The new process solves the problem of the monoglycol ethers in an advantageous manner or glycol half esters of the aromatic compounds containing hydroxyl groups or the carboxylic acids in pure form and with almost no formation of polyglycols. This makes it easier to work up the resulting monoglycol ethers.

Some of them are so pure that they can be used directly. Another advantage is that when using, in particular, more highly chlorinated Phenols no elimination of halogen occurs.

Finally, it is of particular importance that in the presence of a phosphoric acid triamide as a catalyst practically no discoloration occurs and the reaction products can be processed further immediately.

1,2-epoxides are preferably suitable for the process according to the invention with 2 to 12 carbon atoms and one epoxy group in the molecule. The preferred 1,2-epoxides are derived from aliphatic, cycloaliphatic or araliphatic Hydrocarbons that may be unsaturated or have substituents, like chlorine atoms. Ethylene oxide and propylene oxide are preferably used for the reaction. Other 1,2-epoxides that are accessible to the reaction are, for example: isobutylene oxide, Butadiene monoxide, cyclohexene oxide, cyclooctene oxide, cyclododecatriene (1, 5,9) monoxide, Epichlorohydrin or styrene oxide.

Preferred aromatic compounds containing hydroxyl groups conduct differs from benzene or naphthalene. You can have one or more hydroxyl groups contained in the molecule and also indifferent substituents under the reaction conditions have, such as halogen atoms, carbon ester, aldehyde, alkyl, nitro or cyano groups as well as hydrocarbon radicals of 1 to 4 carbon atoms bound via ether bridges.

Compounds suitable for the reaction are, for example: phenol, 36-naphthol, ß-naphthol, pyrocatechol, - resorcinol, hydroquinone, phloroglucinol, pyrogallol, 2-chlorophenol, 4-chlorophenol, 2,4-dichlorophenol, o-cresol, 2,4,6-trichlorophenol, 2,4-dinitrophenol or pentachlorophenol. Also polyphenols that are catalyzed by acid condensation accessible from phenols with aldehydes or ketones, such as 4,4-dihydroxydiphenylmethane or 4,4-dihydroxydiphenylpropane- (2,2) are suitable starting materials.

Aliphatic, cycloaliphatic and aromatic acids are suitable as carboxylic acids saturated and unsaturated carboxylic acids, as well as polycarboxylic acids. One can e.g. Acetic acid, acrylic or methacrylic acid or their polymers, lauric acid, oleic acid, I.inoleic or linolenic acid, cyclohexanoic acid, benzoic acid, phthalic acid or terephthalic acid use.

One equivalent of one hydroxyl group is generally applied 1 to 10 equivalents, preferably 1.1 to 1.5 equivalents of a 1,2-epoxy.

The reaction proceeds in the presence of catalytic amounts of a phosphoric acid triamide The amide is used in amounts of, for example, 0.01 to 10% by weight, based on the hydroxyl group containing aromatic compound used. Gets particularly good results when using 1 to 5% by weight.

A phosphoric acid amide which does not contain any hydrogen bonded to amide groups and which corresponds to the general formula (I) is particularly advantageous to use for the reaction: in which R1 and / or R2 is an alkyl radical with, for example, 1 to 5 carbon atoms or a cycloalkyl radical with 5 to 10 carbon atoms, or in which R1 and together with N form a morpholinyl or piperidyl radical.

A catalyst according to the invention is obtained in a known manner e.g. by reacting phosphorus oxychloride with a secondary amine in the presence an acid acceptor.

the process according to the invention is expediently carried out at temperatures from 40 to 200 ° C. It is particularly advantageous to work at temperatures of 60 to 140 ° C.

In order to be able to use technically simple apparatus, one works preferentially pressureless. The reaction can, however, e.g. if substances are gaseous at room temperature are present, can also be carried out under pressure.

If solid, hydroxyl-containing at the reaction temperature aromatic compounds or carboxylic acids or 1,2-epoxides are used it is appropriate to carry out the reaction in the presence of an inert under the reaction conditions Run solvent. Suitable solvents are, for example, hydrocarbons, such as toluene or xylene, also chlorinated hydrocarbons, such as ethylene chloride or chlorobenzene or ketones such as

Cyclohexanone.

The new method is carried out, for example, in detail so that aromatic compounds containing hydroxyl groups or Carboxylic acids, optionally dissolved in a solvent, and the chosen phosphoric acid amide Submitted in a suitable amount and with stirring at the temperature mentioned, the 1,2-epoxy metered in in the desired ratio.

If you use gaseous 1,2-epoxides as starting materials, you can they are introduced as gases without pressure or metered in in liquid form under pressure. The reaction is generally over after 3 to 4 hours. Then will the resulting monoglycol ether or glycol half-ester by fractional distillation cleaned.

The separated catalyst can be used again for the reaction will. It is also possible to carry out the reaction continuously using suitable equipment perform.

Monoglycol ethers made by the process of the invention are suitable as textile auxiliaries or for the production of print pairs or as starting materials for the production of polyesters. Glycol half esters can also be found technical use, E.g. the glycol half esters of acrylic acid excellent monomers for the production of paints and dispersions.

The parts given in the following examples relate to the weight.

Example 1 94 parts of phenol and 1.4 parts are used in a stirred kettle Submitted hexamethylphosphoric triamide. Then one passes under at 140 to 1500C Stir in 45 parts of gaseous ethylene oxide. The reaction is after about 4 hours completed. The reaction mixture is then distilled in vacuo. You get 134 parts (97% of theory, based on phenol) phenyl monoglycol ether.

The refractive index of the glycol ether is nD20 = 1.5340.

Example 2 94 parts of phenol and 1.5 parts are used in a stirred kettle Submitted phosphoric acid trmorpholide. 45 parts are then passed at 140 ° C. with stirring gaseous ethylene oxide. The reaction is over after about 4 hours. Afterward the reaction mixture is distilled in vacuo. 135 parts are obtained (98 of the theory, based on phenol) phenyl monoglycol ether. The refractive index of the glycol ether is nD20 = 1.5340.

EXAMPLES 3 to 8 Proceed as described above under Use of various other phenols. The results are in the table below listed.

Example phenol ethylene oxide catalyst temperature duration reaction product [g] hexamethylphos- [° C] [hours] phosäuretriamid [g] 3 2-chlorophenol 52 1.7 140 - 145 4 2-Chlophenylmonoglykol- Kp1 = 106 ° C 128.5 g ether 159 g (yield: 92%) nD20 = 1.5531 4 4-chlorophenol 95 2.5 120 5 2-chlorophenyl monoglycol- bp1 = 114 ° C 128.5 g ether 328 g (yield: 95%) nD20 = 1.5513 5 2,4-dichlorophenol 52 1.8 130 5 2,4-dichlorophenyl mono- Bp1 = 128 ° C 128.5 g glycol ether 197 g (yield: 95%) nD20 = 1.5668 6 o-cresol 46 1.0 130 6 o-cresyl monoglycol-128.5 g ether 152 g crude nD20 = 1.5291 (yield: 100%) 7 2,4,6-trichlorophenol 197 g 48 1,0 130 8 2,4,6-trichlorophenyl monoglycol ether 228 g (yield: 94.5%) melting point 67/68 ° C. 8 2,4-dinitrophenol 184 g 48 1.0 120 6 2,4-dinitrophenyl monoglycol ether 182 g (yield: 80%) m.p. 89 ° C Example 9 In a stirred kettle 187.5 parts of a technical ricinoleic acid and 1 part of hexamethylphosphoric acid triamide submitted. Purge the kettle three times with nitrogen. Be at 90 to 1000G 28 parts of ethylene oxide injected in about 12 hours under a pressure of 2 atmospheres. Man lets react for 5 hours at 1000C until the pressure has dropped. One evacuates and cools down. 210 kg of ricinoleic acid glycol half-ester are obtained as a pale yellow clear Oil.

SZ = 0.25.

Example 10 In a stirred autoclave, 600 parts of 4,4'-bis (hydroxyphenyl) propane (2.2) and 3 parts of hexamethylphosphoric triamide and 50 parts of propylene oxide. The mixture is heated to 140 ° C. and a further 390 parts of propylene oxide are pressed at this temperature on. The pressure increases to 7 atm. Duration of the reaction: 30 hours.

900 parts (99.5% of theory) of 4,4'-bis (2-hydroxy-isopropoxyphenyl) propane, 2) are obtained 31s viscous oil. OH number calculated. 326, OH number found. 325; nD20 = 1.5509.

Example 11 In a stirred vessel, 648 parts of acrylic acid and 20 Parts of hexamethylphosphoric triamide and 540 parts of propylene oxide at 60 to 7000 added over 10 hours. The reaction is allowed to continue for 2 hours and then drawn unreacted propylene oxide in vacuo. This leaves 1160 parts (99% of the Theory) Propylene glycol monoacrylate as a colorless liquid with a residual acid content from 1% acrylic acid. nD20 = 1.4457.

Claims (1)

Claim Process for the production of monoglycol ethers or glycol half-esters of aromatic compounds containing hydroxyl groups or of carboxylic acids by reacting 1,2-epoxides with aromatic compounds containing hydroxyl groups respectively. Carboxylic acids at elevated temperature in the presence of a catalyst, optionally in the presence of an inert solvent, characterized in that that a phosphoric acid triamide is used as a catalyst.