EPOXIDES AND COMPOUNDS HAVING ACTIVE HYDROGEN ATOMS

Technical Field of Invention

The present invention relates to a catalyst used for the production of addition products of epoxides and compounds having at least one active hydrogen atom.

Technical Background of the Invention

It is well known that epoxides, such as epichlorohydrin and alkylene oxides, may be reacted with compounds having active hydrogen atoms, such as alcohols, fatty acids, amines and thiols, to produce addition products. It is also known that these reactions may be performed in the presence of various catalysts. The product resulting from the said reaction will normally be a mixture of several addition products where one, two or more epoxides have been added to the compound having at least one active hydrogen atom.

The most common catalysts used in epoxide addition reactions are basic, such as alkali hydroxides or alkali alcoholates. However, these catalysts are not very selective, and as a result the addition products are characterised by having a broad distribution of adducts.

It is also known to use catalysts that are acid, such as sulphuric acid, SnCI ₄ and BF ₃ . These are very selective, but at the same time they are corrosive and may form other side products, such as 1 ,4-dioxane for reactions where the epoxide is ethylene oxide.

Other catalysts that have been described are neutral mineral salts, such as magnesium or zinc perchlorate. These catalysts have good selectivity and are not corrosive, but there is a considerable risk for explosions when using them on a large scale.

Further, a number of different metal salts comprising organic anions have been disclosed for a variety of reactions.

An important technical field of epoxide addition reactions is the addition reaction of epichlorohydrin to alcohols, which is presented below. The addition products based on epichlorhydrin are valuable intermediates for the synthesis of glycidyl ethers. The reaction scheme is outlined below.

Scheme 1

The alcohol 1_ reacts with epichlorohydrin to yield a first addition product 2, which is the desired product that may be transformed to an alkyl glycidyl ether by reaction with NaOH. However, the first addition product 2 also has a hydroxyl group and may thus react with one more mole of epichlorohydrin to yield the di-adduct 3. The di- adduct 3 is less desirable, since after reaction with NaOH there will result a glycidyl ether which still contains one chlorine atom. The chlorine-containing glycidyl ether product may give rise to side-products in further syntheses where the glycidyl ether mixture is used. Thus, a good catalyst should favour the addition of epichlorohydrin to 1 to give a high ratio of 2 to 3.

Another important technical field of epoxide addition reactions is the addition reaction of an alkylene oxide to different compounds having at least one active hydrogen atom, particularly to alcohols. In this case, as is well known, the aim is not generally to add just one alkylene oxide to the alcohol, but to obtain a product with a narrow distribution of alkyleneoxy units as well as a low amount of remaining alcohol (for more detailed information about th is su bject see for exam ple " N O N I O N I C SURFACTANTS Organic Chemistry" Surfactant Science Series Vol 72, Marcel Dekker, Inc. 1998, Chapter 1 part III and Chapter 3 part III).

US 4,543,430 relates to a process for the reaction of an epoxide, e.g. alkylene oxide or epichlorohydrin, and a hydroxylated compound, e.g. an alcohol, in the homogeneous liquid phase, using a catalyst which is a metal salt of trifluoromethane sulphonic acid, such as aluminium triflate. The working examples only relate to reactions with ethylene oxide and propylene oxide.

US 6,093,793 relates to a process for polyaddition of epoxides to starter compounds having active hydrogen atoms, using a catalyst that is a metal salt of perfluorosulfonic acid. Other suitable anions may also be present in the salt, but the examples only disclose compounds with triflate anions, such as lanthanum triflate. EP 0 545 576 relates to a catalyst which is a salt of triflic acid or perchloric acid with a metal, e.g. cerium, ytterbium, yttrium or lanthanum. The catalysts are used for reaction between an alcohol and epichlorohydrin. In the working examples La(OTf) ₃ is used.

There is thus a need in the art for catalysts with improved selectivity. Summary of the Invention

The object of the present invention is to provide a catalyst for the addition reaction of an epoxide to a compound having at least one active hydrogen atom, where the selectivity index between the product formed by addition of one epoxide, and the product where two or more epoxides have been added, is high. Now it has surprisingly been found that a compound comprising a metal ion that is Al ³⁺ , and two types of anions, where the first type of anion is selected from the group consisting of a perfluorinated C1 -C10 alkylsulfonate and BF ₄ ^" , , and the second type of anion is a C1 -C10 alkylsulfonate, is an excellent catalyst for the addition of an epoxide to a compound having at least one active hydrogen atom.

Thus in a first aspect the present invention relates to the use of the aforementioned compound as a catalyst for the addition reaction of an epoxide to a compound having at least one active hydrogen atom. In a second aspect the present invention relates to a process for obtaining an addition product of an epoxide to a compound having at least one active hydrogen atom by addition of the epoxide to the said compound in the presence of the aforementioned catalyst.

In a third aspect the present invention relates to specific catalyst compounds per se.

These and other aspects of the present invention will be apparent from the following detailed description of the invention.

Detailed Description of the Invention The present invention relates to the use of a compound having the formula

where n is an integer 1 or 2, A-i is a fluorinated anion selected from the group consisting of anions having the formulae CF ₃ (CF2)yS0 ₃ ^" , where y = 0 or an integer 1 - 9, and BF ₄ ^" ; and A ₂ has the formula CH ₃ (CH2) _z S0 ₃ ^" , where z = 0 or an integer 1 -9; as a catalyst for the addition reaction of an epoxide, preferably epichlorohydrin or an alkylene oxide having 2-4 carbon atoms, to a compound having at least one active hydrogen atom.

In one other aspect, the present invention relates to a specific compound (I) per se having the formula

where n is an integer 1 or 2, A-i is a fluorinated anion selected from the group consisting of anions having the formulae CF ₃ (CF ₂ ) _y S0 ₃ ^" , where y = 0 or an integer 1 - 9; and BF ₄ ^" ; and

A ₂ is CH ₃ (CH ₂ ) _z S0 ₃ ^" , where z = 0 or an integer 1 -9.

Suitable examples of compounds having formula (I) are AI ³⁺ (CF ₃ S0 ₃ ^" ) _n (CH ₃ S0 ₃ ^" ) ₃ - _n (la) and AI ³⁺ (BF ₄ ^" ) _n (CH ₃ S0 ₃ ^" ) _3-n (lb), where n is an integer 1 or 2.

A convenient way to prepare compounds of formula (I) is disclosed in e.g. US 2005/0147778, [0086], wherein a method is described in which a compound of a metal, which belongs to Groups 3-12 of the periodic table, for example a metal alkoxide or a metal carboxylate, is dissolved or dispersed in a solvent, and then a strong acid, e.g. sulfonic acid, the conjugate acid of which is as strong as or stronger than sulfuric acid, is added to the resulting solution or suspension.

Another method for making salts with mixed anions is disclosed in WO 94/09055, where appropriate amounts of a solid metal salt containing one kind of anion is mixed with another metal salt containing another kind of anion, the salts are dissolved in THF to obtain a clear solution, and then the solvent is removed.

However, other methods are also possible to use, and the above examples should not be considered to limit the invention in any way.

A compound having an active hydrogen is herein defined as a compound which reacts with methylmagnesium bromide to form metha ne, accord i ng to th e Zerewittenoff process. Examples of such compounds include alcohols, carboxylic acids, amines and thiols.

Herein the compound having at least one active hydrogen atom is preferably an alcohol having the formula RO(CH ₂ CH(Y)0) _p H (II), where R is a hydrocarbyl group having 1 -24 carbon atoms, Y is independently H, CH ₃ or CH ₂ CH ₃ , preferably H, and p = 0-10. Preferably p=0, which will mean that the said compound is an alcohol that has not been alkoxylated. When the compound is an alkoxylated alcohol, p is typically 1 -5.

Suitable examples of compounds of formula (II) are fatty alcohols that may be saturated or unsaturated, linear or branched, such as n-hexanol, n-octanol, 2-ethylhexanol, n-decanol, isodecanol, 2-propylheptanol, dodecanol, 2-butyloctanol, tetradecanol, hexadecanol, octadecanol, oleyl alcohol, eicosanol, docosanol, erucyl alcohol, tetracosanol, C ₉ -Cn alcohol, Cn alcohol, tridecylalcohol, C10-C14 alcohol, C14-C15 alcohol, C12-C14 alcohol and Ci ₆ -Ci ₈ alcohol. The alkylene oxide having 2-4 carbon atoms could be ethylene oxide, propylene oxide, butylene oxide or mixtures thereof. If more than one alkylene oxide is added, then the ethyleneoxy, propyleneoxy and/or butyleneoxy u n its may be add ed randomly or in blocks. The blocks may be added to the compound having at least one active hydrogen atom, preferably an alcohol, in any order.

In one further aspect the invention relates to a process for obtaining an addition product of an epoxide, preferably of epichlorohydrin or an alkylene oxide having 2-4 carbon atoms, to a compound having at least one active hydrogen atom, preferably a compound having formula (II) as described above, by the addition of the epoxide to the said compound having at least one active hydrogen atom in the presence of a compound having formula (I), preferably (la) or (lb), as described above.

Suitably the reaction is carried out in a homogeneous liquid phase at a temperature from 20 to 150°C, preferably from 50 to 120°C and most preferably from 60-105°C, such as from 65 to 100°C.

In one embodiment epichlorohydrin is added to a compound having at least one active hydrogen atom, which preferably has the formula (II), in the presence of 0.1 - 2% by weight of a compound having the formula (I), preferably (la) or (lb), where the amount is counted on the compound having at least one active hydrogen atom. The mole ratio between epichlorohydrin and the compound having at least one active hydrogen atom is between 0.9 and 10, preferably between 0.9 and 5, more preferably between 0.9 and 4, and most preferably between 0.9 and 1.2.

In another embodiment an alkylene oxide having 2-4 carbon atoms is added to the compound having at least one active hydrogen atom, preferably to a compound having the formula (II), in the presence 0.01 -5% by weight, counted on the compound having at least one active hydrogen atom, of a compound having the formula (I), preferably (la) or (lb). The mole ratio between the alkylene oxide and the compound having at least one active hydrogen atom is between 1 and 10, preferably between 1 and 5.

In a typical reaction the compound (I) is added to the compound having at least one active hydrogen atom, preferably compound (II), while stirring and heating to obtain the desired temperature. Then the epoxide is slowly added to the mixture of (I) and (II) with continued stirring and heating. When all epoxide has been added, the reaction mixture is further heated and stirred until analysis shows that there is no epoxide left.

Experiments

General Experimental

Reactions between alcohol and epichlorohydrin (EKH)

The synthesis descriptions in Examples 1 and 2 could generally be followed for syntheses where other catalysts according to the invention are used , provided appropriate adjustments of reaction times and temperatures are made. The synthesis products of a typical reaction essentially contain three components: unreacted alcohol 1_, chloroglyceryl ether 2 and and chloroglyceryl ether reacted with one more epichlorohydrin 3 (see scheme 1 in the technical background part).

The amounts of unreacted alcohol and of the different epoxide adducts were determined by GC analysis of the reaction mixtures. The GC area percentages were approximated to be weight percentages. The selectivity calculations that were performed used only the data for 1_, 2 and 3. The other side-products were disregarded since they were present in amounts lower than 1 %.

In a typical calculation the area% of the signals from 1_, 2 and 3 were divided by the respective molecular weight to obtain the molar relation between them, these recalcu lated values were added , and the molar percentage of each of the components was determined. The selectivity for the chloroglyceryl ether 2 was then obtained by dividing the molar percentage of this compound by the sum of the molar percentages of 2 and 3

Example 1a

Synthesis of a tetradecyl chloroglyceryl ether using AI ³⁺ (CF3SO: )?(CH3SO: ) as a catalyst

1 -Tetradecanol (40.0 g, 0.187 mol) was added to a round-bottom flask and heated to 65-70°C. Then 0.2 g (1 .0 mmol) aluminum triisopropoxide was added, after which triflic acid (0.300 g, 2.0 mmol) and methanesulfonic acid (0.087 g, 0.9 mmol) were added immediately. This mixture was stirred for 15 minutes and then the addition of 18.2 g (0.197 mol) of epichlorohydrin was started dropwise from an addition funnel. The progress of the reaction was followed by GC analysis. When the heating was stopped 7.5 hours after the start of the EKH addition, the reaction mixture had the composition in the table below.

Example 1 b

The reaction was repeated with the same amounts of reagents at 80°C. After 2 hours from the start of the EKH addition the temperature was raised to 95°C for a post- reaction of 1 .5 hours, giving a total reaction time of 3.5 hours. When the heating was stopped the reaction mixture had the composition in table 1 below. Table 1

*

For calculation see General Experimental

The same selectivity is obtained in both of the reactions, but the reaction time was much longer at the lower temperature.

Example 2

Synthesis of a tetradecyl chloroglyceryl ether using Al^fCFsSO^XCHsSO )? as a catalyst

Neodol 45 (40.0 g, 0.182 mol) was heated to 65°C and then 0.36 g (1 .76 mmol) aluminum triisopropoxide was added and slowly dissolved, after which triflic acid (0.265g, 1 .76 mmol) and methanesulfonic acid (0.335 g, 3.5 mmol) were added immediately). Epichlorohydrin (17.4 g, 0.188 mol) was added dropwise over 30 minutes. The reaction mixture was further heated at 65°C, and the progress of the reaction was followed by GC analysis. When the heating was stopped after a total reaction time of 4 hours the reaction mixture had the composition in table 2 below.

The product mixture was also analyzed after heating overnight.

Table 2

*

For calculation see General Experimental Example 3

Synthesis of a C14-C15 alkyl glycidyl ether using AI^BF XCHgSC )? as catalyst in step 1

Step 1 - epichlorohydrin addition to Neodol 45

123 g (0.56 mol) of a C14-C15 alkyl alcohol (Neodol 45) was weighed into a 500 ml round bottom flask, equipped with a mechanical stirrer and an automatically controlled thermocouple sensor. 1 g (0.0049 mol) of aluminum triisopropoxide was added to the alcohol at room temperature. The reactor was heated to 75°C, and the mixture was stirred at 200 rpm for about 15 minutes without getting a clear solution. Then 0.9 g (0.0094 mol) methanesulfonic acid and 0.74 g of an approximately 54 wt% tetrafluoroboric acid solution in diethyl ether (0.0046 mol) were added to the reactor. A clear mixture was obtained after about 15 minutes mixing. Then 54.9 g (0.59 mol) epichlorohydrin was added dropwise from an addition funnel during a period of 50 minutes and the temperature was kept around 74°C during the addition. The reaction mixture was further stirred and heated for up to a total of 10 hours from the start of addition of EKH. Samples were taken out for analysis at the times indicated in the Table 3 below. The samples were analyzed by gas chromatography to determine their composition.

Table 3

*Time is counted from start of EKH addition The selectivity values were calculated for both the case when there was still a lot of EKH left in the reaction mixture, as well as for the case when almost all EKH had reacted. These calculations show that the selectivity values were about the same throughout the reaction.

Step 2 - Ring closure of addition product obtained in step 1 to glycidyl ether

The above intermediate product was stirred at a speed of 960 rpm and heated to 80°C. 1 10.5 g of a 31 .2 wt% sodium hydroxide solution in water was added to the reactor over a two hours period of time. The stirring speed was then decreased to 250 rpm, 33 g de-ionized water was added, and the stirring was continued for about 5 min after the addition. The mixture was then transferred to a separating funnel, and after 15 minutes the bottom phase (water phase) was separated from the organic phase (glycidyl ether) and discarded. The amount of glycidyl ether in the organic phase was determined by epoxide titration to be 3.2 mmol/g, which means an active content of 88.2 wt%. The titration method used to determine the amount of epoxide present in the product is described in Analytical Chemistry 36 (1964) p 667.

Synthesis of tetradecyl chloroglyceryl ether using Al^fBF XCHsSOs ^' )? as catalyst at different temperatures

The same procedure was used as described above for Step 1 , but tetradecanol was added as the starting alcohol. The reaction was performed at 90, 100 and 1 10°C to see the temperature dependence on the conversion/selectivity, and the results are shown in Table 4 below.

Table 4

*Time is counted from start of EKH addition The selectivity is not significantly dependent upon the reaction time. However, it is very dependent upon the temperature, as is shown when comparing the selectivity at 100°C and 1 10°C.

Example 4a

Synthesis of tetradecyl chloroglyceryl ether using Al^fBF MCHsSO ) as catalyst

32.15 g (0.15 mol) of 1 -tetradecanol was weighed into a 250 ml round bottom flask, equipped with a mechanical stirrer and an automatically controlled thermocouple sensor. 0.27 g (0.0013 mol) of aluminum triisopropoxide, 0.125 g (0.0013 mol) of methane sulfonic acid and 0.42 g of an approximately 54 wt% tetrafluoroboric acid solution in diethyl ether (0.0026 mol) were added to the alcohol at room temperature. The reactor was heated to 100°C, and the mixture was stirred at 200 rpm for about 15 minutes to get a clear solution. Then 14.15 g (0.153 mol) epichlorohydrin was added dropwise from an addition funnel during a period of 60 minutes and the temperature was kept around 100°C during the addition. The reaction mixture was further stirred and heated for up to a total of 2 hours and 45 minutes from the start of addition of EKH. The amount of unreacted ECH left in the reaction mixture was then determined by epoxide titration to be 0.07 meq/g, and the product was further analysed by GC to determine its composition.

Example 4b

The same procedu re was used as described above, except that the reaction temperature was kept at 75°C, and samples were taken out for analysis at the times indicated in the Table 5 below.

Table 5

*Time is counted from start of EKH addition

The selectivity is about the same at 100 and 75°C, but the conversion is much higher at the higher temperature.

Synthesis of a a C14-C15 alkyl chloroglvceryl ether using AI ³⁺ (CF3SO as a catalyst (Comparison)

20.3 g (0.0.092 mol) of a C14-C15 alkyl alcohol (Neodol 45) was heated to 75°C and 0.2 g aluminum triisopropoxide (1 .0 mmol) was added to the alcohol, after which 0.45 g (3.0 mmol) of triflic acid was immediately added to the mixture. After 15 minutes stirring, 9.3 g (0.1 mol) epichlorohydrin was added dropwise from an addition funnel. The reaction mixture was further heated at 75°C, and the progress of the reaction was followed by GC analysis. When the heating was stopped the reaction mixture had the composition in the table below.

Synthesis of a tetradecyl ch loroglvceryl ether using AI ³⁺ (BF ^" ½ as a catalyst (Comparison)

40.1 g of 1 -tetradecanol (0.187 mol) was heated to 75°C and 0.39 g aluminum triisopropoxide (1 .9 mmol) was added to the alcohol, after which 0.90 g of an approximately 54 wt% tetrafluoroboric acid solution in diethyl ether (5.5 mmol) was added in one portion. After 15 minutes stirring, 17.8 g (0.192 mol) epichlorohydrin was added dropwise from an addition funnel. The reaction mixture was further heated at 75°C, and the progress of the reaction was followed by GC analysis. When the heating was stopped the reaction mixture had the composition in the table below. Synthesis of a tetradecyl chloroglyceryl ether using BF as a catalyst (Comparison)

40.0 g (0.187 mol) 1 -tetradecanol was added to a round-bottom flask and heated to 45°C, after which boron trifluoride diethyl etherate (0.5 g, 3.5 mmol) was added. 18.2 g (0.197 mol) of epichlorohydrin was then added dropwise with stirring during a period of 30 minutes at a temperature slightly below 50°C. After the addition, the reaction mixture was further heated and stirred for 30 minutes at 50°C, giving a total reaction time of 1 hour. When the heating was stopped the reaction mixture had the composition in the table 6 below.

Table 6

Synthesis of a tetradecyl chloroglyceryl ether using AI ³ (CH SQ ^" ) as a catalyst (Comparison)

Although the reaction was run at 100°C it was very slow, and a large amount of both unreacted EKH and unreacted alcohol was left even after 4.5 hours. The conversion after this reaction time was only around 35 % when using this catalyst, and thus the reaction rate is far too low to be practically useful.

Example 5

Etoxylation of 1 -decanol using Al ³⁺ (CF SQ ^" )?(CH S0 ^" ) (abbreviated as AI(OTf)?(Mes) in Table below) as catalyst

1 10.8 g (0.7 mol) 1 -decanol was weighed into an automatically controlled autoclave. Then 1 .43 g (0.007 mol) aluminum triisopropoxide was added at room temperature, followed immediately by the addition of 0.67 g (0.007 mol) methane sulfonic acid and 2.1 g (0.014 mol) triflic acid into the reactor. The autoclave was closed and the mixture was stirred for 15 minutes to dissolve all components in the alcohol. To remove oxygen and test for leakages, the autoclave was flushed with nitrogen gas up to about 4 bar pressure and evacuated by a water suction pump. This procedure was repeated three times. The reactor mixture was then heated to 80°C, and 0.7 mole ethylene oxide was added automatically at this temperature with a maximum pressure of 3 bar. The addition time was about one hour and the post reaction time 7 minutes. After evacuation of the autoclave 43.3 g of the product 1 -decanol + 1 EO was discharged from the autoclave for analysis.

Etoxylation o f 1 -decanol using AI^CFaSOa ^' XCHaSOa ^" )? (abbreviated as AI(OTf)(Mes)?jn Table below) as catalyst

100 gram (0.63 mole) 1 -Decanol was weighed into a 0.5 liter autoclave at room temperature. Then 1 .29 g (0.0063 mol) aluminum triisopropoxide (1 mole% based on the alcohol), 1 .21 g (0.0126 mole) methane sulfonic acid and 0.95 g (0.0063 mole) trifluoromethane sulfonic acid was added to the autoclave. The autoclave was closed and the mixture was stirred for 15 minutes. To remove oxygen and test for leakages, the autoclave was flushed with nitrogen gas up to about 4 bar pressure and then evacuated by a water suction pump. This procedure was repeated three times. The reactor mixture was then heated to 100°C, and 27.8 g (0.63 mole) ethylene oxide was added automatically during a 15 minutes period of time. After about 6 minutes a constant pressure of 0.16 bar had been obtained. The temperature in the autoclave was decreased to 30°C and then evacuated. 15.2 g (0.075 mole) of 1 -Decanol+1 EO was discharged from the autoclave for analysis.

Ethoxylation of 1 -decanol using Al^fCF^SCV abbreviated AI(OTf)^in Table below) as catalyst (Comparison)

The above synthesis method was followed using 1 mol% aluminum triflate as catalyst, based on the 1 -decanol. The temperature and the molar ratio of ethylene oxide to 1 -decanol was the same as above, and also the reaction time was about the same.

Ethoxylation of 1 -decanol using BF^ as catalyst (Comparison)

The above synthesis method was followed using 1 mol% boron trifluoride diethyl etherate as catalyst, based on the 1 -decanol. The temperature and the molar ratio of ethylene oxide to 1 -decanol was the same as above, and also the reaction time was about the same. It was no problem adding another mol of EO per mol of 1 -decanol+1 EO using any of the catalysts in this example.

Analysis of homologue distribution of products of Example 5 by GC

In Table 6 the homologue distribution is displayed for the products of Example 5 that were obtained by using the comparison catalysts BF ₃ and AI ³⁺ (CF ₃ S0 ₃ ^" )3 and the catalysts which are according to the invention.

Table 6

Example 6

Etoxylation of 1 -decanol using Al^fBF XCH^SQy)? (abbreviated as AKBF^fMes)? in Table below) as catalyst

100 gram 1 -Decanol (0.63 mol) was weighed into a 0.5 liter autoclave at room temperature. 1 .29 g (0.0063 mol) aluminum triisopropoxide (equal to 1 mole% based on the alcohol), 1 .21 g methane sulfonic acid (0.0126 mol) and 1.024 gram tetrafluoroboric acid (as 54% solution in diethyl ether = 0.0063 mol) was added to the autoclave at room temperature. The autoclave was closed and the mixture was stirred for 15 minutes to dissolve all components in the alcohol. To remove oxygen and test for leakages, the autoclave was flushed with nitrogen gas up to about 4 bar pressure and evacuated by means of a water suction pump. This procedure was repeated three times. The reactor mixture was then heated to 100°C, and 27.7 g ethylene oxide (0.63 mol) was added automatically at this temperature during a 38 minutes period of time. The reaction was allowed to continue until a constant pressure of 0.35 bar was reached. The total reaction time, including the addition time, was 5 hours. The temperature was decreased to 30°C and the autoclave was evacuated. 28 g (0.138 mol) of the product 1 -decanol + 1 EO was discharged from the autoclave for analysis.

Etoxylation of 1 -decanol using Al^fBF MCH^SOg ^" ) (abbreviated as AKBF^dVles) in Table below) as catalyst

100 gram 1 -Decanol (0.63 mol) was weighed into a 0.5 liter autoclave at room temperature. 1 .29 g (0.0063 mol) aluminum triisopropoxide (equal to 1 mole% based on the alcohol), 0.6 g (0.0063 mol) methane sulfonic acid and 2.05 g tetrafluoroboric acid (as 54% solution in diethyl ether = 0.0126 mol) was added to the autoclave at room temperature. The autoclave was closed and the mixture was stirred for 15 mc inutes to dissolve all components in the alcohol. To remove oxygen and test for leakages, the autoclave was flushed with nitrogen gas up to about 4 bar pressure and evacuated by means of a water suction pump. This procedure was repeated three times. The reactor mixture was then heated to 100°C, and 27.8 g (0.63 mol) ethylene oxide was added automatically at this temperature during a 10 minutes period of time. The reaction was allowed to continue until a constant pressure of 0.31 bar was reached. The total reaction time, including the addition time, was 5.5 hours. The temperature was decreased to 30°C and the autoclave was evacuated. 12.3 g (0.06 mol) of the product 1 -decanol + 1 EO was discharged from the autoclave for analysis.

Etoxylation of 1 -decanol using AI ³⁺ (BF ^" ½ as catalyst (Comparison)

100 gram 1 -Decanol (0.63 mol) was weighed into a 0.5 liter autoclave at room temperature. 1 .29 g (0.0063 mol) aluminum triisopropoxide (equal to 1 mole% based on the alcohol), and 3.07 gram tetrafluoroboric acid (as 54% solution in diethyl ether = 0.0189 mol) was added to the autoclave at room temperature. The autoclave was closed and the mixture was stirred for 15 minutes to dissolve all components in the alcohol. To remove oxygen and test for leakages, the autoclave was flushed with nitrogen gas up to about 4 bar pressure and evacuated by means of a water suction pump. This procedure was repeated three times. The reactor mixture was then heated to 100°C, and 27.8 g ethylene oxide (0.63 mol) was added automatically at this temperature during a 18 minutes period of time. The reaction was allowed to continue until a constant pressure of 0.31 bar was reached. The total reaction time, including the addition time, was 31 minutes. The temperature was decreased to 30°C and the autoclave was evacuated. 9.5 g (0.047 mol) of the product 1 -decanol + 1 EO was discharged from the autoclave for analysis.

Etoxylation of 1 -decanol using AI ³⁺ (CH SQ ^" ) (abbreviated as AI(Mes)3_in Table below) as catalyst (Comparison)

100 gram 1 -Decanol (0.63 mol) was weighed into a 0.5 liter autoclave at room temperature. 1 .29 g (0.0063 mol) aluminum triisopropoxide (equal to 1 mole% based on the alcohol), and 1 .82 g (0.0189 mol) was added to the autoclave at room temperature. The autoclave was closed and the mixture was stirred for 15 minutes to dissolve all components in the alcohol. To remove oxygen and test for leakages, the autoclave was flushed with nitrogen gas up to about 4 bar pressure and evacuated by means of a water suction pump. This procedure was repeated three times. The reactor mixture was then heated to 100°C, and 27.8 g ethylene oxide (0.63 mol) was added automatically at this temperature during a 15 minutes period of time. The reaction was allowed to continue for about 24 hours, after which the pressure was 0.96 bar and still not reaching a constant value. The temperature was then decreased to 30°C and the autoclave was evacuated. A sample of 1 -decanol + 1 EO was discharged from the autoclave for analysis.

It was no problem adding another mol of EO per mol of 1 -decanol+1 EO using any of the catalysts in this example except for Al ³⁺ (CH ₃ S0 ₃ ) ₃ .

Analysis of homologue distribution of products of Example 6 by GC

In Table 7 the homologue distribution is displayed for the products of Example 5 that were obtained by using the comparison catalysts AI ³⁺ (BF ₄ ^" ) ₃ and Al ³⁺ (CH ₃ S0 ₃ ^" ) ₃ , and the catalysts Al ³⁺ (BF ₄ ^" )(CH ₃ S0 ₃ ^" ) ₂ and Al ³⁺ (BF ₄ ^" ) ₂ (CH ₃ S0 ₃ ^" ) that are according to the invention. Table 7

Homologues AI ³⁺ (BF ₄ ) ₃ AI(Mes) ₃ AKBFjHMes AKBFjUMes)

(comparison)

(comparison)

Homoloques Homoloques

Homologues

Homologues

(area%) (area%) (area%)

(area%)

Decanol 41 .2 39.0 35.0 28.2

Decanol+1 EO 33.8 40.5 46.5 43.0

Decanol+2EO 15.4 13.1 13.7 18.3

Decanol+3EO 5.5 2.5 2.1 4.6

Decanol+4EO 1 .8 0.4 0.2 0.7