CA1074339A - Manufacture of alkyl ethers or ethylene glycols - Google Patents
Manufacture of alkyl ethers or ethylene glycolsInfo
- Publication number
- CA1074339A CA1074339A CA262,438A CA262438A CA1074339A CA 1074339 A CA1074339 A CA 1074339A CA 262438 A CA262438 A CA 262438A CA 1074339 A CA1074339 A CA 1074339A
- Authority
- CA
- Canada
- Prior art keywords
- weight
- glycol
- ether
- reaction
- exchanger
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/04—Saturated ethers
- C07C43/10—Saturated ethers of polyhydroxy compounds
- C07C43/11—Polyethers containing —O—(C—C—O—)n units with ≤ 2 n≤ 10
Abstract
ABSTRACT OF THE DISCLOSURE
The present invention relates to new methyl isopropyl ethers of triethylene glycol, tetraethylene glycol and/or pentaethylene glycol which, in particular, may be used advantageously as gas washing fluids.
The present invention relates to new methyl isopropyl ethers of triethylene glycol, tetraethylene glycol and/or pentaethylene glycol which, in particular, may be used advantageously as gas washing fluids.
Description
The present invention relates to new methyl isopropyl ethers of triethylene glyeol, tetraethylene glycol and/or penta-ethylene glyeol.
Dialkyl ethers of ethylene glyeols are obtained, for example, in accordance with German Laid-Open Application DOS
Dialkyl ethers of ethylene glyeols are obtained, for example, in accordance with German Laid-Open Application DOS
2,028,423 by reaeting the monoalkyl ethers with elementary sodium to give the sodium alcoholates and reaeting the latter with alkyl chlorides to give the dialkyl ethers and sodium ehloride. The use of elementary sodium presents problems in earrying ~ut the process industrially, and the unavoidable produetion of sodium chloride is undesirable.
Aceording to another proeess, alkyl ethers of mono-ethylene glyeol and diethylene glyeol are manufaetured from the eorresponding glyeols and an olefin in the presence of strongly aeid eation exchangers (compare German Laid-Open Applieation DOS 2,450,667). This process is primarily suitable for the manufacture of glycol monoalkyl ethers and is only of limited suitability for the manufacture of symmetrieal glycol dialkyl ethers.
The proeess has deeisive disadvantages as far as the formation of symmetrieal ethers of ethylene glyeol is eoneerned.
Though, for example, propylene reaets more readily under the stated eonditions than does ethylene, the eonversions are low and the yields of diether are poor. For instanee, aeeording to Example 4 of DOS 2,450,667, the mixture obtained contains 57.9~
of uneonverted glycol and only 3.5~ by weight of the diether, in spite of using a 1.5-fold excess of propylene. Aceordingly, eompletely etherified eompounds, above all those wherein the alkyl radieals are of less than 3 earbon atoms, can hardly be obtained economically by this process.
~ evertheless, German Laid-Open Applications DOS 2,350,569 and 2,445,774 propose effecting the addition reaction of isobutene to free alcoholic hydroxyl groups with the aid of an ion exchanger;
in the former reference, methyldiglycol, for example, is used for this purpose, and methyldi~lycol tert.-butyl ether is obtained.
If propylene is used instead of isobutylene, and an exchanger whIch has been brought to the H~ form by conventional methods, is employed, the same process fails.
The new methyl isopropyl ethers of triethylene glycol, tetraethylene glycol and/or pentaethylene glycol may be obtained by the addition reaction of propylene of industrial grade with a monoalkyl ether of ethylene glycol or of a polyethylene glycol selected from monomethyl ether of triethylene glycol, tetraethylene glycol and pentaethylene glycol or a mixture of these compounds in the presence of a cationic ion exchange resin in the acid form, the ion exchange resin being dried before use.
It is advantageous also to use the reactants in a subs-tantially anhydrous form, particularly in continuous operation.
Furthermore, the reaction must be carried out so as to avoid forming substantial amounts of water as a by-product.
These new compounds have interesting properties. They can be used with advantage as constituents of hydraulic fluids or as high-pressure and extreme-pressure lubricants. A particularly important application of these compounds obtainable in accordance with the above process is to wash gases in order to remove hydrogen sulfide therefrom. In this context, reference may be made to U.S.
Patent 3,36~,133. A further application of the compounds is as solvents ; for example, the n-butyl i-propyl ether of diethylene glycol is used to extract propiolic acid from water.
The above process is carried out at from about 20 to 150C and at a pressure of from about 1 to 150 bars. A temperature of from 50 to 150C, in particular from 70 to 130 C, is preferred.
In some cases, the maximum possible wor~ing temperature is determined by the stability of the ion exchanger used. The pressure in general depends on the volatility of the olefin and is, for example, from 2 to 50 bars, especially from 5 to 40 bars, in the case of propylene.
For olefins of 6 or more carbon atoms, superatmospheric pressure is in many cases not necessary.
Monoalkyl ether of ethylene glycol or of a polyethylene glycol selected from monomethyl ether of triethylene glycol, tetraethylene glycol and pentaethylene glycol are used with particular advantage as starting materials. However, (poly)-ethylene glycol monoethers of alcohols of more than 4 carbon atoms can also be used. Instead of a particular glycol mono-ether, mixtures of different compounds of this type, in particular homologs such as are obtained, for example, on reacting excess ethylene oxide with alcohols, can be reacted with propylene, or another olefin, in accordance with the invention.
The olefin used in the above process may be of industrial grade but should, for technical reasons, e.g. because of the problem of off-gas in continuous operation, be of at least 80% strength. Propylene, specifically, can be used in the gaseous or liquid state; the reaction merely requires an olefin which dissolves to a certain degree in the other reactant.
Suitable olefins are those with a terminal or non-terminal double bond, though olefins with a non-terminal double bond only react with difficulty if they are of more than 6 carbon atoms. In principle, olefins of up to about 10 carbon atoms may be used.
The catalyst used in the above process is one of the commercial styrene-based cation exchange resins (converted to the acid (H ) form), which has been manufactured by copQlymerization of styrene with divinylbenzene, in the presence or absence of chemically inert materials intended to produce a macroporous structure, and -generally subsequent - sulfonation.
Typical examples are the commercial products ~ Amberlite 200 and ~074339 Amherlys.t 15 (manufactured by Rohm and Haas). The use of Lewasorb A lQ, ~ Lewatit SPC 108/H and SPC 118/H and especially Lewatit CA 925~ HL (all manufactured by Bayer AG) is particularly advantageous. The manufacture of such resins is well-known and forms no part of the present invention.
The following are examples of suitable processes for drying the ~on exchanger:
OOZ. 31,590 1) Drying by azeotropic distillation: the air-dry ion exchanger is mixed, in a suitable apparatus, with a sufficient amount of benzene or another suitable liquid which does not interfere with the reaction of the glycol monoalkyl ethers with propylene and has a boiling point not above 120C, and the mixture is distilled until no further water passes over. The exchanger is filtered off and, if necessary, is freed from residual benzene or other solvent by heating for several hours at 110C/20 mm Hg.
2) Drying by displacing the H20 with hydrophilic organic liquids a) Batch process: 1 part of exchanger is boiled under reflux with, for example, 2 parts of isopropanol. At intervals of about 2 hours, the agent used to displace the H20 is renewed until the H20 content in the isopropanol is less than 0.1%.
b) Column process: a filter column is filled with about 0.5 bed volume of isopropanol, 1 bed volume of ion exchanger is then introduced and absorbed by the exchanger, and a further 2 - 3 bed volumes of isopropanol are allowed to run slowly (at 2 - 5 liters/h. liter) over the exchanger until the H20 content is less than 0.1%. The column should throughout be kept at 70-75C.
The isopropanol is removed from the exchanger, which has been pre-treated in accordance with a) or b), at 100 mm Hg and 110C.
Using the process of the invention, propylene or another olefin and glycol monoalkyl ethers are reacted in the presence of the exchanger by bringing these constituents into contact, generally under pressure. Too low a reaction temperature entails the disadvantage that the rate of reaction falls, whilst too high a reaction temperature causes side reactions, e.g. the degradation of the glycol monoalkyl ethers and glycol dialkyl ethers to more volatile compounds, and the destruction of the 1~74339 o.z. 31,590 catalystO The ratio Or olefin to glycol monoalkyl ether is in itself not criticalO In general, equimolar amounts, or an excess of olefin, are employed. We assume that the addition reaction of glycol monoalkyl ethers with olefins is an equilibrium reaction.
Accordingly, the ratio of the reactants is only critical in as much as an excess of olefin is necessary to achieve high conver-sions of the glycol monoalkyl ether.
The use of an inert solvent is not essential, but not objec-tionable either.
The amount of the strongly acid cation exchange resin used as the catalyst is not confined to particular limits, but in general from about 0.1 to 50% by weight, based on the glycol mono-alkyl ether, suffices. In the case of a continuous reaction using, for example, a fixed catalyst, the reaction mixture can be brought into contact with a greater or lesser amount of catalyst, depending on the residence time. In such cases, the residence time required for the reaction is, for example, from about 1 mi-nute to 10 hours. In continuous operation, the reaction mixture can be fed in at the appropriate space velocity. The reaction can also be carried out in shaken autoclaves or stirred autoclaves, in which case the catalyst is suspended in the reaction mixture.
Trickle operation is particularly suitable. In this method, the glycol monoalkyl ether and liquid olefin are passed over the fixed catalyst in the reaction chamber. Particularly in the case of propylene~ it is advantageous to pass the olefin and the glycol monoalkyl ether together over the catalyst~ but it is necessary to bear in mind that the olefin is of relatively low solubility in the glycol ether, and good mixing of the two liquid phases is therefore desirable. In another embodiment, the catalyst, sus-
Aceording to another proeess, alkyl ethers of mono-ethylene glyeol and diethylene glyeol are manufaetured from the eorresponding glyeols and an olefin in the presence of strongly aeid eation exchangers (compare German Laid-Open Applieation DOS 2,450,667). This process is primarily suitable for the manufacture of glycol monoalkyl ethers and is only of limited suitability for the manufacture of symmetrieal glycol dialkyl ethers.
The proeess has deeisive disadvantages as far as the formation of symmetrieal ethers of ethylene glyeol is eoneerned.
Though, for example, propylene reaets more readily under the stated eonditions than does ethylene, the eonversions are low and the yields of diether are poor. For instanee, aeeording to Example 4 of DOS 2,450,667, the mixture obtained contains 57.9~
of uneonverted glycol and only 3.5~ by weight of the diether, in spite of using a 1.5-fold excess of propylene. Aceordingly, eompletely etherified eompounds, above all those wherein the alkyl radieals are of less than 3 earbon atoms, can hardly be obtained economically by this process.
~ evertheless, German Laid-Open Applications DOS 2,350,569 and 2,445,774 propose effecting the addition reaction of isobutene to free alcoholic hydroxyl groups with the aid of an ion exchanger;
in the former reference, methyldiglycol, for example, is used for this purpose, and methyldi~lycol tert.-butyl ether is obtained.
If propylene is used instead of isobutylene, and an exchanger whIch has been brought to the H~ form by conventional methods, is employed, the same process fails.
The new methyl isopropyl ethers of triethylene glycol, tetraethylene glycol and/or pentaethylene glycol may be obtained by the addition reaction of propylene of industrial grade with a monoalkyl ether of ethylene glycol or of a polyethylene glycol selected from monomethyl ether of triethylene glycol, tetraethylene glycol and pentaethylene glycol or a mixture of these compounds in the presence of a cationic ion exchange resin in the acid form, the ion exchange resin being dried before use.
It is advantageous also to use the reactants in a subs-tantially anhydrous form, particularly in continuous operation.
Furthermore, the reaction must be carried out so as to avoid forming substantial amounts of water as a by-product.
These new compounds have interesting properties. They can be used with advantage as constituents of hydraulic fluids or as high-pressure and extreme-pressure lubricants. A particularly important application of these compounds obtainable in accordance with the above process is to wash gases in order to remove hydrogen sulfide therefrom. In this context, reference may be made to U.S.
Patent 3,36~,133. A further application of the compounds is as solvents ; for example, the n-butyl i-propyl ether of diethylene glycol is used to extract propiolic acid from water.
The above process is carried out at from about 20 to 150C and at a pressure of from about 1 to 150 bars. A temperature of from 50 to 150C, in particular from 70 to 130 C, is preferred.
In some cases, the maximum possible wor~ing temperature is determined by the stability of the ion exchanger used. The pressure in general depends on the volatility of the olefin and is, for example, from 2 to 50 bars, especially from 5 to 40 bars, in the case of propylene.
For olefins of 6 or more carbon atoms, superatmospheric pressure is in many cases not necessary.
Monoalkyl ether of ethylene glycol or of a polyethylene glycol selected from monomethyl ether of triethylene glycol, tetraethylene glycol and pentaethylene glycol are used with particular advantage as starting materials. However, (poly)-ethylene glycol monoethers of alcohols of more than 4 carbon atoms can also be used. Instead of a particular glycol mono-ether, mixtures of different compounds of this type, in particular homologs such as are obtained, for example, on reacting excess ethylene oxide with alcohols, can be reacted with propylene, or another olefin, in accordance with the invention.
The olefin used in the above process may be of industrial grade but should, for technical reasons, e.g. because of the problem of off-gas in continuous operation, be of at least 80% strength. Propylene, specifically, can be used in the gaseous or liquid state; the reaction merely requires an olefin which dissolves to a certain degree in the other reactant.
Suitable olefins are those with a terminal or non-terminal double bond, though olefins with a non-terminal double bond only react with difficulty if they are of more than 6 carbon atoms. In principle, olefins of up to about 10 carbon atoms may be used.
The catalyst used in the above process is one of the commercial styrene-based cation exchange resins (converted to the acid (H ) form), which has been manufactured by copQlymerization of styrene with divinylbenzene, in the presence or absence of chemically inert materials intended to produce a macroporous structure, and -generally subsequent - sulfonation.
Typical examples are the commercial products ~ Amberlite 200 and ~074339 Amherlys.t 15 (manufactured by Rohm and Haas). The use of Lewasorb A lQ, ~ Lewatit SPC 108/H and SPC 118/H and especially Lewatit CA 925~ HL (all manufactured by Bayer AG) is particularly advantageous. The manufacture of such resins is well-known and forms no part of the present invention.
The following are examples of suitable processes for drying the ~on exchanger:
OOZ. 31,590 1) Drying by azeotropic distillation: the air-dry ion exchanger is mixed, in a suitable apparatus, with a sufficient amount of benzene or another suitable liquid which does not interfere with the reaction of the glycol monoalkyl ethers with propylene and has a boiling point not above 120C, and the mixture is distilled until no further water passes over. The exchanger is filtered off and, if necessary, is freed from residual benzene or other solvent by heating for several hours at 110C/20 mm Hg.
2) Drying by displacing the H20 with hydrophilic organic liquids a) Batch process: 1 part of exchanger is boiled under reflux with, for example, 2 parts of isopropanol. At intervals of about 2 hours, the agent used to displace the H20 is renewed until the H20 content in the isopropanol is less than 0.1%.
b) Column process: a filter column is filled with about 0.5 bed volume of isopropanol, 1 bed volume of ion exchanger is then introduced and absorbed by the exchanger, and a further 2 - 3 bed volumes of isopropanol are allowed to run slowly (at 2 - 5 liters/h. liter) over the exchanger until the H20 content is less than 0.1%. The column should throughout be kept at 70-75C.
The isopropanol is removed from the exchanger, which has been pre-treated in accordance with a) or b), at 100 mm Hg and 110C.
Using the process of the invention, propylene or another olefin and glycol monoalkyl ethers are reacted in the presence of the exchanger by bringing these constituents into contact, generally under pressure. Too low a reaction temperature entails the disadvantage that the rate of reaction falls, whilst too high a reaction temperature causes side reactions, e.g. the degradation of the glycol monoalkyl ethers and glycol dialkyl ethers to more volatile compounds, and the destruction of the 1~74339 o.z. 31,590 catalystO The ratio Or olefin to glycol monoalkyl ether is in itself not criticalO In general, equimolar amounts, or an excess of olefin, are employed. We assume that the addition reaction of glycol monoalkyl ethers with olefins is an equilibrium reaction.
Accordingly, the ratio of the reactants is only critical in as much as an excess of olefin is necessary to achieve high conver-sions of the glycol monoalkyl ether.
The use of an inert solvent is not essential, but not objec-tionable either.
The amount of the strongly acid cation exchange resin used as the catalyst is not confined to particular limits, but in general from about 0.1 to 50% by weight, based on the glycol mono-alkyl ether, suffices. In the case of a continuous reaction using, for example, a fixed catalyst, the reaction mixture can be brought into contact with a greater or lesser amount of catalyst, depending on the residence time. In such cases, the residence time required for the reaction is, for example, from about 1 mi-nute to 10 hours. In continuous operation, the reaction mixture can be fed in at the appropriate space velocity. The reaction can also be carried out in shaken autoclaves or stirred autoclaves, in which case the catalyst is suspended in the reaction mixture.
Trickle operation is particularly suitable. In this method, the glycol monoalkyl ether and liquid olefin are passed over the fixed catalyst in the reaction chamber. Particularly in the case of propylene~ it is advantageous to pass the olefin and the glycol monoalkyl ether together over the catalyst~ but it is necessary to bear in mind that the olefin is of relatively low solubility in the glycol ether, and good mixing of the two liquid phases is therefore desirable. In another embodiment, the catalyst, sus-
3 Fended in the glycol monoalkyl ether, can be passed, together withpropylene, through the reaction zone. It is particularly ad-vantageous to use the submerged method, in which the reaction mixture i5 passed over the fixed catalyst, in the reaction chamber, in such a way that the catalyst always remains covered by the liquid phase.
The unconverted olefin is separated off, e.g. by flash evaporation or by distillation, whilst the catalyst is, if required, removed by filtration from the mixture discharged from the reaction, which is liqu;d under normal conditions. This liquid product is worked up, if desired, by distillation under reduced pressure or, in certain cases, by extraction, because in some cases the mono-ether and diether have different solubilities, for example inwater, but very similar boiling points. The glycol alkyl isopropyl ethers in general boil at lower temperatures than the corresponding monoalkyl ethers, and these in turn boil at lower temperatures than the corresponding glycols. In some cases (the isobutyl ethers and isoamyl ethers of certain glycol monoalkyl ethers) the desired end product however boils at a higher temperature than the monoalkyl ether. It the process is carried out continuously, unconverted olefin and glycol monoalkyl ether are recycled.
1074339 o . z . 31, 590 The methyl isopropyl ethers of triethylene glycol, tetra-ethylene glycol and pentaethylene glycol are new and exceptionally suitable for use as extractants. One of their advantages over conventional extractants is that they have a particularly low ViS COSity .
The Examples which follow illustrate the invention. In these Examples, the term "volatiles" is applied globally to all reaction products which have a lower boiling point than the glycol monoalkyl ether employed and the corresponding glycol alkyl i-propyl ether. Compounds which boil at a higher tamperature than the glycol monoalkyl ether employed may be formed in small amounts as by-products. The reaction prod~tis freed from volatiles by, for example, distillation or extraction, and the distillation residue is analyzed by quantitative gas chromatography. The % by weight, based on reaction product, is quoted. The exchanger used is in each case in the acid form and is air-dry at the start of the experiment.
0.37 mole of triethylene glycol monomethyl ether, 1.03 moles of propylene and 26 g of dry Lewatit CA 9259 HL (from Bayer AG), ZO a macro-reticular cation exchanger based on styrene~divinylbenzene and containing sulfonic acid groups, which was dried by azeotropic distillation with benzene, are shaken in a 250 ml stainless steel autoclave for one hour at 100 C under autogenous pressure. At the end of the reaction, the unconverted propylene is removed by flash evaporation and the ion exchanger is filtered off. The composition of the product thus obtained is: 3.9% by weight of volatiles, 85.5%
by weight of triethylene glycol methyl isopropyl ether and 10.6%
by weight of triethylene glycol monomethyl ether.
If the procedure described in Example 1 is followed, using exchanger which has not been (specially) dried (i~e. using air-dry 1~)'74339 o~z. ~1,590 exchanger), the composition of the reaction product is: 5. 8g by weight of volatiles and 94~2% by weight of triethyle~ glycol mono-methyl ether.
0.29 mole of tetraethylene glycol monomethyl ether an 0.76 mole of propylene are reacted, by the method described in Example 1, over 20 g of dry Lewatit CA 9259 HL exchangerO The composition of the reaction product is 3.1% by weight of volatiles, 88.3%
by weight of tetraethylene glycol methyl isopropyl ether and 8.6%
by weight of tetraethylene glycol monomethyl etherO
This is carried out as described in Example 2, but using 20 g of dry Amberlyst 15 exchanger (a macro-reticular cation exchanger containing sulfonic acid groups, a commercial product of Rohm & Haas). The composition of the reaction product is:
2.6% by weight of volatiles, 55.7% by weight of tetraethylene glycol methyl isopropyl ether and 41.7% by weight of tetraethylene glycol monomethyl ether.
0.24 mole of pentaethylene glycol monomethyl ether and 0.63 mole of propylene are reacted, by the method described in Example 1, over 20 g of dry Lewatit CA 9259 HL exchanger. The composition of the reaction product is: 2~3% by weight of volatiles, 46.8%
by weight of pentaethylene glycol methyl isopropyl ether and 50.9% by weight of pentaethylene glycol monomethyl ether.
0.33 mole of triethylene glycol monoethyl ether and 0.76 mole of propylene are reacted, by the method described in Example 1, over 40 g of dry Lewasorb A 10 exchanger (a pulverulent macro-reticular cation exchanger with sulfonic acid groups, a commer-cial product of Bayer AG)o The composition of the reaction pro-duct is: 9~4~ by weight of volatiles, 84.7% by weight of tri-_ g _ 1~74339 O.Z. 31,590 ethylene glycol ethyl isopropyl ether and 5.9% by weight of tri-ethylene glycol monoethyl etherO
0.28 mole of tetraethylene glycol monoethyl ether and 0.76 mole of propylene are reacted, by the method described in Example 1, over 20 g of dry Lewatit CA 9259 HL. The composition of the reaction product is: 605% by weight of volatiles, 89.0% by weight of tetraethylene glycol ethyl isopropyl ether and 4.5% by weight of tetraethylene glycol monoethyl ether.
1.34 moles of triethylene glycol monomethyl ether and 2.28 moles of propylene are reacted, in a 1 liter stainless steel autoclave, over 40 g of dry Lewatit CA 9259 HL, whilst stirring, by the method described in Example 1. The composition of the reaction product is: 5.6% by weight of volatiles, 87. 5% by weight of triethylene glycol methyl isopropyl ether and 6.9% by weight of triethylene glycol monomethyl ether.
1.92 moles of tetraethylene glycol monomethyl ether and 3.04 moles of propylene are reacted, by the method described in Example 1, over 80 g of dry Lewatit CA 9259 HL. The composition of the reaction product is: 3. 7% by weight of volatiles, 82.7%
20 by weight of tetraethylene glycol methyl isopropyl ether and 13.6%
by weight of tetraethylene glycol monomethyl ether.
1.0 mole of pentaethylene glycol monomethyl ether and 2.28 moles of propylene are reacted, by the method described in Example 1, over 60 g of dry Lewatit CA 9259 HL. The composition of the reaction product is: 5.3% by weight of volatiles, 72.4% by weight of pentaethylene glycol methyl isopropyl ether and 22.3% by weight of pentaethylene glycol monomethyl ether.
O~Z. 31,590 1~25 moles of triethylene glycol monoethyl ether and 2.27 moles of propylene are reacted, by the method described in Example 1, over 40 g of dry Amberlyst 15O The composition of the reaction product is: 4O2% by weight of volatiles, 82~9% by weight of tri-ethylene glycol ethyl isopropyl ether and 12.9% by weight of tri-ethylene glycol monoethyl ether.
1.25 moles of triethylene glycol monoethyl ether and 2.27 moles of propylene are reacted at 120C, by the method described in Example 1, over 40 g of dry Amberlite 200 exchanger (a macro-reticular cation exchanger with sulfonic acid groups, a commercialproduct of R8hm & Haas). The composition of the reaction product is: 4.8% by weight of volatiles, 79.0% by weight of triethylene glycol ethyl isopropyl ether and 16.2% by weight of triethylene glycol monoethyl ether.
1.85 moles of diethylene glycol mono-n-butyl ether and 4.56 moles of propylene are reacted, by the method described in Example 7, over 60 g of dry Lewatit CA 9259 HL exchanger. The composition of the reaction product is: 8.9% by weight of volati-les, 69.2% by weight of diethylene glycol n-butyl isopropyl ether and 21.9% by weight of diethylene glycol mono-n-butyl ether.
A 1 m long stainless steel pressure tube of 26 mm internal diameter and 500 ml capacity is filled with Lewatit CA 9259 HL
which has ~irst been dried by azeotropic distillation, and then been swollen overnight at 100C in a mixture of triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether and penta-ethylene glycol monomethyl etherO 0023 mole/h of a mixture of 32%
by weight of triethylene glycol monomethyl ether, 46% by weight of tetraethylene glycol monomethyl ether, 21% by weight of penta-1~74339 o . z . 31, 590 ethylene glycol monomethyl ether and 1% by weight of hexaethyleneglycol monomethyl ether (the rate being based on the number of moles of monoether per hour) and 0 5 mole/h of propylene under autogenous pressure (12 bars) are passed continuously through this reaction column at 100C. At the outlet, the excess propylene is removed by flash evaporation through a valve. The liquid reac-tion product thus obtained contains 6.5% by weight of volatiles, 86.4% by weight of tri- to hexa-ethylene glycol methyl isopropyl ethers in the ratio of the monomethyl ethers employed, and 7.1%
by weight of tri- to hexa-ethylene glycol monomethyl ethers in the ratio of the mixture employed.
2.5 moles of ethylene glycol and 6.25 moles of propylene are reacted, by the method described in Example 1, for 5 hours over 65 g of dry Lewatit CA 9259 HL. The composition of the reaction product is: 52.3% by weight of ethylene glycol monoisopropyl ether, 1.7% by weight of ethylene glycol diisopropyl ether, 39.0~ by weight of ethylene glycol and 7.0% by weight of dioxane.
Methylpolyglycol (a mixture of triethylene glycol to hepta-ethylene glycol monomethyl ethers) (0.46 mole/h) and propylene (1.3 moles/h) are reacted at 100C/35 bars in a 500 ml fixed bed reactor (or internal diameter 40 mm), which is filled with dried Lewatit SPC 118 H ion exchanger, to give the corresponding methyl isopropyl ethers. The reaction product is examined by gas chroma-tography, and its water content is determined by the Karl-Fischer method. Even small amounts of water in the methylpolyglycol pro-duce a marked reduction in the conversion.
Water content of the methylpolyglycol Conversion L% by weight] [% o~ theory~
0 98.4 2 78.2 21.7 1~74339 O.Z. 31,590 The drying of the catalyst, required in order to achieve high conversions, can be carried out with the reaction mixture under the stated working conditions, as is shown by the experiment which follows.
The ion exchanger is swollen in 500 ml of methylpolyglycol and introduced together with supernatant liquid into the reactor.
The liquid is run off, the reactor is heated to 100C and the pumps are started, which supply appropriate quantities of reactants to the reactor. The reaction product is examined periodically.
The time tmaX at which complete conversion (Cmax) is reached, and the H20 content of the reaction product at the same point of time, are recorded. Volatiles are left out Or account.
The conversion and H20 content of the product are plotted as a function of time. The H20 content of the exchanger is determined before and after the experiment. l Water content of the t C Water content of the exchanger max max product at t [% by weigh~ [h] ~ of theor~ max before after ~ by weigh~
56.6 0.16 16 98.2 0.11 (swollen in H20)
The unconverted olefin is separated off, e.g. by flash evaporation or by distillation, whilst the catalyst is, if required, removed by filtration from the mixture discharged from the reaction, which is liqu;d under normal conditions. This liquid product is worked up, if desired, by distillation under reduced pressure or, in certain cases, by extraction, because in some cases the mono-ether and diether have different solubilities, for example inwater, but very similar boiling points. The glycol alkyl isopropyl ethers in general boil at lower temperatures than the corresponding monoalkyl ethers, and these in turn boil at lower temperatures than the corresponding glycols. In some cases (the isobutyl ethers and isoamyl ethers of certain glycol monoalkyl ethers) the desired end product however boils at a higher temperature than the monoalkyl ether. It the process is carried out continuously, unconverted olefin and glycol monoalkyl ether are recycled.
1074339 o . z . 31, 590 The methyl isopropyl ethers of triethylene glycol, tetra-ethylene glycol and pentaethylene glycol are new and exceptionally suitable for use as extractants. One of their advantages over conventional extractants is that they have a particularly low ViS COSity .
The Examples which follow illustrate the invention. In these Examples, the term "volatiles" is applied globally to all reaction products which have a lower boiling point than the glycol monoalkyl ether employed and the corresponding glycol alkyl i-propyl ether. Compounds which boil at a higher tamperature than the glycol monoalkyl ether employed may be formed in small amounts as by-products. The reaction prod~tis freed from volatiles by, for example, distillation or extraction, and the distillation residue is analyzed by quantitative gas chromatography. The % by weight, based on reaction product, is quoted. The exchanger used is in each case in the acid form and is air-dry at the start of the experiment.
0.37 mole of triethylene glycol monomethyl ether, 1.03 moles of propylene and 26 g of dry Lewatit CA 9259 HL (from Bayer AG), ZO a macro-reticular cation exchanger based on styrene~divinylbenzene and containing sulfonic acid groups, which was dried by azeotropic distillation with benzene, are shaken in a 250 ml stainless steel autoclave for one hour at 100 C under autogenous pressure. At the end of the reaction, the unconverted propylene is removed by flash evaporation and the ion exchanger is filtered off. The composition of the product thus obtained is: 3.9% by weight of volatiles, 85.5%
by weight of triethylene glycol methyl isopropyl ether and 10.6%
by weight of triethylene glycol monomethyl ether.
If the procedure described in Example 1 is followed, using exchanger which has not been (specially) dried (i~e. using air-dry 1~)'74339 o~z. ~1,590 exchanger), the composition of the reaction product is: 5. 8g by weight of volatiles and 94~2% by weight of triethyle~ glycol mono-methyl ether.
0.29 mole of tetraethylene glycol monomethyl ether an 0.76 mole of propylene are reacted, by the method described in Example 1, over 20 g of dry Lewatit CA 9259 HL exchangerO The composition of the reaction product is 3.1% by weight of volatiles, 88.3%
by weight of tetraethylene glycol methyl isopropyl ether and 8.6%
by weight of tetraethylene glycol monomethyl etherO
This is carried out as described in Example 2, but using 20 g of dry Amberlyst 15 exchanger (a macro-reticular cation exchanger containing sulfonic acid groups, a commercial product of Rohm & Haas). The composition of the reaction product is:
2.6% by weight of volatiles, 55.7% by weight of tetraethylene glycol methyl isopropyl ether and 41.7% by weight of tetraethylene glycol monomethyl ether.
0.24 mole of pentaethylene glycol monomethyl ether and 0.63 mole of propylene are reacted, by the method described in Example 1, over 20 g of dry Lewatit CA 9259 HL exchanger. The composition of the reaction product is: 2~3% by weight of volatiles, 46.8%
by weight of pentaethylene glycol methyl isopropyl ether and 50.9% by weight of pentaethylene glycol monomethyl ether.
0.33 mole of triethylene glycol monoethyl ether and 0.76 mole of propylene are reacted, by the method described in Example 1, over 40 g of dry Lewasorb A 10 exchanger (a pulverulent macro-reticular cation exchanger with sulfonic acid groups, a commer-cial product of Bayer AG)o The composition of the reaction pro-duct is: 9~4~ by weight of volatiles, 84.7% by weight of tri-_ g _ 1~74339 O.Z. 31,590 ethylene glycol ethyl isopropyl ether and 5.9% by weight of tri-ethylene glycol monoethyl etherO
0.28 mole of tetraethylene glycol monoethyl ether and 0.76 mole of propylene are reacted, by the method described in Example 1, over 20 g of dry Lewatit CA 9259 HL. The composition of the reaction product is: 605% by weight of volatiles, 89.0% by weight of tetraethylene glycol ethyl isopropyl ether and 4.5% by weight of tetraethylene glycol monoethyl ether.
1.34 moles of triethylene glycol monomethyl ether and 2.28 moles of propylene are reacted, in a 1 liter stainless steel autoclave, over 40 g of dry Lewatit CA 9259 HL, whilst stirring, by the method described in Example 1. The composition of the reaction product is: 5.6% by weight of volatiles, 87. 5% by weight of triethylene glycol methyl isopropyl ether and 6.9% by weight of triethylene glycol monomethyl ether.
1.92 moles of tetraethylene glycol monomethyl ether and 3.04 moles of propylene are reacted, by the method described in Example 1, over 80 g of dry Lewatit CA 9259 HL. The composition of the reaction product is: 3. 7% by weight of volatiles, 82.7%
20 by weight of tetraethylene glycol methyl isopropyl ether and 13.6%
by weight of tetraethylene glycol monomethyl ether.
1.0 mole of pentaethylene glycol monomethyl ether and 2.28 moles of propylene are reacted, by the method described in Example 1, over 60 g of dry Lewatit CA 9259 HL. The composition of the reaction product is: 5.3% by weight of volatiles, 72.4% by weight of pentaethylene glycol methyl isopropyl ether and 22.3% by weight of pentaethylene glycol monomethyl ether.
O~Z. 31,590 1~25 moles of triethylene glycol monoethyl ether and 2.27 moles of propylene are reacted, by the method described in Example 1, over 40 g of dry Amberlyst 15O The composition of the reaction product is: 4O2% by weight of volatiles, 82~9% by weight of tri-ethylene glycol ethyl isopropyl ether and 12.9% by weight of tri-ethylene glycol monoethyl ether.
1.25 moles of triethylene glycol monoethyl ether and 2.27 moles of propylene are reacted at 120C, by the method described in Example 1, over 40 g of dry Amberlite 200 exchanger (a macro-reticular cation exchanger with sulfonic acid groups, a commercialproduct of R8hm & Haas). The composition of the reaction product is: 4.8% by weight of volatiles, 79.0% by weight of triethylene glycol ethyl isopropyl ether and 16.2% by weight of triethylene glycol monoethyl ether.
1.85 moles of diethylene glycol mono-n-butyl ether and 4.56 moles of propylene are reacted, by the method described in Example 7, over 60 g of dry Lewatit CA 9259 HL exchanger. The composition of the reaction product is: 8.9% by weight of volati-les, 69.2% by weight of diethylene glycol n-butyl isopropyl ether and 21.9% by weight of diethylene glycol mono-n-butyl ether.
A 1 m long stainless steel pressure tube of 26 mm internal diameter and 500 ml capacity is filled with Lewatit CA 9259 HL
which has ~irst been dried by azeotropic distillation, and then been swollen overnight at 100C in a mixture of triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether and penta-ethylene glycol monomethyl etherO 0023 mole/h of a mixture of 32%
by weight of triethylene glycol monomethyl ether, 46% by weight of tetraethylene glycol monomethyl ether, 21% by weight of penta-1~74339 o . z . 31, 590 ethylene glycol monomethyl ether and 1% by weight of hexaethyleneglycol monomethyl ether (the rate being based on the number of moles of monoether per hour) and 0 5 mole/h of propylene under autogenous pressure (12 bars) are passed continuously through this reaction column at 100C. At the outlet, the excess propylene is removed by flash evaporation through a valve. The liquid reac-tion product thus obtained contains 6.5% by weight of volatiles, 86.4% by weight of tri- to hexa-ethylene glycol methyl isopropyl ethers in the ratio of the monomethyl ethers employed, and 7.1%
by weight of tri- to hexa-ethylene glycol monomethyl ethers in the ratio of the mixture employed.
2.5 moles of ethylene glycol and 6.25 moles of propylene are reacted, by the method described in Example 1, for 5 hours over 65 g of dry Lewatit CA 9259 HL. The composition of the reaction product is: 52.3% by weight of ethylene glycol monoisopropyl ether, 1.7% by weight of ethylene glycol diisopropyl ether, 39.0~ by weight of ethylene glycol and 7.0% by weight of dioxane.
Methylpolyglycol (a mixture of triethylene glycol to hepta-ethylene glycol monomethyl ethers) (0.46 mole/h) and propylene (1.3 moles/h) are reacted at 100C/35 bars in a 500 ml fixed bed reactor (or internal diameter 40 mm), which is filled with dried Lewatit SPC 118 H ion exchanger, to give the corresponding methyl isopropyl ethers. The reaction product is examined by gas chroma-tography, and its water content is determined by the Karl-Fischer method. Even small amounts of water in the methylpolyglycol pro-duce a marked reduction in the conversion.
Water content of the methylpolyglycol Conversion L% by weight] [% o~ theory~
0 98.4 2 78.2 21.7 1~74339 O.Z. 31,590 The drying of the catalyst, required in order to achieve high conversions, can be carried out with the reaction mixture under the stated working conditions, as is shown by the experiment which follows.
The ion exchanger is swollen in 500 ml of methylpolyglycol and introduced together with supernatant liquid into the reactor.
The liquid is run off, the reactor is heated to 100C and the pumps are started, which supply appropriate quantities of reactants to the reactor. The reaction product is examined periodically.
The time tmaX at which complete conversion (Cmax) is reached, and the H20 content of the reaction product at the same point of time, are recorded. Volatiles are left out Or account.
The conversion and H20 content of the product are plotted as a function of time. The H20 content of the exchanger is determined before and after the experiment. l Water content of the t C Water content of the exchanger max max product at t [% by weigh~ [h] ~ of theor~ max before after ~ by weigh~
56.6 0.16 16 98.2 0.11 (swollen in H20)
4.8 - 8 98.6 (expelled with cyclohexane) The wet catalyst (as received, containing 56.6% by weight of H20) is dried completely by the reaction mixture. The conver-sion is inversely proportional to the H20 content of the exchanger (represented, in the present case, by the H20 content of the reaction product). The catalyst is dry (~0.2% by weight of H20) 1~)74339 O.Z. 31,590 after 16 hours and at the same time the conversion reaches its maximum (98.2% of theory)~
If a substantially dry (4.8% by weight H20) catalyst - from which the water has been expelled with cyclohexane - is employed, tmaX is reduced by 50% and becomes of the order of magnitude of the conventional start-up effect.
Drying under atmospheric pressure, with methylpolyglycol alone, under otherwise identical conditions, is less effective. After 15 hours, the reaction product and catalyst still respectively con-tain 1.0% by weight and 2.4% by weight of water.
A good drying effect is achieved by treating the catalyst (5.0 g, 57% by weight of H20) with warm air (100C, 100 liters (S.T.P.)/h, 6 h, 1.6% by weight of H20). Conversions of more than 98% of theory are also achieved with air-dry exchanger.
If a substantially dry (4.8% by weight H20) catalyst - from which the water has been expelled with cyclohexane - is employed, tmaX is reduced by 50% and becomes of the order of magnitude of the conventional start-up effect.
Drying under atmospheric pressure, with methylpolyglycol alone, under otherwise identical conditions, is less effective. After 15 hours, the reaction product and catalyst still respectively con-tain 1.0% by weight and 2.4% by weight of water.
A good drying effect is achieved by treating the catalyst (5.0 g, 57% by weight of H20) with warm air (100C, 100 liters (S.T.P.)/h, 6 h, 1.6% by weight of H20). Conversions of more than 98% of theory are also achieved with air-dry exchanger.
Claims
1. The methyl isopropyl ethers of triethylene glycol, tetraethylene glycol and/or pentaethylene glycol.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19752544569 DE2544569C3 (en) | 1975-10-04 | 1975-10-04 | Methyl isopropyl ether of tri-, tetra- and / or pentaethylene glycol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1074339A true CA1074339A (en) | 1980-03-25 |
Family
ID=5958378
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA262,438A Expired CA1074339A (en) | 1975-10-04 | 1976-09-30 | Manufacture of alkyl ethers or ethylene glycols |
Country Status (5)
| Country | Link |
|---|---|
| BE (1) | BE846663A (en) |
| CA (1) | CA1074339A (en) |
| DE (1) | DE2544569C3 (en) |
| FR (1) | FR2326402A1 (en) |
| NL (1) | NL7610699A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2611613B2 (en) * | 1976-03-19 | 1979-04-26 | Basf Ag, 6700 Ludwigshafen | Process for the separation of CO2 and / or H25 from gases containing these components |
| US4330305A (en) * | 1976-03-19 | 1982-05-18 | Basf Aktiengesellschaft | Removal of CO2 and/or H2 S from gases |
| DE2801793B1 (en) * | 1978-01-17 | 1979-06-07 | Basf Ag | Process for the production of dialkyl ethers of mono- and polyethylene glycols |
| DE2923012A1 (en) * | 1979-06-07 | 1980-12-18 | Basf Ag | METHOD FOR THE SIMULTANEOUS REMOVAL OF WATER AND SULFURIUM FROM GASES |
| US4282386A (en) | 1980-05-02 | 1981-08-04 | The Dow Chemical Company | Alkyl, cycloalkyl diethers of (poly)alkylene glycols |
| RU2470006C1 (en) * | 2011-09-23 | 2012-12-20 | Открытое акционерное общество "ЭКТОС-Волга" | Method of producing dialkyl esters of ethylene glycol |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1354325A (en) * | 1962-02-06 | 1964-03-06 | Rohm & Haas | Olefin-terminated alkylphenoxypolyethanols |
| DE2028423C3 (en) * | 1970-06-10 | 1979-06-07 | Allied Chemical Corp., New York, N.Y. (V.St.A.) | Process for the preparation of dialkyl ethers of polyalkylene glycols |
-
1975
- 1975-10-04 DE DE19752544569 patent/DE2544569C3/en not_active Expired
-
1976
- 1976-09-27 NL NL7610699A patent/NL7610699A/en not_active Application Discontinuation
- 1976-09-28 BE BE171005A patent/BE846663A/en not_active IP Right Cessation
- 1976-09-30 FR FR7629345A patent/FR2326402A1/en active Granted
- 1976-09-30 CA CA262,438A patent/CA1074339A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2544569A1 (en) | 1977-04-07 |
| DE2544569C3 (en) | 1984-06-07 |
| FR2326402A1 (en) | 1977-04-29 |
| NL7610699A (en) | 1977-04-06 |
| DE2544569B2 (en) | 1977-12-22 |
| BE846663A (en) | 1977-03-28 |
| FR2326402B1 (en) | 1981-03-27 |
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