GB1566770A - Etherification of polyocyalkylene compounds - Google Patents

Description

(54) ETHERIFICATION OF POLYOXYALKYLENE COMPOUNDS (71) We, KURARAY CO. LTD., a body corporate organized and existing under the laws of Japan, of 1621, Sakazu, Kura shiki city, Japan, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to the preparation of etherified polyoxyalkylene derivatives.

Ethedfication of a polyoxyalkylene compound having at least one terminal hydroxyl group has hitherto generally ben effected by first reacting the polyoxyalkylene compound with an alkali metal or its hydride or alcoholate, such as sodium metal, potassium metal, sodium hydride or sodium methylate, and then reacting the resultant alcoholate with an organic halide. This method enables one to produce various etherified polyoxyalkylene derivatives, but the expensive alkali metal or its hydride or alcoholate is consumed stoichiometrically, and the yield of the desired product is at most 60%.

It is also known that ethers of polyoxyalkylene glycol can be prepared by reacting polyoxyalkylene glycol with an organic halide in the presence of a finely powdered alkali meal hydroxide at an elevated temperature, but this method cannot be carried out con tenuously and usually requires a higher tem- perature exceeding 1000C to facilitate the reaction.

As a very special case, It is also known that polyoxyalkylene glycol diallyl ether can be produced by reacting polyoxyalkylene glycol with an allyl halide (well known as a highly reactive organic halide) even in the presence of an aqueous solution of alkali metal hydroxide. In this case, a part of the allyl halide is hydrolysed and the yield of diallyl ether of polyoxyalkylene glycol is low.

It is also known that a polyoxyalkylene glycol dialkyl ether can be produced by reacting an aliphatic alcohol or mono-, di- or tri-oxyalkylene glycol monoalkyl ether with a ,ss,ss-dihalogenodialkyl ether in the presence of an aqueous solution of over 20 wt.% concentration of alkali metal hydroxide (German Patent No. 1,129,147). According to the specifications of the German Patent No.

1,129,147, although the methods affords the desired product, i.e. hexa- or octa-alkylene glycol diether, the yield is fairly low (about 58%), and a byproduct, i.e. tetra- or pentaalkylene glycol alkyl vinyl ether, is formed in 3040% yield. Since polyoxyalkylene glycol diethers have a higher boiling point, it is virtually impossible to separate the desired product exclusively from the reaction mixture containing the desired product and high-boiling products.

In addition to the methods described above, the following methods for the etherification of polyoxyalkylene compounds having at least one terminal hydroxyl group are known: (i) converting the terminal hydroxyl group of the polyoxyalkylene compound into chlorine atom by reacting with thionyl chloride, followed by reaction of the resultant chlorinated polyoxyalkylene compound with a metal alkoxide; (ii) converting the terminal hydroxyl group of the polyoxyalkylene compound into tosylate by reacting with a tosyl halide, i.e. p-toluene sulfonyl halide, and then reacting the tosylate with an alkyl halide; (iii) etherification by a dialkyl sulfate; and '(it) methyl etherification by formaldehyde. The methods (i) and (ii) are disadvantageous since they require two-stage reactions. Moreover, the raw materials used in these methods, i.e. thionyl chloride, metal alkoxides and tosyl halides, are too expensive to be quantitatively consumed. Dialkyl sulfate used in method (iii) is expensive and practically limited only to dimethyl sulfate which is extremely harmful to people's health. Method (iv) is applicable only to methyl etherification.

According to the present invention there is provided a method of preparing an etherified polyoxyalkylene derivative having the general formula

in which each of m and n, which are the same or different, is 0 or a positive mteger and m + n > 4; Q is a radical of formula OCH2R, COR1, N--(CH2R)RS, -N(CH2R)COR2, -NR2RS, --.N(RS)COR2,

or -N(COR2) [(CH2CH2O),

R is a hydrogen atom or a group of formula CR4R5R6; each of R1, R2 and R, which are the same or different, is a hydrocarbon group or a substituted hydrocarbon group having substituents that do not affect the reaction; each of R4, R5 and R', which are the same or different, is a hydrogen atom or a hydrocarbon group; and each of p and q is 0 or a positive integer and p + q > 0, that comprises reacting a polyoxyalkylene compound having the general formula

in which Q' is as previously defined for Q or a radical of formula -OH, -NHR', -NHCOR2,

where m, n, R2, p and q are as previously defined, with an organic halide having the general formula R-CH2-X (III) where X is chlorine or oromine atom and R is as previously defined, in the presence of an aqueous solution of sodium or potassium hydroxide having an initial alkali metal hydroxide concentration of at least 30% by weight, the molar ratio of the organic halide to the hydroxyl group of the polyoxyalkylene compound being at least 1.2:1 and the molar ratio of the alkali metal hydroxide to the hydroxyl group of the polyoxyalkylene compound being at least 1:1.

It has been found that polyoxyalkylene compounds of the formula (II) can be etherified easily and almost quantitatively by reaction with an organic halide of the formula (III) under mild reaction conditions by the method of the present invention. It is well known that the replacement reaction between an alcohol and an organic halide never or hardly proceeds in the presence of an aqueous solution of alkali metal hydroxide except when highly reactive halides such as allylic halides are used. It was therefore surprising to find that the reaction of the polyoxyalkylene compound and the organic halide can proceed smoothly even in the presence of an aqueous solution of alkali metal hydroxide.

It is partfcularly important for the polyoxyalkylene compound used as starting material to have at least four and preferably at least six oxyalkylene units so that the reaction may proceed smoothly, since using such compounds enables activation of hydroxide anion to occur characteristically, and consequently the etherified product may be obtained almost quantitatively at an ex tremely high reaction rate. When polyoxyalkylene compounds having three or fewer oxyalkylene units are used, the hydroxide anion may be only slightly activated, the reaction is generally too slow, and many undesirable side reactions may occur.

The process of the present invention, as disclosed in the specific Examples later in the specification, possesses the following advantages over the known methods: , I) A wide range of desired terminally etherified polyoxyalkylene derivatives can be produced by using an aqueous solution of sodium or potassium hydroxide, which is inexpensive and easy to handle, and a variety of common, easily available and less reactive organic halides.

(II) Quantitative etherification can be performed in a reaction involving only one stage.

III) Separation and purification of the product are extremely easy.

IV) Symmetrical or unsymmetrical etherified polyoxyalkylene derivatives of high purity can be obtained by varying the combination of the raw materials, the polyoxyalkylene compound (II) and the organic halide (III).

The polyalkylene compounds (II) used in the present invention include compounds of the following types:

In the above formulae, R', R2, R, m, n, p and q have the meanings as defined hereinbefore: m and n may take values such that 4 # (m + n) # 40, preferably 6 # (m + n) # 25 and p and q amke take values such that m + n + p + 1 # about 40, preferably m + n + p + q # about 25. In polyoxyalkylene compounds having oxyethylene and oxypropylene units in the same molecule, the order of the oxyalkylene units is insignifi cant. They can be in a random or block form.

The number of carbon atoms in the hydro carbon group, represented by Rl, R2 and RS. can range from 1 to 20. Examples of hydro carbon groups suitable for R, R and R are saturated aliphatic hydrocarbon groups, such as methyl, ethyl, n-propyl, iso-propyl, nbutyl, n-amyl, isoamyl, n-hexyl, 2-methylpentyl, 2-ethylbutyl, n-heptyl, 2-methylhexyl, 2-ethylpentyl, 2,4-dimethylpentyl, noctyl, 2-ethylhexyl, nonyl, 3-methyl-S-ethylhexyl, 3,5,5 - trimethylhexyl, 2 - ethyl - 4,4 dimethylpentyl, n-decyl, 2,6-dimethyloctyl, 2,4,6 - trimethyheptyl, undeceyl, n - dodecyl, 3,5,5,7,7 - pentamethyloctyl, 4,6,8 - trimethylnonyl, cetyl and stearyl; unsaturated aliphatic hydrocarbon groups, such as allyl, pentenyl, decenyl and oleyl; cycloaliphatic hydrocarbon groups, such as cyclohexyl, methylcyclohexyl and ethylcyclohexyl; substituted and unsubstituted phenyl groups, such as phenyl, butylphenyl, nonylphenyl, decylphenyl, undecylphenyl and dodecyl phenyl; and substituted and unsubstituted benzyl groups, such as benzyl, methylbenzyl and nonylbenzyl. The hydrocarbon residues of synthetic alcohols obtained by the Ziegler process, the oxo process or the paraffin oxida tion process are included in the examples of suitable values of R1, R2 and Rt. These hydrocarbon groups can have substituents that do not affect the reaction of the polyoxyalkylene compound with the organic halide. It is preferred that the total number of carbon atoms in R2 and R3 be 25 or less in the polyoxyalkylene compounds of the types (IIe) and (Il-f). The polyoxyalkylene compound (II) used in the present invention can be generally obtained by the (co)polymerization of ethylene oxide and/or propylene oxide or by the (co)polyaddition of ethylene oxide and/or propylene oxide to the corresponding alcohol, amine or amide. Most of the polyoxyalkylene compounds (tri) are produced commercially.

From the viewpoint of usefulness of the product, the preferred polyoxyalkylene compound to be used as a starting material is a polyoxyethylene compound of any of the foregoing types, but especially of type (II--a) or (Il b) having from 4 to 20 (particularly 6 to 13) oxyethylene units.

When R in the general formula R-CH2-X in the group -CR4R5R6, R4, R5 and R6 are independently hydrogen or hydrocarbon and the hydrocarbon group can be, for example, an alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkaryl group. The total number of carbon atoms in R4, R5 and R6 taken together is preferably in the range 0 to 20 and it is particularly preferred that two of R4, R6 and Rz are hydrogen atoms or C14 alkyl. Preferable examples of the organic halide (III) include saturated Cl~1s aliphatic chlorides and bromides, such as methyl chloride, methyl bromide, ethyl bromide, n-propyl chloride, npropyl bromide, butyl chloride, butyl bromide, isoamyl chloride, isoamyl bromide, hexyl chloride, hexyl bromide, octyl chloride, octyl bromide, decyl chloride, decyl bromide, lauryl chloride, lauryl bromide, myristyl chloride, myristyl bromide, cetyl chloride, cetyl bromide, stearyl chloride and stearyl bromide; unsaturated aliphatic chlorides and bromides (except for allylic chlorides and bromides), such as 9-decenyl chloride, 9-decenyl bromide, 9-dodecenyl chloride, 9-dodecenyl bromide, oleyl chloride, oleyl bromide, 9,12-octadecadienyl chloride and 9,12-octadecadienyl bromide; 2-cyclohexylethyl chloride, 2-cyclo hexylethyl bromide, 2-phenylethyl chloride and 2-phenyl bromide. A variety of alkyl bromides and alkyl chlorides derived from synthetic alcohols produced by the Ziegler process, the oxo process or the paraffin oxidation process are included m the preferable examples of the organic halide (III). The preferred organic halides are saturated C,-1, aliphatic primary chlorides and bromides.

When performing the present invention, at least 1.2 and preferably from 2 to 5 moles of the organic halide (III) is used per mole of the hydroxyl group or groups of the polyoxyalkylene compound (II). It is usually desirable to complete the etherification of the polyoxyalkylene compound (II) by using a large excess of the organic halide (III) as a solvent.

In the process of the present invention, sodium hydroxide or potassium hydroxide (both could be used together) is used in the form of an aqueous solution having an initial alkali metal hydroxide concentration of at least 30% by weight, preferably from 40 to 75% by weight. When the initial concentration of alkali metal hydroxide is lower than 30% by weight in its aqueous solution, the reaction rate becomes much slower and it becomes difficult to separate the product from the reaction mixture. In this specification, the initial concentration of alkali metal hydroxide in its aqueous solution means the degree of its concentration upon the start of the reaction or upon the use of the said aqueous solution.

The molar ratio of alkali metal hydroxide to hydroxyl group of the polyoxyalkylene compound (II) is at least 1:1 and is preferably in the range of from 1.5:1 to 5:1. As the reaction proceeds, the alkali metal hydroxide is consumed. Although it is possible to supply an additional amount of alkali metal hydroxide during the reaction, this is usually unnecessary except when the alkali metal hydroxide is supplied together with the polyoxyalkylene compound (II) and the organic halide (III).

The reaction of the present invention is conveniently carried out by agitating a heterogeneous mixture consisting essentially of the polyoxyalkylene compound (II), the organic halide (III) and the aqueous solution of alkali metal hydroxide. With a view to facilitating the separation of product from the reaction mixture, the reaction may be carried out in the presence of an organic solvent that is chemically stable in the reaction system but is not freely soluble in water. Examples of suitable solvents include hydrocarbons such as hexane, heptane, octane, cyclohexane, benzene, toluene and xylene, substituted benzenes such as chlorobenzenes and benzonitrile; and ethers such as dibutyl ether and anisole. There is no special limitation to the amount of the organic solvent that may be used. From the viewpoint of the reaction efficiency and economy, however, it is desirable to set the volume ratio between the aqueous phase and the organic phase in the reaction system within a range of from 5:1 to 1:10. The reaction temperature generally ranges from 200C to 150"C, preferably from 50"C to 1200 C. The optimum reaction temperature varies depending on the type of the raw materials, particularly of the organic halide (III). In a preferred embodiment of the present invention, the reaction is carried out at the boiling point of the organic halide and/or solvent in order to remove the reaction heat by refiuxing them. The etherification reaction is usually performed under atmospheric pressure. When an organic halide having a very low boiling point, e.g. methyl bromide or ethyl chloride, is used, it is desirable to carry out the reaction under an increased pressure from the viewpoint of the reaction rate. The etherification reaction according to the present invention is carried out preferably under nitrogen gas atmosphere or other inert gas atmosphere so that the colouring of the product can be minimized.

Even when the reaction is performed under an inert gas atmosphere, a coloured product is occasionally formed. In such a case, the colouring of the product can be reduced or virtually eliminated by hydrogenation. This hydrogenation treatment is usually performed by subjecting the etherified product to contact with molecular hydrogen (H2) for several hours, not exceeding say 20 hours, in the presence of from 0.1 to 10% by weight (based on the weight of the etherified polyoxyalkylene derivative) of a hydrogenation catalyst such as Raney nickel, nickel on diatomaceous earth, palladium black, palladium on carbon, palladium on silica, platinum black or a supported platinum catalyst, preferably but not necessarily in the presence of a substantially inert solvent, for example, water; an alcohol, such as methanol, ethanol, propanol or butanol; an ether, such as tetrahydrofuran, dioxane or diethyl glycol dimethyl ether; or a hydrocarbon, such as hexane, heptane, octane, cyclohexane, benzene, toluene or xylenc, at a temperature ranging from room temperature to 2G0 C, preferably at 500C to 1500 C, under hydrogen pressure of from 1 to 200 atmospheres, preferably 1 to 100 atmospheres.

It has been found that a slightly coloured or virtually colourless product can be obtained when the starting polyoxyalkylene compound (II) is pre-treated with hydrogen under the same conditions as mentioned above in the presence of the hydrogenation catalyst, or the etherification reaction is carried out in the presence of an inorganic reductant. Examples of suitable inorganic reductants are sodium sulfide, potassium sulfide, sodium sulfite, potassium sulfite, sodium polysulfide, ammonium sulfide, sodium thiosulfate, sodium hypochlorite, phosphorus trisulfide, sodium phosphite, sodium pyrosuffite, potassium pyro sulfite, sodium formate, potassium formate, hydrazine hydrate, hydrogen sulfide, stannous chloride, ferrous sulfate, ferrous hydroxide, cuprous hydroxide, sodium nitrite and potassium nitrite. The optimum amount of the inorganic reductant is generally from 0.05 to 10% by weight based on the weight of the polyoxyalkylene compound (II).

The reaction between the polyoxyalkylene compound (II) and the organic halide (III) can be carried out either in batchwise or continuous manner. The resulting product can be recovered from the reaction mixture by conventional separation methods. For example, when the etherified polyoxyalkylene derivatives are less soluble in water, they can be isolated as a residue by separating the reaction mixture into an aqueous layer and an organic layer, adding a solvent insoluble in water to the organic layer wherever necessary, completely washing the organic layer with water, and then removing the solvent, unreacted organic halide and low-boiling byproducts from the organic layer. When the etherified polyoxyalkylene derivatives are relatively soluble in water, they can be isolated bv ,aeurralie:ing the reaction mixture with an acid, evaporating water from the mixture, removing precipitated inorganic salts from the mixture by filtration at an elevated tempera ture, and evaporating the remaining lowerboiling compounds from the filtrate, if necessary. In this case, the organic solvent and the unreacted organic halide contained in the reaction mixture can be removed simul taneously with or prior to the removal of water or after the filtration, according to their respective physical properties.

The etherified polyoxyalkylene derivatives produced by the process of the present invention are chemical compounds shown in the foregoing general formula (I): formulae (I-a) to (I-h) below correspond to the foregoing polvoxyalkylene starting materials (Il-a) to (lI-h).

When the polyoxyalkylene compound (II) of the type (lI-c) or (II--d) is used, the etherified product of the following type of (I-c') or (Id'), respectively, may be formed occasionally together with or in place of the etherified product of the type (I-r:) or (Id), respectively.

In the above formulae, R, Rl, R2, Rs, m, n, p and q are as defined above.

Depending on the type of their terminal groups, the etherified polyoxyalkylene derivatives produced by the process of the present invention are useful, for example, as surfaceactive agents, solvents, solubilizing agents for inorganic salts, and accelerators or catalysts for ionic organic reactions.

The following are Examples intended to facilitate the understanding of the present invention.

EXAMPLE 1.

In a l-litre four-necked round-bottomed flask, equipped with a thermometer, a reflux condenser and a mechanical stirrer, were placed 97 g of tetraethylene glycol, HO(C2H4O)4H, 411 g of n-butyl bromide, 1 g of sodium thiosulfate and 240 g of 50 wt.% aqueous sodium hydroxide solution. The mixture was vigorously stirred at 90"C for 5 hours under a nitrogen atmosphere. After completion of the reaction, the mixture was cooled to room temperature. The mixture was separated into organic and aqueous layers by using a separatory funnel. The organic layer was distilled under reduced pressure to recover part of nbutyl bromide (approx. 200 g). After distillation, 500 ml of n-hexane was added to the organic layer. The organic layer was then washed twice with 300-ml portions of water and dried over anhydrous sodium sulfate. The solid material was removed from the organic layer by filtration. The organic layer was then subjected to distillation to remove n-hexane, n-butyl bromide and lower-boiling substances and to obtain 151 g of colourless liquid as a residue. Gas chromatographic analysis showed that the colourless liquid consisted substantially of tetraethylene glycol di-n-butyl ether and contained neither tetraethylene glycol nor tetraethylene glycol mono-n-butyl ether.

Yield of the tetraethylene glycol di-n-butyl ether based on the tetraethylene glycol charged: 99%.

Yield of.the tetraethylene glycol di-n-butyl ether based on the n-butyl bromide reacted: 95%.

Transmittance at wave length of 450 nm (cell width; 1 cm): 99%.

By-products were 4% of n-butene and 1% of di-n-butyl ether (both based on the reacted n-butyl bromide).

EXAMPLE 2.

In the same flask as in Example 1 were placed 300 ml of benzene, 100 g of polyethylene glycol (average molecular weight; 400), 300 g of 2-ethylhexyl bromide, 5 g of sodium sulfite and 130 g of 60 wt.% aqueous sodium hydroxide solution. The mixture was refluxed for 9 hours under a nitrogen atmosphere with vigorous stirring. After the reaction, the reaction mixture was treated in the same manner as in Example 1 to obtain 151 g of colourless liquid as a residue. Neither polyethylene glycol nor polyethylene glycol mono-2-ethylhexyl ether was detected in gaschromatographic analysis of the colourless liquid. Part of the polyethylene glycol di-2ethylhexyl ether obtained was made into 20% benzene solution whose light transmittance was measured in a 10-cm-wide ceI1 at wave length of 450 nm to be 98%.

Yield of the polyethylene glycol diether based on the polyethylene glycol charged: 97%.

Yield of the polyethylene glycol diether based on the 2-ethylhexyl bromide reacted: 96%.

EXAMPLE 3.

In the same flask as in Example 1 were placed 175 g of polyethylene glycol mono-2ethylhexyl ether (average molecular weight 350), 250 g of 3,5,5-trimethylhexyl chloride, 120 g of 60 wt.% aqueous sodium hydroxide solution and 1 g of sodium nitrite. The mixture was vigorously stirred at 100"C for 10 hours under a nitrogen atmosphere. After completion of the reaction, the reaction mixture was treated in the same manner as in Example 1 to obtain 210 g of polyethylene glycol 2-ethylhexyl 3,S,5-trimethyihexyl ether (average molecular weight 476, yield based on the polyethylene glycol mono-2-ethylhexyl ether charged 90%).

EXAMPLE 4.

In the same flask as in Example 1 were placed 200 ml of monochlorobenzene, 240 g of CH1-CH4-O ( C2R0) CH, 240 g of n-hexyl chloride and 280 g of 50 wt.% aqueous potassium hydroxide solution and the mixture was vigorously stirred at 100"C for 15 hours under a nitrogen atmosphere. After completion of the reaction, the reaction mixture was treated in the same manner as in Example 1 to obtain 280 g of pale-yellow liquid as a residue. To 2.0 g of the residue was added 10 ml of 10 wit.% trimethyl aluminum benzene solution. The amount of methane evolved was 0.2 millimole. This result, together with gas chromatographic analysis, indicated that the reaction mixture contained 264 g of p-C,H,.,-C,H,-o(C,H,0) ,C,H,,.

The transmittance was measured in the same manner as in Example 2 to be 80%.

COMPARATIVE EXAMPLE 1.

In the same flask as in Example 1 were placed 200 ml of benzene, 50 g of diethylene glycol, 340 g of n-butyl bromide and 200 g of 50 wt.% aqueous potassium hydroxide solution, and the mixture was refluxed for 15 hours under a nitrogen atmosphere with vigorous stirring. After completion of the reaction, the reaction mixture was extracted with n-butanol. Analysis of the n-butanol layer by means of gas chromatography showed that the yield of diethylene glycol di-n-butyl ether produced was only 15% and the yield of diethylene glycol mono-n-butyl ether was 38% (both yields based on the diethylene glycol charged).

EXAMPLE 5.

In a 500-ml autoclave were placed 100 g of commercial polyethylene glycol (average molecular weight; 300), 100 g of water and 3 g of nickel-on-diatomaceous-earth catalyst (nickel content 50 wt.%). The mixture was fiydrogenated at 100"C for 2 hours under a hydrogen pressure of 50 atm with vigorous stirring. One hundred grams (100 g) of the hydrogenated polyethylene glycol was placed in the same flask as in Example 1, and 160 g of 50 wt.% aqueous sodium hydroxide solution and 380 g of n-octyl bromide were added.

The mixture was vigorously stirred at 900C under a nitrogen atmosphere for 5 hours.

After the reaction, the reaction mixture was treated in the same manner as in Example 1 to obtain 175 g of polyethylene glycol din-octyl ether as a residue. In gas chromographic analysis of the residue, neither polyethylene glycol nor polyethylene glycol monon-octyl ether was detected. The transmittance of the product, measured in the same manner as in Example 2, was 99.5%.

EXAMPLE 6.

Example 5 was repeated except that polyethylene glycol (average molecular weight 300) in the same lot as used in Example 5 was not hydrogenated. As a result, 173 g of polyethylene glycol di-n-octyl ether was obtained. The transmittance of the product measured in the same manner as in Example 2 was 59%.

In a I-litre autoclave were placed 100 g of the above crude polyethylene glycol di-noctyl ether, 600 ml of ethanol and 3 g of nickel-on-diatomaceous-earth catalyst (nickel content SOX ) and the mixture was hydrogenated at 1000C under a hydrogen pressure of 50 atm with vigorous stirring for 3 hours.

After completion of the reaction the catalyst was removed from the reaction mixture by filtration and then ethanol was distilled off to obtain 99 g of colourless polyethylene glycol di-n-octyl ether as a residue. Light transmittance of the product was also measured in the same manner as in Example 5 to be 98%.

COMPARATIVE EXAMPLE 2.

In the same flask as in Example 1 were placed 300 ml of benzene, 70 g of polyethylene glycol, HO (C2H4O) h.cH (average molecular weight 300), 300 g of 15 wt. /ó aqueous sodium hydroxide solution and 170 g of n-butyl bromide, and the mixture was refluxed for 9 hours under a nitrogen atmosphere with vigorous stirring. After

as a residue. Analysis by means of gel permeation chromatography showed that the average molecular weight of the residue was 850, while no bromine was detected in the elementary analysis of the residue.

EXAMPLE 9.

In the same flask as in Example 1 were placed 100 ml of dibutyl ether, 100 g of nbutyl bromide, 2 g of potassium thiosulfate, 75 g of 10 wt.% aqueous potassium hydroxide solution and 120 g of

(average number of oxyethylene units 20), and the mixture was reacted at 800C under a nitrogen atmosphere for 10 hours with rapid stirring. After completion of the reaction, the reaction mixture was separated into organic and aqueous layers. 200 ml of n-butanol was added to the organic layer, which was then washed twice with 300 ml of water. The organic layer was treated in the same manner as in Example 1 to obtain 128 g of

as a residue. The average molecular weight of the product was confirmed by means of gel permeation chromatography to be 1,275 and the absorption at 1650 cm-1 was observed in its infrared spectrum.

EXAMPLES 10--22.

The etherification reaction of various polyoxyalkylene compounds with various organic halides under varying conditions produced the corresponding etherified polyoxyalkylene derivatives. The reaction in Examples 17 and 22 was carried out by using a litre autoclave, while the reaction in Examples 10~16 and 18-21 was performed by using the same flask as in Example 1. The results are summarized in Table 1.

TABLE 1

Alkali metal Starting material hydroxide Yield based on aqueous Polypxyalkylene Reducing polyoxyalkylene solution Example compound Halide Solvent agent Conditions compound charged 10 CH3O(C2H4O)6.5H n-C8H17Br 30% NaOH - - 80 C, 15hrs 92% CH3O(C2H4O)6.5n-C8H17 (100 g) (250 g) (170 g) 11 CH3O(C2H4O)6.5H n-C8H17Br 70% NaOH - - 80 C, 4hrs 99% CH3O(C2H4O)6.5n-C8H17 (100 g) (250 g) (73 g) 12 CH3O(C2H4O)6.5H n-C8H17Br 50% NaOH - - 80 C, 6hrs 99% CH3O(C2H4O)6.5n-C8H17 (100 g) (250 g) (102 g) 13 CH3O(C2H4O)6.5H n-C8H17Br 50% KOH - - 80 C, 6hrs 99% CH3O(C2H4O)6.5n-C8H17 (100g) (250g) (143g) 14 CH3O(C2H4O)6.5H n-C8H17Br 50% NaOH - - 80 C, 8hrs 72% CH3O(C2H4O)6.5n-C8H17 (100g) (61g) (102g) 15 CH3O(C2H4O)6.5H n-C8H17Br 50% NaOH - - 80 C, 8hrs 98% CH3O(C2H4O)6.5n-C8H17 (100g) (130g) (102g) 16 HO(C2H4O)8.7H n-C18H37Br 60% KOH C6H5 Cl FeSO4.5H2O 90 C, 6hrs 99% n-C18H37O(C2H4O)8.7n-C18H37 (80g) (400g) (150g) (200ml) (0.5g) 17 HO(C2H4O)8.7H C2H5Cl 60% KOH - KNO2 90 C, 10hrs 92% C2H5O(C2H4O)8.7C2H5 (100g) (130g) (230g) (0.5g) CH3 18 HO(C2H4O)m(CHCH2O)nH n-C18H35Br 50% NaOH C6H5 OCH3 Na2SO3 90 C, 7hrs 99% n-C18H35O(C2H4O)m (Mw=1650, m/n=40/60) (100g) (40g) (100ml) (1g) CH3 (80g) -(CHCH2O)nn-C18H35 TABLE 1 (continued)

e m material Alkali mental gQ E U~Z i YieldQ O X X o 3 N o aqueous Reducing polyoxyalkyl U Z U Z Example Halide solution Solvent agent Conditions u ~ D n-C4HO(C2H4O)m 19 CH3 iso- " oo > s (40g) (lOOmI) m m d -E FI rd F.

(Mw 1400 m/n=40/60) (CHCH20)ni so-C5 " (lOg) V C6H5O(C2H4O)15H C6H11CH2Br 60% NaOH - KH2P032H20 800C, 6hrs 99% C6Hò(c,H4o)15CH2C6H11 (iSOg) rz (130g) (1.5g) O C12H2NH(C2H4O)5H n-C4H9Cl H N C6H Na2SO3 800C, i4hrs N C4H ;e nor (140g) (lOOml) (1.5g) To N(C2H4O)5 n-C4H 22 Cisll,7NH(C2H4O)ioH CH3Br Z NaOH (C4H9)20 Z = ~ w Ê Z Ê = E n = 1M o o 3 =s, ~ > ) o o o o o < = e 6n U) Y X ~ 9 jo U o v < z É O g ô t = > CL 8 c I 2 v U V O 2 O > m H l

Claims (12)

WHAT WE CLAIM IS:1. A method of preparing an etherified polyoxyalkylene derivative having the general formula in which each of m and n, which are the same or different, is 0 or a positive integer and m + n # 4 the order of units when neither m or n is 0 being immaterial and being random or block; Q is a radical of formula -OCH2R, -OR, -N(CH2R)R, -N(CH2R)COR, -NRR , -N(R8)COR, CH8 -N(R)[(CH2CH2O)v(CHCH2O)qCH2R] or (CORP) F(CH2CH2O)n R is hydrogen atom or a group of formula -CR4R5R6; each of R, R and R8 which are the same or different, is a hydrocarbon group or a hydrocarbon group having substituents that do not affect the reaction defined hereinafter; each of R4, Rfi and R6, which are the same or different, is a hydrogen atom or a hydrocarbon group; and each of p and q is O or a positive integer and p + q > O, that comprises reacting a polyoxyalkylene compound having the general formula in which Q' is as previously defined for Q or a radical of formula --OH, --NHRP, -NHCORP, where m, n, R2, p and q are as previously defined, with an organic halide having the general formula R-CH2-X (III) where X is chlorine or bromine atom and R is previously defined, in the presence of an aqueous solution of sodium or potassium hydroxide having an initial alkali metal hydroxide concentration of at least 30% by weight, the molar ratio of the organic halide to the hydroxyl group or groups of the polyoxyalkylene compound being at least 1.2:

1 and the molar ratio of the alkali metal hydroxide to the hydroxyl group or groups of the polyoxyalkylene compound being at least 1:1.

2. A method as claimed in claim 1 in which the polyoxyalkylene compound of formula (II) is a polyoxyethylene compound having from 4 to 20 oxyethylene units and the organic halide of formula (III) is a saturated aliphatic chloride or bromide having from 5 to 18 carbon atoms.

3. A method as claimed in claim 2 in which the polyoxyethylene compound is polyoxyethylene glycol.

4. A method as claimed in claim 2 in which the polyoxyethylene compound is a polyoxyethylene glycol monoether.

5. A method as claimed in any preceding claim in which the reaction is carried out in the presence of an inorganic reductant.

6. A method as claimed in any preceding claim in which the polyoxyalkylene compound of formula (II) is used for the etherification after hydrogenation.

7. A method as claimed in any preceding claim in which the reaction temperature ranges from 200C to lS0 C.

8. A method as claimed in claim 7 in which the reaction temperatures ranges from 500C to 1200C.

9. A method as claimed in any preceding claim in which the initial concentration of alkali metal hydroxide in the aqueous solution is in the range 40 to 75% by weight.

10. A method as claimed in any preceding claim in which the molar ratio of the organic halide to the hydroxyl group or groups of the polyoxyalkylene compound is in the range 2:1 to 5:1.

11. A method as claimed in claim 1, substantially as hereinbefore described in any one of the Examples.

12. An etherified polyoxyalkylene derivative obtained by a method as claimed in any one of the preceding claims.