CH616399A5 - Process for the preparation of alkylene glycol etherates of carboxylic acids - Google Patents

Description

The present invention relates to a new process for the preparation of the alkylene glycol ether esters of carboxylic acids and, in particular, to a new process for the production of mono- or polyalkylene glycol ether esters of carboxylic acids, starting from esters of carboxylic acids and oxiranes by direct reaction of the Oxirans with the ester of carboxylic acid.

It is known that alkylene glycol ether esters cannot be produced by directly reacting the alkylene oxide with the ester of the organic carboxylic acid. For example, the alkylene glycol ether esters of organic carboxylic acids are prepared by esterifying an alkylene glycol monoalkyl ether with an organic carboxylic acid, or these compounds are prepared by an ester exchange between an ester of an organic carboxylic acid and an alkylene glycol alkyl ester. As an improvement This two-step reaction is described in Japanese Patent Publication No. SH045-20286, in which an addition reaction of an alkylene oxide and an ester exchange reaction take place by introducing alkylene oxide into a mixture of an ester of an organic carboxylic acid and an alcohol. However, this process takes a very long time to complete the reaction and the separation of the material obtained is very difficult and troublesome.

The aim of the present invention was to provide a process in which an alkylene glycol ether ester of a carboxylic acid is prepared in a one-step reaction, starting from an ester of a carboxylic acid and an oxirane.

Another object of the present invention was to develop a method by which it is possible to use alkylene

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to produce glycol ether esters of carboxylic acids in high yields.

Furthermore, the alkylene glycol ether ester of the carboxylic acid should be easily separable from the reaction mixture in this process.

It has now surprisingly been found that some compounds which contain aluminum, titanium, iron, zinc or tin have a catalytic effect on the addition reaction of oxirane with the formation of alkylene glycol ether esters of organic carboxylic acids and that some compounds, the elements of group 5b of the periodic table have a catalytic effect as promoters on those compounds which contain aluminum, titanium, iron, zinc or tin.

According to the process of the invention, the alkylene glycol ether ester of the carboxylic acid is prepared by reacting oxirane with the ester of the carboxylic acid, the reaction being carried out in the presence of a catalyst which consists of halides or organometallic compounds of the metals zinc, aluminum, titanium, Tin and iron is selected. The reaction preferably takes place in the presence of a cocatalyst which is selected from the group of compounds which has at least one nitrogen atom or phosphorus atom or antimony atom or arsenic atom or bismuth atom, and in which at least one halogen atom or a carbon atom directly to the nitrogen atom, phosphorus atom, arsenic atom , Antimony atom or bismuth atom is bound. The preferred temperature range is between 50 and 300 ° C.

The reaction of the oxirane with the ester of the carboxylic acid is explained using the following reaction scheme and both polyalkylene glycol ether ester and monoalkylene glycol ether ester of the carboxylic acids are obtained:

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O -

V T? 3

R "-C-OK ,, + n r3> C-C <^ 3

R3R.3r3r3 r "-c - (- o-V-c ^ T-or o

Kl

In this reaction scheme, the first named compound is the ester of carboxylic acid, while the second named compound is oxirane. The product obtained is the alkylene glycol ether ester of the carboxylic acid.

In the formula scheme given above, the radicals R "are identical to or different from one another, and these radicals represent substituted or unsubstituted hydrocarbon groups having 1 to 20 carbon atoms or the radicals R" are hydrogen atoms.

The radicals R '"are identical to or different from one another and they mean different groups of substituted or unsubstituted hydrocarbons which have 1 to 20 carbon atoms.

The radicals R3 are identical to or different from one another and represent different groups of substituted and unsubstituted hydrocarbons having 1 to 10 carbon atoms, or the radicals R3 can also have the meaning of hydrogen atoms.

Different types of oxiranes can be used to carry out the process according to the invention. The most commonly used oxiranes are the products mentioned below, which can be used either as individual compounds or in mixtures of 2 or more such compounds:

Ethylene oxide, propylene oxide, isobutylene oxide, 1,2-butylene oxide, 2,3-butylene oxide or styrene oxide. When these oxiranes are used, corresponding alkylene glycol ether esters of organic carboxylic acids are obtained as the product.

The esters of organic carboxylic acids which can be used to carry out the process according to the invention are the esters of different types of organic carboxylic acids, and in general it is most common if the radicals R "and R '" are identical to one another or have different meanings from one another, these being Alkyl radicals, cycloalkyl radicals, aryl, alkaryl and aralkyl radicals mean.

Typical examples of esters of organic carboxylic acids which can be used to carry out the process according to the invention are the following esters:

Formic acid methyl ester, formic acid ethyl ester, formic acid propyl ester, formic acid amyl ester, formic acid octyl ester, formic acid decyl ester, formic acid 55 dodecyl ester, formic acid tetradecyl ester, ethyl acid, ethyl acetate, acetic acid, hexadate vinyl esters, propyl acetate, isopropyl acetate, butyl acetate, hexyl acetate, octyl acetate, 60-decyl acetate, undecyl acetate, tridecyl acetate, pentadecyl acetate, propyl acetate, heptadecyl acetate methyl ester, propionic acid ethyl ester, propionic acid propyl ester, propionic acid decyl ester, butyric acid amyl ester, butyric acid heptyl ester, butyric acid decyl ester, vale-65 rian acid butyl ester, valeric acid hexyl ester, valeric acid octyl ester, the ethyl ester of cyclopentate carboxylic acid (ethyl-cyclopenta-carboxylate), methyl caproate (methyl-caproate), ethyl caproate, caproic acid e vinyl ester,

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Caproic acid propyl ester, caproic acid allyl ester, caproic acid butyl ester, caproic acid octyl ester, caproic acid dode cyl ester, caproic acid pentadecyl ester, cyclohexacarboxylic acid ethyl ester (ethyl cyclohexacarboxylate), oenanthic acid methyl ester (methyl, oenanthate) butyl ester, octanthate, methyl benzoate, ethyl benzoate, ethyl benzoate, isopropyl benzoate, n-butyl benzoate, isobutyl benzoate, isoamyl benzoate, phenyl benzoate, methyl caprylic acid (methyl caprylate), caprylic acid -propyl ester, caprylic acid amyl ester, caprylic acid heptyl ester, pelargonic acid ethyl ester (ethyl pelargonate), pelargonic acid vinyl ester, capric acid methyl ester (methyl caprate), capric acid vinyl ester, capric acid isopropyl ester, capric acid hept esters (methyl laurate), ethyl laurate, vinyl laurate, propyl laurate, octyl laurate, octyl laurate, dodecyl laurate, octadecyl laurate, myristine Acid methyl ester (ethyl myristate), myristic acid butyl ester, palmitic acid methyl ester (methyl palmitate), palmitinic acid ethyl ester, palmitic acid amyl ester, stearic acid ethyl ester (ethyl stearate), stearic acid octyl ester, stearadec sic acid , Oleic acid methyl ester (methyl oleate), oleic acid ethyl ester, oleic acid propyl ester, oleic acid isopropyl ester, oleic acid isobutyl ester, oleic acid isoamyl ester, oleic acid oleylester, ricinoleic acid methyl ester (methyl ricinoleolate), ricinoleic acid , Propyl ricinole and heptyl ricinole.

Other esters of organic carboxylic acids which have a radical R '"which is a substituted alkyl group, in particular an alkyl group substituted by hydroxyl groups or hydroxyalkoxy groups, can be used. For example, esters which are obtained by esterification of an organic carboxylic acid, such as, for example, formic acid , Acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, cyclohexylcarboxylic acid, enanthic acid, benzoic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, tri-decylcarboxylic acid (tridecylcarboxylic acid), palmitic acid, stearic acid, oleic acid and ricinoleic acid compound with a polyalkylene compound or examples of polyhydroxyalkylenes or polyalkylene glycols which can be used in the esterification include: ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, glycerol, pentaerythritol, sorbitol and the like. In addition, esters of dicarboxylic acids, wi e for example esters of oxalic acid, citric acid or terephthalic acid can be used.

Halogenated compounds of the formula I of the metals zinc, aluminum, titanium, tin or iron are used as catalysts. They have the following formula I.

MQn (I)

on in the

M is an atom from the group Zn, Al, Ti, Sn or Fe,

n represents the valency of the metal M and the groups

Q are identical to or different from one another and halogen atoms or groupings of the formula

R, OR, SR, NR2 or PR2

represent in which the remains

R are identical to or different from one another, and are optionally substituted hydrocarbon groups having 1 to 20 carbon atoms or hydrogen atoms.

When the metal atom M is zinc, then n is usually 2 and Q is either a halogen atom or a radical R or -OR. Particularly preferred halogen atoms are chlorine, bromine, iodine or fluorine atoms.

*

Examples of radicals R are alkyl, cycloalkyl, allyl, aryl or aralkyl radicals and specific examples of such radicals are the following:

Methyl, ethyl, vinyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, decyl, stearyl, phenyl, naphthyl, benzyl, touyl, cyclopentyl, cyclohexyl, cyclopentadiphenyl or derivatives of these preferred radicals R.

The following are typical examples of zinc compounds in which n is 2 and one radical Q is a halogen atom, while the other radical Q is a radical R: iodomethyl zinc iodide, ethyl zinc chloride, ethyl zinc jo-did, isopropyl zinc iodide, allyl zinc bromide, crotyl zinc bromide, phenyl zinc iodide.

The following compounds are mentioned as examples of zinc compounds in which n is 2 and both radicals Q have the meaning of radicals R:

Dimethyl zinc, diethyl zinc, divinyl zinc, ethyl propyl zinc, dipropyl zinc, diisopropyl zinc, ethyl isopropyl zinc, ethyl isobutyl zinc, ethyl cyclopentadienyl zinc, propyl isobutyl zinc, Dibutyl-zinc, diisobutyl-zinc, di-secondary-butyl-zinc, isobutyl-isoamyl-zinc, dicyclopentadienyl-zinc, diisoamyl-zinc, phenylcyclopentadienyl-zinc, bis-chlorophenyl-zinc, diphenyl-zinc, Ditoluyl zinc, dipheptyl zinc, bis-2-phenylpropyl zinc and di-ß-naphthyl zinc.

As examples of zinc compounds in which n is 2 and one of the two radicals

Q is a radical R, while the other of the two radicals Q represents a group —OR, the following compounds are mentioned:

Methyl-ethoxy-zinc, ethyl-isopropoxy-zinc.

Of the above examples of organozinc compounds, those in which both radicals Q represent groups R are particularly preferred.

If in the metal compounds of the formula given above

M is an aluminum atom, then n preferably has a value of 3 and the 3 radicals Q are identical or different from one another, and examples of such radicals Q are: halogen atoms or groups of the formula

R, OR, SR, NR2 or PR2.

Particularly preferred halogen atoms are chlorine atoms, bromine atoms, iodine atoms and fluorine atoms. Examples of radicals R in the above groups are: hydrogen atoms, alkyl radicals, cycloalkyl radicals, allyl radicals, aryl radicals or aralkyl radicals. Specific examples of such radicals R are the following:

Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, decyl, dodecyl, stearyl, phenyl, naphthyl, benzyl, touyl, cyclopentyl, cyclohexyl or derivatives of these preferred radicals.

The following are typical examples of aluminum compounds which can be used: aluminum compounds in which all of the radicals Q are halogen atoms, such as, for example, aluminum chloride, aluminum iodide, aluminum fluoride and aluminum bromide.

The following compounds may be mentioned as examples of such aluminum compounds in which the radicals Q have the meaning of halogen atoms as well as of radicals R.

Methyl aluminum dichloride, ethyl aluminum dichloride, isobutyl aluminum dichloride, ethyl aluminum dibromide, allyl aluminum dichloride, vinyl aluminum dichloride, methyl aluminum sesquichloride, ethyl aluminum sesquichlo rid, methyl-aluminum-sesquibromide, ethyl-aluminum-ses-quiiodide, isobutyl-aluminum-sesquichloride, hexyl-alumi-

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nium sesquichloride, cyclohexyl aluminum sesquichloride, phe-nyl aluminum dichloride, phenyl aluminum dibromide, dimethyl aluminum bromide, diethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum iodide, Diisobutyl aluminum chloride, ethyl phenyl aluminum chloride, dodecyl aluminum chloride and diphenyl aluminum chloride.

The following compounds may be mentioned as examples of aluminum compounds in which the radicals Q are R, where R is an organic radical or is a hydrogen atom:

Aluminum hydride, trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum, tri-phenyl aluminum, tri-n-hexyl aluminum, tri-benzyl aluminum, trioctyl aluminum, Trichloromethyl aluminum, tri-p-toluyl aluminum, tridodecyl aluminum, methyl diethyl aluminum, ethyl dihexyl aluminum, diethyl aluminum hydride and diisobutyl aluminum hydride.

Examples of aluminum compounds in which the radicals 0 are groups of the formula -OR are mentioned:

Trimethoxy aluminum, triethoxy aluminum, triisoprop oxy aluminum and tributoxy aluminum.

Examples of aluminum compounds in which the radicals Q are groupings of the formula NR2 are:

Tri- (ethylamino) aluminum, tri- (diethylamino) aluminum, tri- (isopropylamino) aluminum, tri- (diisopropylamino) aluminum, tri- (butylamino) aluminum, tri- (dibutylamino) ) aluminum, tri- (hexylamino) aluminum, tri- (cyclohexylamino) aluminum, trianilino aluminum and tri- (N-ethylanilino) aluminum.

Examples of aluminum compounds in which the radicals Q are groupings of the formula —SR are mentioned:

Aluminum trimethyl mercaptide, aluminum triethyl mer captide, aluminum tripropyl mercaptide, aluminum tributyl mercaptide or aluminum triphenyl mercaptide.

Examples of aluminum compounds in which the radicals Q stand for groupings of the formula PR2 are:

Aluminum tri (isopropyl phosphide), aluminum tri (butyl phosphide), aluminum tri (benzyl phosphide), aluminum tri (phenyl phosphide), aluminum tri (diethyl phosphide) or aluminum tri ( methylphenyl phosphide).

Examples of aluminum compounds are now given in which the radicals Q denote both halogen atoms and groups of the formula -OR:

Methoxy aluminum dichloride, ethoxy aluminum dichlo-rid, ethoxy aluminum dibromide, isopropoxy aluminum di-chloride, butoxy aluminum dichloride, phenoxy aluminum di-chloride, dimethoxy aluminum chloride, diethoxy aluminum chloride, diethoxy aluminum bromide and diphenoxy aluminum chloride.

The following are examples of such aluminum compounds in which the radicals Q have the meaning of both groups R and of groups -OR:

Methoxy-dimethyl-aluminum, ethoxy-diethyl-aluminum, phenoxy-diethyl-aluminum, isopropoxy-diethyl-aluminum, methoxy-diisobutyl-aluminum, ethyl-diethoxy-aluminum, ethyl-diphenoxy-aluminum or isobutyl-diethoxy-aluminum.

Examples of aluminum compounds in which the radicals Q are both halogen atoms and groupings of the formula —SR are the following compounds:

Methylmercapto-aluminum-dichloride, ethyl mercapto-aluminum-dichloride, ethyl-mercapto-aluminum-dibromide, iso-propylmercapto-aluminum-dichloride, phenylmercapto-aluminum-dichloride, diethylmercapto-aluminum-chloride, di-ethyl-ethylobutto-capto aluminum chloride and diphenyl mercapto aluminum chloride.

The following may be mentioned as examples of such aluminum compounds in which the radicals Q stand both for groups R and for groups —SR:

Diethyl aluminum methyl mercaptide, diethyl aluminum ethyl mercaptide, diethyl aluminum isobutyl mercaptide, diethyl aluminum cyclohexyl mercaptide, diethyl aluminum phe-nyl mercaptide, diethyl aluminum lauryl mercaptide, ethyl aluminum aluminum diethyl mercaptide diphenylmer-captid.

The following are examples of such aluminum compounds in which the radicals Q have the meaning of halogen atoms as well as of groups of the formula NR2:

Methylamino-aluminum dichloride, ethylamino-aluminum-dichloride, diethylamino-aluminum-dibromide, dimethyl-amino-aluminum-dichloride, ethylamino-aluminum-dichloride, iso-propylamino-aluminum-dichloride, cyclohexylamine-aluminum-aluminum chloride, Laurylamino aluminum dichloride, anilino aluminum dichloride, N-ethylanilino aluminum dichloride, benzylamino aluminum dichloride, toluylamino aluminum dichloride, bis (dimethylamino) aluminum chloride, bis (di-ethylamino) - aluminum chloride and Dianilino aluminum chloride.

Examples of aluminum compounds in which the radicals Q denote both groups R and groupings NR2 are:

Diethyl aluminum methyl amide, diethyl aluminum ethyl amide, diethyl aluminum butyl amide, diethyl aluminum cyclohexyl amide, diethyl aluminum phenyl amide, diethyl aluminum alu lauryl amide, diethyl aluminum benzyl amide, diethyl aluminum diethylamide, diethyl-aluminum-diphenylamide, ethyl-aluminum-bis- (diethylamide) and ethyl-aluminum-bis- (N-methyltoluylamide).

The following are examples of such aluminum compounds in which the radicals Q denote both halogen atoms and groups of the formula PR2:

Methylphosphino aluminum dichloride, ethylphosphino aluminum chloride, butylphosphino aluminum dichloride, cyclohexylphosphino aluminum dichloride, dimethylphosphino aluminum dibromide, diethylphosphino aluminum di-bromide, phosphino aluminum dichloride, phenylphosphine aluminum dichloride, methylphenylphosphino aluminum di-chloride, dimethylphosphino aluminum chloride, diethylphosphino aluminum chloride, dibutylphosphino aluminum chloride or diphenylphosphino aluminum chloride.

These aluminum halides mentioned can be produced by reacting a corresponding alcohol, a corresponding mercaptan, a corresponding amine or a corresponding phosphine with an aluminum halide according to known working methods.

Examples of such aluminum compounds are now given in which the radicals Q have the meaning both of radicals R and of groups of the formula PR2:

Diethyl aluminum methyl phosphide, diethyl aluminum ethyl phosphide, diethyl aluminum butyl phosphide, diethyl aluminum cyclohexyl phosphide, diethyl aluminum diethyl phosphide, diethyl aluminum dibutyl phosphide, diethyl aluminum phenyl phosphide, ethyl aluminum diethyl phosphide, ethyl aluminum diphenyl phosphide, ethyl aluminum bis (diethyl phosphide) and ethyl aluminum bis (diphenyl phosphate).

These aluminum compounds can be produced by reacting a corresponding alcohol, a corresponding mercaptan, a corresponding amine or phosphine with a trialkyl aluminum.

As examples of aluminum compounds in which the radicals Q have the following meanings, OR and SR or

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OR and NR2 or OR and PR2 or NR2 and PR2 or SR and PR2 the following compounds may be mentioned:

Ethoxy-aluminum-diethyl mercaptide, diethoxy-aluminum-ethyl-mercaptide, ethoxy-aluminum-bis (diethylamide), diethoxy-aluminum-diethylamide, ethoxy-aluminum-bis (diphenyl-phosphide), diethoxy-aluminum-diphenyl-phosphide, Bis (diethylamino) aluminum ethyl mercaptide, diethyl amino aluminum aluminum diethyl mercaptide, bis (diethylamino) aluminum miniphenyl phosphide, diethylamino aluminum bis (diphenyl phosphide), diethyl mercapto aluminum diphenyl phosphide or ethyl mercapto aluminum bis (diphenylphosphide).

These compounds can be prepared by reacting a corresponding alcohol, a corresponding mercaptan, a corresponding amine or a corresponding phosphine with an alkyl aluminum alkoxide or alkyl aluminum mercaptide or alkyl aluminum amide or alkyl aluminum phosphide.

If the aluminum compound is an aluminum halide, the radicals Q can have, for example, the following meanings: halogen and R and OR or halogen and R and SR or halogen and R and NR2 or halogen and R and PR2 or Halogen and OR and NR2 or halogen and OR and SR or halogen and OR and PR2 or halogen and SR and NR2 or halogen and NR and PR2 or halogen and SR and PR2. Typical examples of aluminum compounds of this type are the following compounds:

Methyl-ethoxy-aluminum-chloride, ethyl-isopropoxy-aluminum-chloride, ethyl-phenoxy-aluminum-chloride, ethyl-mercapto-aluminum-chloride, ethyl-mercapto-aluminum-chloride, ethyl-diethylamino-aluminum-chloride, ethyl- diphe-nylamino-aluminum chloride, ethyl-diethylphosphino-aluminum-chloride, ethyl-di-phenyl-phosphino-aluminum chloride, ethoxyphenylmercapto-aluminum-chloride, ethoxy-diethyl-amino-aluminum-chloride, ethoxyphenylphosphino-aluminum chloride, ethyl mercapto-diethylamino aluminum chloride, diethylamino diphenyl mercapto aluminum chloride and ethyl mercapto diphenylphosphino aluminum chloride.

These compounds can be prepared by reacting a corresponding alcohol, a corresponding mercaptan, a corresponding amine or a corresponding phosphine with an alkyl aluminum halide by known working methods.

Furthermore, the residues Q in the aluminum compounds can have the following meaning:

R and OR and NR2 or R and OR and SR or R and OR and PR2 or R and NR2 and SR or R and NR2 and PR2 or P and SR and PR2 or OR and NR2 and SR or OR and NR2 and PR2 or OR and SR and PR2 or NR2 and SR and PR2 and typical examples of such compounds are the following aluminum compounds:

Ethyl-ethoxy-aluminum-diethylamide, ethyl-ethoxy-aluminum-diphenylphosphide and ethyl-diethylamino-aluminum-diphenylphosphide. These compounds can be prepared by starting with trialkyl aluminum and using known working methods.

If the aluminum compound is used alone as a catalyst, then those aluminum compounds are preferred which, in combination, have the elements aluminum and oxygen, aluminum and halogen, aluminum and nitrogen or aluminum and phosphorus. Aluminum compounds which have the elements aluminum and halogen or aluminum and nitrogen or aluminum and phosphorus combined are particularly preferred.

If M is titanium in the metal compounds used, then n is usually tetravalent and the radicals Q in such compounds are the same or different from one another. These Q radicals can in turn be halogen atoms or R radicals or OR radicals. From a practical point of view, titanium halides and organotitanium halides are preferably used. The halogen atoms in these compounds are preferably chlorine, bromine, iodine or fluorine atoms and the following are preferred as groups R: alkyl, cycloalkyl, aryl, allyl and aralkyl groups. The following radicals may be mentioned as examples of such groupings:

Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, decyl, dodecyl, stearyl, phenyl, naphthyl, benzyl, toluyl, cyclopentyl, cyclohexyl or derivatives of these radicals. The radicals mentioned represent preferred meanings for R.

Typical examples of usable titanium compounds are mentioned below:

Titanium compounds in which all of the radicals Q are halogen atoms, such as, for example, titanium tetrachloride, titanium tetrabromide and titanium tetrafluoride.

Titanium compounds in which the radicals Q have the meaning of halogen atoms as well as radicals R. Examples of such compounds may be mentioned: methyl-titanium trichloride, ethyl-titanium trichloride, cyclopenadienyl-titanium trichloride, dimethyl-titanium dichloride, diethyl-titanium dichloride.

Titanium compounds in which the Q radicals are both halogen atoms and groups of the formula —OR. Examples of such connections are:

Trimethoxy-titanium chloride, triethoxy-titanium chloride, triiso-propoxy-titanium chloride, tributoxy-titanium chloride, triamyloxy-titanium-chloride, 2-ethyl-hexyloxy-titanium chloride, triphenoxy-titanium chloride, Tribenzyloxy-titanium chloride, tricyclohexyloxy-titanium chloride, dimethoxy-titanium dichloride, diethoxy-titanium dichloride, dibutoxy-titanium dichloride, diamyloxy-titanium dichloride, di-2-ethylhexyIoxy-titanium dichloride, dicyclohexyloxy dichlo-rid, diphenoxy-titanium dichloride, methoxy-titanium trichloride, eth-oxy-titanium trichloride, butoxy-titanium trichloride, cyclohexyloxy-titanium trichloride, phenoxy-titanium trichloride, benzyloxy-titanium tri-chloride and the corresponding bromine compounds of titanium, which are obtained when the chlorine atom in the above-mentioned chlorine-containing titanium compounds is replaced by a bromine atom.

If the titanium compounds are used alone as catalysts, then those titanium compounds which have halogen-titanium bonds are preferred and the catalytic activity of such compounds generally increases with the number of halogen-titanium bonds in these compounds.

If the metallic component M in the metal compounds used is tin, then n usually has a value of 4 and the radicals Q can be identical to or different from one another. Examples of radicals Q are: halogen atoms and groupings of the formula R, OR, SR, NR2 or PR2.

If the radicals Q have the meaning of halogen atoms, preferred such atoms are chlorine atoms, bromine atoms or iodine atoms and fluorine atoms. The following are preferred as radicals R in the groups listed above:

Alkyl groups, cycloalkyl groups, aryl groups, allyl groups and aralkyl groups and as examples of preferred such radicals the following may be mentioned: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, decyl, dodecyl, stearyl, phenyl, naphthyl, benzyl , Toluyl, cyclopentyl, cyclohexyl or derivatives of these radicals.

Typical examples of tin compounds that can be used are given below:

Tin compounds in which all residues Q are halogen

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are atoms such as tin tetrachloride, tin tetrabro-mid, tin tetraiodide and tin tetrafluoride.

Tin compounds in which the radicals Q have the meaning of halogen atoms as well as of groups R. Examples of such compounds are: dimethyl-tin-chloride, diethyl-tin-dichloride, di-n-pro-pyl-tin-dichloride, di-n-butyl-tin-dichloride, diphenyl-tin-dichloride, ditoluyl tin dichloride, dibenzyl tin dichloride, di-1-naphthyl tin dichloride, di-1-propenyl tin dibromide, divinyl tin dichloride, bis (p-chlorophenyl) tin dichloride. In these compounds mentioned above there are 2 residues Q halogen atoms and 2 residues Q groups R.

The following tin compounds also have groups Q which are halogen atoms and those which are radicals R, wherein in the individual compounds in each case 3 groups Q are radicals R and one is a halogen atom. Examples of such connections are:

Trimethyl-tin-chloride, trivinyl-tin-chloride, triethyl-tin-chloride, triisopropyl-tin-chloride, tripropyl-tin-chloride, tributyl-tin-chloride, triisoamyl-tin-chloride, triphenyl-tin-chloride, isohexyl- tin chloride, tribenzyl tin chloride, tri-octyl tin chloride, ethyldimethylhl tin iodide, methylethylpropyl tin iodide, butyldimethyl tin iodide, diethyl isobutyl tin bromide, dibutyl vinyl tin chloride, Diamylmethyl-tin-iodide as well as corresponding bromotin compounds, iodotin compounds and fluorotin compounds, which have the same structure as the chlorine-tin compounds specified above, but in each case the chlorine atom is replaced by one of the other halogen atoms mentioned.

The tin compounds mentioned can be prepared by known processes, and if such tin compounds are used as the only compounds as a catalyst alone, the catalytic activity increases with the increase in the number of halogen-tin bonds in the tin compounds mentioned.

If compounds are used as catalyst in which the metallic component is iron, the radicals Q are preferably halogen atoms, and particularly preferred compounds of this type are iron (III) chloride, iron (III-bro-mid), iron (III) iodide and Iron III fluoride, of the above-mentioned compounds, ferrichloride is particularly preferred.

The catalytic activity of these catalysts can be increased when used in combination with one or more catalyst compounds containing nitrogen, phosphorus, arsenic, antimony or bismuth.

As such cocatalysts, namely as compounds which contain an element of the 5th main group of the periodic table, such as nitrogen, phosphorus, antimony, arsenic or bismuth, preferred are those in which a halogen atom and / or a carbon atom directly on the nitrogen , the arsenic, the phosphorus, the antimony or the bismuth is bound. The following formula II has particularly preferred cocatalysts of this type

ARI (II)

on, and in this formula is

A is an atom of an element of the 5th main group of the periodic table and the residues

R2 are identical to or different from one another and represent halogen atoms, hydrogen atoms, substituted or unsubstituted hydrocarbon radicals having 1 to 20 carbon atoms or 2 radicals R2 together can represent a cyclic hydrocarbon radical and at least one of the radicals R2 is simultaneously a hydrocarbon grouping.

The R 2 radicals are usually halogen atoms, such as chlorine, bromine, iodine or fluorine atoms, or they are 616 399

indicate hydrocarbon groups, such as, for example, alkyl, allyl, aryl or aralkyl groups. Typical examples of hydrocarbon groups are the groups listed below:

Methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, tetradecyl, stearyl, phenyl, toluyl, benzyl, naphthyl and cyclohexyl.

If there is a nitrogen atom in the aforementioned formula II A, primary, secondary or tertiary polyamines or monoamines can be used as examples of such compounds. Specific examples of such amines are:

Methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, isopropylamine, triisopropylamine, hexylamine, cyclohexylamine, laurylamine, aniline, N-methyl-aniline, N, N-methylethylaniline, diphenylamine, a- or / 3-aminonaphthalene, benzylamine, toluidine Piperidine, pyridine, morpholine, N-methyltoluidine, piperazine, triethylenediamine, quinoline, oxazine and quinuclidine. Of these usable amines mentioned, those which have saturated, straight-chain carbon chains or have cycloalkyl chains are more preferred.

If there is a phosphorus atom in the compounds of the formula II A, these phosphorus compounds can be primary or secondary monophosphines or polyphosphines. Examples of phosphorus compounds which can be used in practice are: methylphosphine, ethylphosphine, propylphosphine, butylphosphine, pentylphosphine, cyclohexylphosphine, benzylphosphine, dimethylphosphine, diethylphosphine, diisopropylphosphine , Trimethyl-phosphine, triethyl-phosphine, ethyl-dimethyl-phosphine, triisopropyl-phosphine, trivinyl-phosphine, phenyl-phosphine, diphenyl-phosphine, triphenyl-phosphine, allyl-diphenyl-phosphine, methyl-phenyl-phosphine, ethyl-di -chlorophosphine, propyl-dichlorophosphine, isobutyl-dichlorophosphine, chloromethylhl-dichlorophosphine, dimethyl-bromophosphine, dichlorophenyl-phosphine, diphenyl-chlorophosphine, methyl-dibromophosphine, phenyl-dichloro -phosphine, dimethyl-bromophosphine, methyl-dichlorophosphine, diethyl-chlorophosphine, dibromo-chlorophosphine, ethyl-methyl-chlorophosphine, 1-naphthyl-dichlorophosphine, dimethyl-vinyl-phosphine , Naphthyl-diphenyl-phosphine, 1-methyl-cyclotetramethylene-phosphine, 1-phenyl-cyclotetramethylene-phosphine and 1-ethyl-pentamethylene-phosph there.

Of these compounds, the tertiary phosphines are more preferred.

If there is an arsenic atom in the compounds of formula II A used, then the compounds in question can be primary, secondary and tertiary monoarsines or poly-arsines. The following are examples of arsine compounds which can be used in practice:

Methyl dichloro arsine, ethyl dichloro arsine, butyl dichloro arsine, p-bromophenyl dichloro arsine, phenyl dichloro arsine, phenyl dibromo arsine, phenyl diiodo arsine, dimethyl chloro arsine, dimethyl-iodine-arsine, diethyl-chlorine-arsine, diphenyl-chlorine-arsine, methyl-arsine, dimethyl-arsine, trimethyl-arsine, ethyl-arsine, diethyl-arsine, triethyl-arsine, triallyl-arsine, tri- n-propyl-arsine, phenyl-arsine, p-aminophenyl-arsine, benzyl-arsine, p-toluyl-arsine, dichloro-arsine, tri-phenyl-arsine, tetraethyl-di-arsine, tetra-phenyl-di-arsine.

Of these arsine compounds mentioned, the tertiary arsines are more preferred.

If in the compounds of formula II A stands for antimony, then compounds can be used which are derived from stibine, ie the antimony hydrogen of the formula SbH3. In this case, primary, secondary or tertiary monostibins or polystibines can be used. Examples of useful antimony compounds are:

7

5

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15

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30th

35

40

45

50

55

60

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616 399

Methyl-dibromo-stibine, methyl-dichloro-stibine, phenyl-di-chloro-stibine, a-naphthyl-dichloro-stibine, dimethyl-bromo-stibine, dimethyl-chloro-stibine, dimethyl-iodo-stibine, diethyl-bromo- stibine, diisopropyl-bromo-stibine, dibutyl-chloro-stibine, diphenyl-chloro-stibine, di-a-naphthyl-iodo-stibine, methyl-stibine, dimethyl-stibine, trimethyl-stibine, triethyl-stibine, Trivinyl-stibine, tri-n-propyl-stibine, tributyl-stibine, tri-p-toluyl-stibine, tetraethyl distibin and tetraphenyl distibin.

Of these stibine compounds mentioned, the tertiary stibines are more preferred.

If bismuth is present in the compounds of the formula II, appropriate primary, secondary or tertiary bismuth compounds can be used. The following can be mentioned as practical bismuth compounds:

Methyl-bismuth-dibromide, methyl-bismuth-dichloride, methyl-bismuth-diiodide, ethyl-bismuth-dibromide, phenyl-bismuth-dibromide, dimethyl-bismuth-chloride, diphenyl-bismuth-chloro-rid, di-a- naphthyl bismuth chloride, trimethyl bismuth, tri-ethyl bismuth, triphenyl bismuth, diphenyl-a-naphthyl bismuth and tri-ß-naphthyl bismuth.

Of the compounds mentioned above, the amines, the phosphines, the arsines and the stibines are more effective than the corresponding bismuth compounds and the amines and the phosphines have the greatest effectiveness.

In the process according to the invention, in addition to the cocatalyst compound, which is an electron donor and which leads to a coordinative bond with the catalyst or to an interaction with the catalyst,

a second cocatalyst can also be used. This second cocatalyst contains an element of the 6th or 7th main group of the periodic system (that is, an element of groups 6a or 7a of the periodic system) and the following compounds are mentioned as typical examples of such second cocatalysts:

Straight-chain or cyclic ethers, such as, for example, dimethyl ether, diethyl ether, diisopropyl ether, methylphenyl ether, ethylene glycol, diethyl ether and tetrahydrofuran. Further examples may be mentioned: halogenated hydrocarbons, such as methyl chloride, ethyl chloride, butyl chloride, chlorobenzene, ethyl bromide, ethyl iodide. Sulfides such as dimethyl sulfide, diethyl sulfide, ethyl isopropyl sulfide, dibutyl sulfide and diphenyl sulfide can also be used for this purpose. Furthermore, aldehydes and ketones, such as methyl ethyl ketone, diethyl ketone, formaldehyde and acetaldehyde, can also be used.

Of the compounds of the formula I, in particular the aluminum compounds which have bonds between halogen atoms and aluminum, oxygen atoms and aluminum, nitrogen atoms and aluminum or phosphorus atoms and aluminum, as well as the halogenated titanium compounds and the multi-halogenated organic titanium compounds, the halogenated tin compounds, the multi-halogenated organotin compounds and the halogenated iron compounds themselves have an extremely good catalytic activity without the addition of a cocatalyst.

When a cocatalyst is used in combination with the catalyst, the catalytic efficiency is increased. Particularly in those cases where the catalyst alone does not have sufficient catalytic activity, the influence of the cocatalyst becomes significant, and the activity of the catalyst and the cocatalyst sometimes becomes equal to or higher than the activity of the catalyst when used alone, and thereby becomes sufficient catalytic effect achieved.

In general, the amount in which the catalyst or the cocatalyst is used is not restricted, and usually 0.01 to 20% by weight, preferably 0.1 to, is used

5% by weight of the catalyst to the ester of the carboxylic acid and the atomic ratio of the 5th main group element contained in the cocatalyst to the number of metal atoms contained in the catalyst is 0.05 to 10, preferably 0.2 to 5.

In the practical implementation of the process, the catalyst or the catalyst and the cocatalyst are used directly or indirectly in the reaction. Before the reaction, the catalyst and the cocatalyst are preferably pretreated by carrying out a dewatering, that is to say a dehydration or a dehydrocarbonation reaction, between the catalyst and the cocatalyst. The condition of the pretreated catalyst consisting of catalyst and cocatalyst differs depending on the atomic ratio used. For example, if one mole of triethyl aluminum is used as a catalyst and less than 4 moles of triethyl amine are used for the pretreatment, a catalytic mixture is obtained which contains covalent compounds of mono-, di- and tri- (diethylamino) aluminum. If 1 mol of triethyl aluminum and more than 4 moles of triethyl amine are used, a catalytic mixture is obtained which contains coordinated compounds which are composed of tri (diethylamine) aluminum and are coordinated with di-ethylamine.

The coordination of an atom of the 5th main group of the periodic system to a metal atom M or the interaction of an atom of the 5th main group of the periodic system with a metal atom M is achieved by mixing the catalyst and the cocatalyst in a ratio other than a ratio in which the catalyst and the cocatalyst form a covalent compound. The pretreatment of the catalyst and the cocatalyst can be carried out in the presence or in the absence of an inert solvent at an elevated temperature or at room temperature. Various types of organic solvents can be used as the inert solvent, such as ethers, ketones or esters. Examples of organic solvents which can be used are: hexane, heptane, octane, petroleum ether, benzene, toluene, xylene, cyclohexane and other solvents, the solvents mentioned being preferred. The pretreated catalyst can be used with or without the solvent, and if necessary, the pretreated catalyst can be cleaned. Further, when the catalyst and the cocatalyst are added directly to the reaction system containing the ester of the carboxylic acid and the oxirane, the catalyst can be rearranged or converted during the reaction of the oxirane and the ester of the carboxylic acid. Because oxygen and water tend to decompose the catalyst, it is preferable to treat and handle the catalyst in an inert atmosphere.

If the catalyst is used, it can be used without a support material or together with a solid support material, for example α-aluminum oxide, and the reaction of the alkylene oxide with the ether of the carboxylic acid can be carried out continuously or batchwise in a liquid phase. If you are working batchwise, the required amount of oxirane can either be added all at once or gradually.

The molar ratio between the oxirane and the ester of the carboxylic acid is not limited, and if small molar numbers of the oxirane are to be added to the ester of the carboxylic acid, a small number of moles of the oxirane are added and if a large number of moles of the oxirane is required , then a large amount, based on the molecular weight of the oxirane, is added.

If you add a large amount of the oxirane to the ester of

8th

s

10th

15

20th

25th

30th

35

40

45

50

55

60

65

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616 399

Carboxylic acid is added, then the oxirane is preferably gradually added to avoid a violent exothermic reaction. The reaction temperature is usually in the range from 50 to 300 ° C. and preferably in the range from 120 to 200 ° C. The reaction can be carried out either at an elevated pressure or at the vapor pressure which prevails at the reaction temperature. Usually a pressure of less than 50 kg / cm2 is used, and if one starts to work, the pressure drops as the reaction proceeds and becomes constant as soon as the reaction is complete.

Once the reaction is complete, if desired, the catalyst can be decomposed with water and the products obtained can be purified by distillation of the reaction mixture. If the catalyst is in solid form in the reaction mixture, then the reaction mixture is preferably filtered and then distilled to obtain the product. However, when the catalyst is dissolved in the reaction mixture, the reaction mixture is preferably distilled without prior filtration. The catalyst can be recycled to the process if the reaction is carried out in a suitable atmosphere.

When the process according to the invention is carried out, no substantial amounts of glycol ether are formed, and the ethylene glycol ether ester of the carboxylic acid is formed in high yields.

The invention will now be explained in more detail by means of examples.

Examples 1 to 21 Dry ethyl acetate, ethylene oxide and the catalyst were introduced into a dry stainless steel autoclave, the autoclave being equipped with a magnetic stirrer. The quantitative ratios of the starting materials and the catalyst listed in Table I were used. The raw materials and the catalyst were treated under a dry nitrogen gas. The reaction was started at a pressure of less than 15 kg / cm 2 and was stopped when the pressure reached equilibrium. The reaction mixture obtained was filtered, and the unreacted ethyl acetate was recovered by distillation under atmospheric pressure. Then the mixture was distilled under reduced pressure to obtain the desired product.

Table I lists the products, given in grams, which are contained in the respective reaction mixture. The terms used have the following meaning:

EO-1: ethylene glycol-ethyl ether acetate, EO-2: diethylene glycol-ethyl ether acetate, EO-3: polyethylene glycol-ethyl ether acetate, higher than triethylene glycol-ethyl ether acetate.

Examples 22 to 45 Dry ethyl acetate, ethylene oxide and catalyst were introduced into a dried stainless steel autoclave in the same manner as that used in Example 1. The quantitative ratios listed in Table II were used.

The ethylene oxide was added all at once and the reaction was carried out at a temperature of 160 ° C under an atmosphere of dry nitrogen. When the pressure reached equilibrium, the autoclave was cooled and about 90% of the amount of water based on the amount of water sufficient to decompose all of the catalyst was added to the reaction mixture. The precipitated aluminum hydroxide or titanium hydroxide was filtered off, and the unreacted ethyl acetate was distilled off. The desired product was obtained by distillation under reduced pressure.

The results obtained in the reaction are summarized in Table II below, and in this table the components listed in the reaction mixture mean the following:

EO-1: Ethylene glycol-ethyl ether acetate, EO-2: Diethylene glycol-ethyl ether acetate and EO-3: Polyethylene glycol-ethyl ether acetate, which is higher than triethylene glycol ethyl ether acetate.

Examples 46 and 47 According to the process described in Example 5, ethyl acetate and propylene oxide or isobutylene oxide were reacted. A catalyst made of aluminum chloride and triethylamine was used in this reaction and the reaction was allowed to proceed at 160 ° C.

In this reaction, the results listed in Table III were achieved and the products appearing in the reaction mixture have the following meanings: AO-1: alkylene glycol alkyl ether acetate, AO-2: dialkylene glycol alkyl ether acetate, AO-3: polyalkylene glycol alkyl ether acetate, which is higher than trialkylene glycol alkyl ether acetate.

Examples 48 and 49 According to the process described in Example 23, ethyl acetate and propylene oxide or isobutylene oxide were reacted with one another by using a catalyst composed of tri-ethoxy aluminum and triethylamine and letting the reaction proceed at 160 ° C.

The results shown in Table IV were obtained, the products listed in the reaction mixture having the following meanings: AO-1: alkylene glycol alkyl ether acetate, AO-2: dialkylene glycol alkyl ether acetate, AO-3: polyalkylene glycol alkyl ether acetate that is higher than trialkylene glycol alkyl ether acetate.

Examples 50 to 53 The procedure described in Example 5 was repeated, except that the ester of the carboxylic acid and the ethylene oxide were reacted with one another in the proportions given in Table V, using aluminum chloride and triethylamine as the catalyst.

The carboxylic acid esters used were the formic acid ethyl ester, the acetic acid ethyl ester, the acetic acid n-butyl ester and the propionic acid ethyl ester.

The results obtained with this implementation are summarized in Table V, and the names mean the following:

AO-1: Ethylene glycol alkyl ether ester of carboxylic acid, AO-2: Diethylene glycol alkyl ether ester of carboxylic acid, AO-3: Polyethylene glycol alkyl ether ester of carboxylic acid which is higher than the triethylene glycol alkyl ether ester of carboxylic acid.

Example 54

The procedure described in Example 5 was repeated, except that 148.5 g of the methyl ester of lauric acid and 28.6 g of ethylene oxide were reacted with each other using 0.853 g of aluminum chloride and 0.405 g of triethylamine. The reaction was carried out at 160 ° C for 1V2 hours.

After the reaction, the catalyst was filtered off and the unreacted methyl laurate was filtered off.

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

616 399

10th

This gave 67 g of a product which had a high boiling point. This product consisted of the ethylene glycol ethyl ether laurate, the diethylene glycol ethyl ether laurate and the polyethylene glycol ethyl ether laurate, and the average number of moles of the ethylene oxide groups added to the s laurate was 2.9.

Example 55

The procedure described in Example 6 was repeated, except that 150 g of the ethyl benzoate and 22 g of ethylene oxide were reacted with one another, using 190 g of aluminum chloride and 0.25 g of triethylamine as the catalyst. The reaction was carried out at 160 ° C for half an hour.

This reaction gave 32.5 g of 15 as product

Ethylene glycol-ethyl ether-benzoate, 10.7 g of diethylene glycol-ethyl ether-benzoate and 11.6 g of polyethylene glycol-ethyl ether-benzoate, which was higher than triethylene glycol-ethyl ether benzoate.

Example 56 20

Example 5 was repeated except that

that 22.5 g of phenyl acetate and 13.2 g of ethylene oxide were reacted. 1.33 g of aluminum chloride and 0.25 g of triethylamine were used as the catalyst. The reaction took place at 140 ° C for 0.4 hours. As a result, 29.4 g of the ethylene glycol phenyl ether acetate, 11.3 g of the diethylene glycol phenyl ether acetate and 9.2 g of the polyethylene glycol phenyl ether acetate were obtained.

Example 57 30

The procedure described in Example 6 was repeated, except that 150 g of glycerol trioleate and 15 g of ethylene oxide were reacted with each other. 1.9 g of titanium tetrachloride and 0.6 g of triphenylphosphine were used as the catalyst. The reaction temperature was 160 ° C. and the reaction was allowed to take place over 2.0 hours. As a result, 53 g of addition products of ethylene oxide with glycerol trioleate were obtained.

Example 58 40

The procedure described in Example 23 was repeated, except that 18 g of n-butyl acetate and 16 g of ethylene oxide were reacted. 1.3 g of triethoxy-aluminum and

0.51 g of triethylamine. The reaction was carried out at 160 ° C for 5 hours.

The product obtained was 18.2 g of ethylene glycol n-butyl ether acetate, 4.4 g of diethylene glycol n-butyl ether acetate and 6.0 g of polyethylene glycol n-butyl ether acetate, the tri-ethylene glycol was n-butyl ether acetate or higher than triethylene glycol n-butyl ether acetate.

Example 59

The procedure described in Example 32 was repeated, except that 170 g of ethyl propionate and 18.3 g of ethylene oxide were reacted using 1.6 g of triisopropoxy aluminum and 0.51 g of triethyl used amine and carried out the reaction at 160 ° C. for 5 hours. The product obtained was 20.6 g of ethylene glycol ethyl ether propionate (the yield was 35.9% based on the ethylene oxide used) and 3.5 g of diethylene glycol ethyl ether propionate (the yield was 9.4% based on the ethylene oxide used) and 7.9 g of polyethylene glycol-ethyl ether propionate.

Example 60

The procedure described in Example 23 was repeated, except that 114 g of ethyl laurate and 22 g of ethylene oxide were reacted, using 1.3 g of triethoxy aluminum and 0.5 g of triethylamine as the catalyst and the Reaction carried out at 160 ° C for 2 hours. The catalyst was then filtered off and the unreacted ethyl ester of lauric acid was recovered. The product obtained was 51 g of a polyethylene glycol-ethyl ether laurate, in which an average of 3.9 mol of ethylene oxide had been added.

Examples 61 to 65

The procedure described in Example 38 was repeated, except that the ethylene oxide was reacted with the acetic acid ester of a synthetic higher alcohol or with dimethyl terephthalate or with glycerol triacetate or with ethylene glycol diacetate or with dodecyl acetate has been. A mixture of diethyl aluminum chloride and triphenyl phosphine or aluminum tri-ethoxide and triethyl amine or di (n-butoxy) titanium dichloride and diethyl amine was used as the catalyst. The results listed in Table VI were obtained.

Table I

At

Source material

Catalyst in grams

Reaction

Mix the reaction game in g

catalyst

Cocatalyst

conditions products in grams

No.

Esters

Oxirane

Tempe

time in

the car

(Äthy

ratur in

Hours

bonic acid lenoxide)

° C

Vinegar-

acid-

ethyl-

ester)

EO-1

EO-2

EO-3

1

170

17th

AICI3

1.14

-

0

160

6.0

13.2

3.1

6.7

2nd

170

17th

FeCl3

3.24

-

0

170

8.0

18.0

8.3

10.1

3rd

170

17th

TiCl4

1.90

-

0

160

4.5

25.5

8.5

5.6

4th

170

17th

SnCl4

5.2

-

0

170

9.0

17.2

6.2

10.5

(55.5%)

(22.7%)

5

200

20th

AICI3

1.4

Triethylamine

0.60

160

1.4

33.2

9.0

4.4

(49.8%)

(27.8%)

6

160

20th

TiCl4

1.58

Triethylamine

0.53

160

0.5

29.6

11.0

5.7

7

170

17th

FeCl3

1.30

Triethylamine

0.51

160

4.0

21.9

6.4

5.1

8th

135

22.5

AICI3

1.05

Pyridine

0.37

160

3.0

27.9

9.8

5.7

9

170

17th

AICI3

1.13

n-butyl amine

0.39

160

5.0

24.8

6.8

5.2

10th

170

17th

AICI3

1.07

Di-n-propylamine

0.51

160

3.0

26.1

6.1

4.3

11 616 399

Table i (continued)

At

Source material

Catalyst in grams

Reaction

Mix the reaction game in g

catalyst

Cocatalyst

conditions products in grams

No.

Esters

Oxirane

Tempe

time in

the car

(Äthy

ratur in

Hours

bonic acid lenoxide)

° C

Vinegar-

acid-

ethyl-

ester)

EO-1

EO-2

EO-3

11

170

17th

A1CU

1.07

Tri-n-butylamine

0.92

160

2.0

28.0

6.9

3.6

12

170

17th

AICI3

1.07

N-ethyl piperidine

0.57

160

1.5

25.8

5.3

4.7

13

170

17th

TiCLt

1.52

Piperidine

0.43

160

1.5

27.2

9.0

5.4

14

170

17th

TiCl4

1.33

N-ethylmorpholine

0.50

160

2.0

28.5

9.2

3.4

15

160

20th

AICI3

1.33

Triphenylphosphine

0.66

160

1.5

29.0

7.9

5.1

16

160

20th

AICI3

1.33

Triphenyl arsine

0.67

170

4.0

21.5

6.8

3.3

17th

160

20th

AICI3

1.33

Diphenylchloro-

0.63

170

4.0

21.5

6.8

3.3

18th

phosphine

160

20th

TiCl4

1.90

Triphenylphosphine

0.66

160

0.7

28.6

10.1

4.5

19th

160

20th

TiCl4

1.90

Triphenyl arisine

0.67

170

1.5

26.1

8.7

5.1

20th

160

20th

FeCl3

1.62

Tributylphosphine

0.40

160

5.0

20.0

5.8

5.1

21st

160

20th

S11CI4

2.60

Triphenylphosphine

0.66

170

5.0

22.2

6.3

4.3

If percentages are given for the products in the reaction mixture, they relate to the yield of ethylene oxide.

Table II

Starting material catalyst in grams reaction mixture of the reaction game in g catalyst cocatalyst conditions products in g

No. Ethyl-Ethylene Temp. Time EO-1 EO-2 EO-3

acetate oxide

° C

H

22

170

17th

Al (OEt) 3

1.30

Triethylamine

0

160

6.0

15.1 (52.5)

3.7 (18.1)

6.0

23

170

17th

Al (OEt) 3

1.30

Triethylamine

0.51

160

2.5

25.2

5.8

5.7

24th

170

17th

Al (OEt) 3

1.40

Tri-n-propyl amine

0.31

160

4.0

22.8

6.2

5.8

25th

170

17th

Al (OEt) 3

1.50

Diethylamine

0.76

160

3.0

27.1

5.8

5.2

26

170

17th

Al (OEt) 3

1.40

Piperidine

0.39

160

4.0

24.6

6.8

4.4

27th

170

17th

Al (OEt) 3

1.40

Quinuclidine

0.45

160

5.0

21.8

5.2

5.1

28

170

17th

Al (OEt) 3

1.40

Triethylenediamine

0.52

160

3.5

22.2

7.0

5.1

29

170

17th

Al (OEt) 3

1.40

N, N-diethylamine

0.28

160

5.0

25.4

5.8

4.9

30th

170

17th

Al (OEt) 3

1.40

-

0.60

160

5.0

18.7

3.1

6.0

31

170

17th

Al (0-iPr) 3

1.63

Triethylamine

0

160

6.0

18.0 (56.4)

4.0 (20.0)

6.0

32

170

17th

Al (0-iPr) 3

1.63

Triethylamine

0.51

160

2.0

27.4

6.5

3.9

33

170

17th

Al (0-nBu) 3

1.70

Triethylamine

0.44

160

5.0

25.6

5.7

4.4

34

150

25th

AlEt3

1.14

Diethylamine

0.25

160

1.0

31.3

12.6

5.5

35

150

25th

AlEt3

1.14

-

0.37

160

0.5

30.6

12.2

6.4

37

160

20th

Et2AlCl

1.21

Triethylamine

0

160

2.5

25.6

6.2

4.3

38

160

20th

Et2AlCl

1.21

Triethylamine

0.25

160

0.5

28.4

9.5

6.1

39

160

20th

Et3Al2Cl3

1.30

0.25

160

0.5

29.1

5.7

8.6

40

160

20th

Et2AlCl

1.21

Triphenylphosphine

0.26

160

0.6

28.7

6.0

6.2

41

160

20th

(n-BuO) 3TiCl

3.03

Triethylamine

0.25

160

4.0

21.3

4.7

4.1

42

160

20th

(n-BuO) 2TiCl2

2.65

Triethylamine

0.25

160

1.0

29.7

8.2

4.8

43

160

20th

(n-BuO) 2TiCl

3.03

-

0

160

7.0

21.7

6.0

8.0

44

160

20th

(n-BuO) 2TiCl2

2.65

-

0

160

3.0

28.0

7.5

8.5

45

160

20th

(n-BuO) 2TiCl2

2.65

Tributylphosphine

0.26

160

1.3

30.3

11.0

5.7

45 '

160

20th

ZnEt2

1.24

Triethylamine

0.51

160

4.0

20.5

7.7

6.4

45 "

160

20th

ZnEt2

1.24

Triphenylphosphine

1.31

160

4.0

19.6

7.3

6.1

In the Catalyst column, the abbreviation OEt means O-ethyl, the abbreviation O-iPr stands for O-isopropyl and the abbreviation O-nBu means O-n-butyl. The percentages given in brackets in connection with the reaction mixture indicate the percent yield based on the ethylene oxide used.

616 399

12

Table III

Example output no. material in g

Ethyl acetate

Catalyst in grams of alkylene oxide A1C13

Reaction triethyl conditions amine Temp. Time in ° C in h

Mixture of the reaction products in grams of AO-1 AO-2 AO-3

46

47

160 160

Propylene oxide 21

Isobutylene oxide 26

1.07 0.51 160 5.0 1.07 0.51 160 10.0

Table IV

29.2 4.6 3.3 22.8 5.4 3.6

Example starting catalyst in grams of reaction

No. material alkylene oxide triethylamine conditions in g oxyaluamine temp. Time

Ethyl acetate min ° C in h

48

49

160 160

Propylene oxide 21

Isobutylene oxide 26

1.94 0.76 160 4.0 1.94 0.76 160 6.0

Mixture of the reaction products in grams of AO-1 AO-2 AO-3

38.9 3.6 2.6 33.9 2.4 2.7

Table V

example

Starting material in g

Catalyst in grams

Reaction

Mix the reaction

No.

Esters of carboxylic acid

Ethylene

A1C13

Triethyl conditions products in grams

oxide

amine

Tem. in ° C

Time in h

AO-1

AO-2

AO

50

Formic acid ethyl ester 170

20th

1.07

0.51

160

4.0

24.5

8.3

4.4

51

Ethyl acetate 170

20th

1.07

0.51

160

5.0

25.0

5.0

6.4

52

n-butyl acetate 170

16

1.07

0.51

160

2.5

19.2

8.0

4.9

53

Ethyl propionate 170

18th

1.07

0.51

160

3.0

24.3

8.1

6.3

Table VI

example

Starting material in g.

Catalyst in g

.

Products obtained in reaction in g

No.

Esters of carboxylic acid

Ethylene oxide

catalyst

Cocatalyst time in h

61

Polyal acetate

22

Et2AlCl

Triphenyl

1.0

Ethylene glycol or

(94)

(1.21)

phosphine (1.31)

Diethylene glycol or polyethylene glycol higher alkylene ether acetate (16)

62

Dimethyl

terephthalate

(97)

44

Et2AlCl

Triphenylphosphine (1.31)

1.0

Methyl - (/ 3-methoxyethyl) phthalate or bis - (/ j-methoxyethyl) phthalate or bis - (/ 5-meth-oxy- / 3-ethoxy - ä thy 1) - phthalate

63

Glycerol

triacetate

(109)

22

Al (OEt) 3

Triethylamine (0.70)

3.2

Tris (ß-acetoxy ethyl) glyceride and higher glycerides (63)

64

Ethylene glycol

diacetate

(146)

44

Al (OEt) 3

Triethylamine (0.50)

2.0

Diethylene glycol diacetate and polyethylene glycol diacetate (83)

65

Dodecyl acetate

22

(n-BuO) 2-

Triethylamine

4.0

Ethylene glycol or

(114)

TiCl2

(0.25)

Diethylene glycol or polyethylene glycol dodecyl ether acetate (59)

The abbreviation Et means ethyl and the abbreviation Bu means butyl.

s

Claims (17)

616 399 2nd PATENT CLAIMS 1. A process for the preparation of alkylene glycol ether esters of carboxylic acids, characterized in that an oxirane is reacted with an ester of a carboxylic acid, the reaction being carried out in the presence of a catalyst in the form of a compound of the formula MQn (I) takes place in the M is a metal atom from the group zinc, aluminum, titanium, tin or iron, n illustrates the valence of M and the radicals Q are identical or different from one another and halogen atoms or groups of the formula R, OR, SR, NR2 or PR2 represent in which the remains R are identical to or different from one another and represent substituted or unsubstituted hydrocarbon groups having 1 to 20 carbon atoms or hydrogen atoms. 2. The method according to claim 1, characterized in that the reaction further takes place in the presence of at least one cocatalyst which is selected from a group of compounds which has at least one nitrogen atom or phosphorus atom or antimony atom or arsenic atom or bismuth atom, and in which at least one halogen atom or a carbon atom is directly attached to the nitrogen, arsenic, phosphorus, antimony or bismuth atom. 3. The method according to claim 1 or 2, characterized in that one uses an oxirane which has the following formula in which the radicals R3 are identical to or different from one another and represent substituted or unsubstituted hydrocarbon radicals having 1 to 10 carbon atoms or hydrogen atoms. 4. The method according to claim 1 or 2, characterized in that the ester of carboxylic acid used has the following formula O II R "—C — OR '" in which the rest R "is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and R '"represents a substituted or unsubstituted hydrocarbon radical having 1 to 20 carbon atoms, in which case a mixture of several such esters in which the radicals R" or R' "have a different meaning is optionally used to carry out the process. 5. The method according to claim 4, characterized in that an ester of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, cyclopentane-carboxylic acid, caproic acid, enanthic acid, benzoic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid as the ester of carboxylic acid , Palmitic acid, stearic acid, oleic acid or ricinoleic acid are used. 6. The method according to claim 3, characterized in that as oxirane ethylene oxide, propylene oxide, isobutylene oxide, 1,2-butylene oxide, 2,3-butylene oxide or styrene oxide used. 7. The method according to claim 1 or 2, characterized in that in the catalyst M is a zinc atom. 8. The method according to claim 1 or 2, characterized in that in the catalyst M denotes an aluminum atom. 9. The method according to claim 1 or 2, characterized in that in the catalyst M is a titanium atom. 10. The method according to claim 1 or 2, characterized in that in the catalyst M is a tin atom. 11. The method according to claim 1 or 2, characterized in that a compound from the group of iron halides is used as catalyst. 12. The method according to claim 2, characterized in that a cocatalyst of the following formula (II) ARI (II) used in the A is a nitrogen, phosphorus, antimony, arsenic or bismuth atom and the residues R2 are identical to or different from one another and represent halogen atoms, hydrogen atoms or substituted or unsubstituted hydrocarbon groups having 1 to 20 carbon atoms, where 2 radicals R2 can represent a cyclic hydrocarbon and at least one of the radicals R2 is a hydrocarbon grouping. 13. The method according to claim 12, characterized in that the cocatalyst is a compound from the group of amines, phosphines, arsines or stibines (derivatives of the antimony hydrogen). 14. The method according to claim 7, characterized in that the organozinc compound used has the formula ZnR2 in which the two residues R are identical to or different from one another and are optionally substituted hydrocarbon groups having 1 to 20 carbon atoms. 15. The method according to claim 8, characterized in that a catalyst of the formula A1Q3 used in which the 3 residues Q are identical to or different from one another and halogen atoms or groupings of the formula R, OR, SR, NR2 or PR2 mean in which the remnants R are identical to or different from one another and are optionally substituted hydrocarbon groups having 1 to 20 carbon atoms or hydrogen atoms. 16. The method according to claim 9, characterized in that in at least one Q is a halogen atom and one is a grouping of the formula R, OR, SR, NR2 or PR2 where R cannot be hydrogen. 17. The method according to claim 10, characterized in that Q is a halogen atom or at least one halogen atom and a grouping of the formula R is OR, SR, NR2 or PR2, where R cannot be hydrogen. 5 10th 15 20th 25th 30th 35 40 45 50 55 60 65