WO2013010316A1

WO2013010316A1 - Process for preparing epoxide derivatives and sulfation product thereof

Info

Publication number: WO2013010316A1
Application number: PCT/CN2011/077276
Authority: WO
Inventors: Galder Cristobal; Yan Zhao; Zhaoyu FAN
Original assignee: Rhodia (China) Co., Ltd.
Priority date: 2011-07-18
Filing date: 2011-07-18
Publication date: 2013-01-24

Abstract

A process for producing an epoxide derivative, comprising reacting an alcohol of formula (I) with an epoxide of formula (II) in the presence of a simple metal salt of rare earth element as a catalyst, in formula (I)-(II), R¹ represents the skeleton moiety of the alcohol, R² represents a linear or branched alkyl group, p is an integer ranging from 1 to 100, and q is 0 or 1. A process for preparing a sulfation product of the epoxide derivative is also provided.

Description

PROCESS FOR PREPARING EPOXIDE DERIVATIVES AND

SULFATION PRODUCT THEREOF

Field of the Invention

[0001] The application relates to a process for preparing an epoxide derivative and a process for preparing the sulfation product thereof, particularly to a process for preparing alkyl (poly)glyceryl ether derivatives or alkyl-substituted epoxide derivatives and a process for preparing the sulfatation product thereof, and more particularly to a process for preparing an alkyl (poly)glyceryl ether derivatives from alkyl glycidyl ether and (poly)glycerol and a process for preparing the sulfation product from the alkyl (poly)glyceryl ether derivatives.

Background of the Invention

[0002] Glyceryl ether derivatives are compounds useful as solvents, emulsifiers, dispersants, detergents, foaming agents, etc. (Poly)glyceryl ether can be used as an ingredient of cosmetic composition, and provides excellent moisturizing effect and excellent extendibility when applied to the skin, hair and the like, and has excellent emulsion stability.

[0003] The conventional method of producing the polyglyceryl ether derivatives is to react an alcohol with glycidol in the presence of an alkali as a catalyst. In the conventional method, after reaction of the alcohol with an alkali, glycidol is dropped into the obtained reaction product to allow the alcohol to react therewith.

[0004] However, the above conventional method using the alkali tends to have problems such as low conversion rate of the alcohol used in the reaction and large burden upon purification for removal of the unreacted alcohol.

[0005] US20090275784A discloses an improved process for producing polyglyceryl ether derivatives by reacting an alcohol with glycidol in the presence of a simple metal salt of rare earth element. [0006] However, in the above processes, glycidol is expensive or not easy to make and can hardly be prevented from self-polymerizing. The self-polymerization of glycidol will substantially decrease the conversion rate and greatly increase the cost of post-treatment.

[0007] Therefore, there is still a need for an improved process for preparing (poly)glyceryl ether derivatives.

Summary of the Invention

[0008] The inventors of the present invention have surprisingly found that alkyl (poly)glyceryl ether derivatives or alkyl-substituted epoxide derivatives could be prepared via a new route in a more efficient and costless way— reacting an alcohol, especially glycerol or polyglycerol, with alkyl glycidyl ether or alkyl-substituted epoxide in the presence of a simple metal salt of rare earth element. Thereby, the present invention relates to a process for producing an epoxide derivative, comprising reacting an alcohol of formula

(I)

I,

wherein R represents the skeleton moiety of the alcohol, p is an integer ranging from 1 to 100, with an epoxide of formula II)

wherein R² represents a linear or branched alkyl group, q is 0 or 1 , preferably 1 , in the presence of a simple metal salt of rare earth element as a catalyst. [0009] The present invention especially relates to a process for producing an alkyl (poly)glyceryl ether derivative,

comprising reacting an alcohol of formula (I)

I, wherein R¹ represents the skeleton moiety of a polyglycerol with 3-4 glycerol units and p is 4-5, with an alkyl glycidyl ether of formula (II)

H, wherein R is defined as above, and q is 1 ,

in the presence of a simple metal salt of rare earth element as a catalyst.

[0010] The present invention further relates to a process for preparing a sulfatation product of the epoxide derivative obtained by the present process by a sulfation step.

Detailed Description Of The Invention

[0011] As used herein, the abbreviation "AGE" refers to alkyl glycidyl ether, "MAGE" refers to mono alkyl glyceryl ether.

[0012] As used herein, the term "alkyl" means a linear or branched alkyl group optionally substituted with one or more substituent selected from the group consisting of lower alkyl, lower alkoxy, lower alkylsulfanyl, lower alkylsulfenyl, lower alkylsulfenyl, oxo, hydroxy, mercapto, amino optionally substituted by alkyl, carboxy, carbamoyl optionally substituted by alkyl, aminosulfonyl optionally substituted by alkyl, nitro, cyano, halogen, or lower perfluoroalkyl, multiple degrees of substitution being allowed. Examples of "alkyl" as used herein include, but are not limited to, n-butyl, n-pentyl, isobutyl, isopropyl, and the like. Herein, the term "lower" means that the alkyl moiety of a group has 1 5 to 30, preferably 1 to 20, still more preferably 1 to 10 carbon atoms.

[0013] As used herein, the term "polyglycerol" includes an oligomeric and/or polymeric chain composed of monomeric glycerol (i.e. , HOCH₂CH(OH)CH₂OH) bonded together by ether linkages at the hydroxyl residue.

[0014] As used herein, the term "skeleton moiety of the alcohol" means the other I o portion of the alcohol than the hydroxyl groups.

[0015] As one aspect, the present invention relates to a process for producing an epoxide derivative,

comprising reacting an alcohol of formula (I)

15 with an epoxide of formula II)

II,

in formula (I) and (II), R represents the skeleton moiety of the alcohol; R"0 represents a linear or branched alkyl group, preferably having 1 to 36, more preferably 4 to 24, still more preferably 6 to 20, even more preferably 8 to 18, and most preferably 12-14 carbon atoms; p is an integer ranging from 1 to 100, preferably 1 to 90, more preferably 2 to 20, and most preferably 4 to 5; q is 0 or 1 , and preferably 1. 5 [0016] Examples of the linear or branched alkyl groups include but not limited to methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, various hexyl groups, various octyl groups, various decyl groups, various dodecyl groups, various tetradecyl groups, various hexadecyl groups, various octadecyl groups, various icosyl groups, various tetracosyl groups, various triacontyl groups. Among them, preferred are dodecyl and tetradecyl.

[0017] In the present invention, as the alcohol that is one of the raw materials, there may be used a monoalcohol (a) containing one hydroxyl group in a molecule thereof, and a polyol (b) containing 2 to 6 hydroxyl groups in a molecule thereof.

[0018] For convenience, in the present invention, the alcohols including the monoalcohol (a) and the polyol (b are represented by the following formula (I)

I,

wherein R¹ represents the skeleton moiety of the alcohol, and p represents the number of hydroxyl group(s) in the alcohol and is an integer ranging from 1 to 100, preferably 1 to 90, more preferably 1 to 20, and most preferably 4 to 5.

[0019] Specific examples of the monoalcohol (a) include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, sec-butyl alcohol, pentyl alcohol, isopentyl alcohol, hexyl alcohol, cyclohexyl alcohol, 2-ethylhexyl alcohol, octyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol monopropyl ether, polyethylene glycol monobutyl ether, polypropylene glycol monomethyl ether, polypropylene glycol monoethyl ether, polypropylene glycol monopropyl ether and polypropylene glycol monobutyl ether. These monoalcohols (a) may be used alone or in the form of a mixture of any optional two or more thereof Among these monoalcohols (a), from the viewpoint of a good applicability of the resultant polyglyceryl ether derivatives, especially preferred are lauryl alcohol, 2-ethylhexyl alcohol and isostearyl alcohol. On the other hand, specific examples of the polyol (b) having 2 to 6 hydroxyl groups include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1 ,4-butylene glycol, 1,6-hexylene glycol, 1 ,8-octylene glycol, 1 ,10-decylene glycol, neopentyl glycol, trimethylol ethane, trimethylol propane, glycerol, diglycerol, pentaerythritol and sorbitol. These polyols (b) may be used alone or in the form of a mixture of any optional two or more thereof. Among these polyols (b), from the viewpoint of a good applicability of the resultant polyglyceryl ether derivatives, preferred are glycerol, polyglycerol or mixtures thereof The most preferred polyglycerols useful in the present invention have 2 to 30, preferably 2-20, more preferably 2-10, and most preferably 3-4 glycerol units.

[0020] When glycerol is used as the alcohol, the epoxide derivative produced by the present process can be represented by the following formula (III),

wherein Rr represents a linear or branched alkyl group, preferably having 1 to 36, more preferably 4 to 24, still more preferably 8 to 24, still more preferably 6 to 20, even more preferably 8 to 18, and most preferably 12- 14 carbon atoms; q is 0 or 1 , and preferably 1. When glycerol is used as the alcohol, the moiety

H-(C\H₆0₂)- in the formula (III) should be changed to H-(C₃H₆0₂)_m- wherein m represents an average number of glycerol units of polyglycerol which is usually from 1 to 20, and preferably from 2 to 10.

[0021] According to some particularly preferred embodiments, the alcohol is a (poly)glycerol and the produced epoxide derivative is a (poly)glyceryl ether derivative. In this case, the produced derivative can be represented by the following formula (IV)

H(C₃H₆0₂)_m+1O IV

wherein m represents the average number of glycerol units of polyglycerol which is usually from 1 to 20, and preferably from 2 to 10.

[0022] According to some embodiments, an alkyl-substituted epoxide is used to react with an alcohol to produce the epoxide derivative. Especially, glycerol or polyglycerol is used herein as the alcohol. In this case, the obtained epoxide derivative can be represented by the following formula (V)

H(C₃H₆0₂)_m+1OC(R²)HCH₂OH V wherein m represents the average number of glycerol units of polyglycerol which is usually from 1 to 20, and preferably from 2 to 10, and R² has the meaning as defined above.

[0023] In the present invention, as the catalyst, there is used the simple metal salt of rare earth element (hereinafter occasionally referred to merely as a "rare earth-based catalyst"). The "simple metal salt" used herein means such a metal salt in the form of a primary compound except for a composite salt and a complex salt.

[0024] The simple metal salt of rare earth element may be usually used in the form of an inorganic acid salt and/or an organic acid salt. From the viewpoints of realizing the highly-selective addition reaction and enhancing a conversion rate of the alcohol, the inorganic acid salt is suitably a perchloric acid salt, and the organic acid salt is suitably a sulfonic acid salt.

[0025] Examples of the preferred rare earth element contained in the simple metal salt include lanthanoid elements such as scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium. Among these rare earth elements, more preferred are scandium, lanthanum, samarium, europium, erbium, lutetium and ytterbium, still more preferred are scandium, lanthanum, samarium and ytterbium, and further still more preferred are lanthanum and/or samarium.

[0026] Examples of the sulfonic acid salts of the rare earth elements include those compounds represented by the general formula (VI):

M(OS0₂R³)x (VI)

wherein M is a rare earth element; R³ is a hydrocarbon group, an alkoxyl group or a substituted or unsubstituted aryl group whose hydrogen atoms may be partially or wholly substituted with a fluorine atom; and x is an integer equal to a valence of M.

[0027] In the general formula (VI), examples of the hydrocarbon group and the alkoxyl group as R³ include those hydrocarbon and alkoxyl groups having 1 to 12 carbon atoms. Specific examples of the hydrocarbon group and the alkoxyl group as R¹ include methyl, ethyl, butyl, hexyl, octyl, decyl, dodecyl, methoxy, ethoxy, butoxy, hexyloxy, octyloxy, decyloxy, dodecyloxy, trifluoromethyl, pentafluoroethyl, nonafluorobutyl, trifluoromethoxy, pentafluoroethoxy and nonafluorobutoxy. Among these hydroxyl groups and alkoxyl groups, especially preferred is trifluoromethyl.

[0028] Examples of the substituted or unsubstituted aryl group as R³ include those aryl groups having 6 to 25 carbon atoms in total. Specific examples of the aryl group as R¹ include phenyl, tolyl, xylyl, ethylphenyl, butylphenyl, octylphenyl, dodecylphenyl, naphthyl, methylnaphthyl and dimethylnaphthyl. Among these aryl groups, especially preferred are dodecylphenyl and tolyl,

[0029] Examples of the preferred sulfonic acid salts of the rare earth elements represented by the general formula (VI) include triflates (trifluoromethanesulfonates), dodecylbenzenesuifonates and toluenesulfonates of scandium, lanthanum, samarium and ytterbium. Among these sulfonic acid salts, more preferred are triflates, dodecylbenzenesuifonates and toluenesulfonates of lanthanum and samarium.

[0030] In the present invention, the above simple metal salts of the rare earth elements may be used, as the catalyst, alone or in combination of any two or more thereof.

[0031] The amount of the rare earth-based catalyst used in the present invention is usually from 0.001 to 0.2 mol, preferably 0.002 to 0,5 mol, more preferably 0.002 to 0.1 mol and even more preferably from 0,005 to 0,05 mol per 1 mol of the alcohol used, from the viewpoint of a good balance between reaction rate and economy.

[0032] Although the reaction may be conducted under a solvent-free condition, an organic solvent may be used in an appropriate amount for the purpose of facilitating mixing of the raw materials. Examples of the organic solvent include hexane, diethyl ether, tetrahydrofuran, dichloromethane, acetonitrile, nitromethane, benzene, toluene, xylene, chloroform, dioxane, cyclohexane, dimethyl sulfoxide (DMSO), dimethylformamide and dimethylacetamide.

[0033] According to some preferred embodiments, the reaction is carried out in the absence of solvent and glycerol is used as starting material.

[0034] According to some other preferred embodiments, polyglycerol is used as the alcohol and the reaction is carried out in a solvent, for example, dimethyl sulfoxide. Since hydrophilic glycerol/polyglycerol and hydrophobic glycidyl ether tend to form biphasic mixture due to their differences in polarity, they do not readily react. It has now been found that the phase separation problem can be overcome if DMSO was used as solvent and that the metal salt of rare earth element can effectively catalyze the reaction of glycerol/polyglycerol and alkyl glycidyl ether in DMSO.

[0035] According to some particularly preferred embodiments, a mono alkyl glyceryl ether (MAGE) can be produced by reacting a CI 2-20 alkyl glycidyl ether.

[0036] In addition, the reaction may be conducted in air, but is preferably conducted in an inert gas, for example, in a nitrogen atmosphere or in an argon atmosphere, for the purpose of suppressing production of by-products. [0037] The reaction temperature varies depending upon kind of the alcohol used, kind and amount of the catalyst used, etc. From the viewpoints of practical reaction time, yield and quality of the resultant product, the reaction temperature is usually from about 60 to about 300 "C , preferably from 90 to 250^°C , more preferably from 120 to 200 °C and most preferably from 150 to 180°C . Also, the reaction time varies depending upon the reaction conditions, and is, therefore, not particularly limited. The reaction time is usually from about 30 min to about 100 h, preferably from 1 to 50 h and more preferably from 1 to 30 h. When solvent is used, the reaction temperature can be lower than the reaction carried out in absence of solvent.

[0038] After completion of the reaction, the obtained reaction solution is optionally subjected to washing treatment according to the requirements, and then treated by the methods such as filtration, distillation and extraction, thereby obtaining the polyglyceryl ether derivative as aimed. If required, the resultant polyglyceryl ether derivative may be further purified by an ordinary method such as silica gel column chromatography, distillation and recrystallization. At this time, the used rare earth-based catalyst may be recovered and reused. For this purpose, the polyglyceryl ether derivative is preferably obtained by the extraction. More specifically, after extracting the polyglyceryl ether derivative, an aqueous solution containing the rare earth-based catalyst is recovered, and water is distilled off from the aqueous solution, thereby isolating the rare earth-based catalyst therefrom. Further, if required, the thus isolated rare earth-based catalyst may be purified and then reused in the process of the present invention.

[0039] The present process for preparing epoxide derivative can achieve unexpected technical effects as compared with the following two catalysts:

- Lewis acids, such as stannic chloride, boron (tri) fluoride etherate, and

Alkali, such as NaOH and sodium methylate.

[0040] According to the present process, the disadvantages of eroding the equipment can be avoided, a highly-selective reaction between the alcohol and alkyl glycidyl ether can be realized, and the conversion rate of alcohol can be increased. [0041] Another aspect of the present invention is to provide a sulfatation product of the epoxide derivative by sulfatating the compound produced by the present process. The sulfatation of the epoxide derivative (for example, the alkyl (poly)glyceryl ether derivative or the alkyl-substituted epoxide derivative) can be carried out by any method already known in the prior art.

Examples

[0042] The Examples which follow serve to illustrate the present invention in more detail without restricting the scope of the invention to the following embodiments by way of example. Unless otherwise indicated, all the percents, ratios, or parts are in terms of weight.

Glossary:

AGE: alkyl glycidyl ether,

PG: polyglycerol,

DMSO: dimethylsulfoxide,

MAGE-4: monoalkyl glyceryl ether (4 is the average number of glycerol units)

MAGE: monoalkyl glyceryl ether

Materials:

Compounds obtained in these examples were analyzed by following techniques.

HPLC conditions:

HPLC main part: waters 2690;

Column: wakosil 5 CI 8 (4.6mm x 250mm, 5 μ m);

Column oven temperature: 35 ^°C ;

Eluent: methanol/water (= 90: 10-80:20),

Flow rate: 0.5 mL/min;

Sampe amount: 20 μ L; Detector: RI detector;

Retention times for respective components are 5-7min for polyglycerol; 8-27min for the monoalkyl polyglycerol ethers; 29-36min for the dialkyl polyglycerol ethers.

Ή-NMR analysis conditions:

NMR system main part: JOEL 300MHz NMR spectrometer

Solvent: D SO (d-6) or CDC13

Chemical shift for monoalkyl polyglycerol ether and polyglycerol are 0.75-5.5ppm.

Example 1 : preparation of dodecyl diglyceryl ether (AGE: Glycerols : 1 .3 in molar ratio, 15Q^°C )

[0043] A 250 mL four-necked flask was charged with 46 g (0.65mol) of glycerol and 2,94g (5.0 mmol) of lanthanum triflate and the reaction flask was then heated to 1 0^°C while stirring under a nitrogen flow. Next, n-dodecyl glycidyl ether (0.5mol) was added gradually over 60 minutes. The reaction was permitted to continue for four hours at 150- 160^°C , after which the reactor was permitted to cool. After completion of the reaction, the product was determined by HPLC, gas chromatography and Ή-NMR analysis. Conversion rate of alkyl glycidyl ether was 100%, there is no unreacted alkyl glycidyl ether by NMR analysis. The dialkyl ether content was 6.3%. ^!H NMR of the product in CDC13: 0.78-0.87 (m, 3H), 1 .16-1 . 19 (m, 1 8H), 1 .45- 1 .52 (m, 2H), 3.3-3.9 (m, 14H).

Example 2: preparation of dodecyl polyglyceryl ether (AGE: PG =1 : 1. 1 , 1 80 °C )

[0044] A 250 mL four-necked flask was charged with 0.55mol polyglycerol having an average of three glycerol units per molecule and 5.0 mmol lanthanum triflate under nitrogen atmosphere, and the solution was heated to 1 80 °C while stirring under a nitrogen flow, n-dodecyl glycidyl ether (0.5mol) was added drop by drop to the solution over 60 minutes. The reaction was permitted to continue for four hours at 180 ^°C . After completion of reaction, the reactor was permitted to cool. The product was determined by HPLC and Ή-NMR analysis. The conversion of alkyl glycidyl ether was 100%, there is no unreacted alkyl glycidyl ether by NMR analysis. The dialkyl ether content was 15.5%. The Ή NMR of product in DMSO (d₆) 0.82-0.85 (m, 3H), 1.22- 1.28 (m, 18H), 1.44- 1.46(m, 2H), 3.31 -3.68 (m, 23H), 4.46-4.77 (m, 5H).

Comparison of foaming properties of monoalkyl glycerol ether and AE07

By the Ross-miles test method; ^b By the drop-weight method

Example 3: preparation of dodecyl polyglyceryl ether (AGE: PG=1 : 1 in molar ratio, 150^°C in DMSO)

[0045] 0.5mol polyglycerol having an average of three glycerol units per molecule and 5.0 mmol lanthanum triflate were dissolved in DMSO in a 250 mL four-necked flask under nitrogen atmosphere, and the solution was heated to 150 ^°C . Then n-dodecyl glycidyl ether (0.5mol) was added drop by drop to the solution over 60 minutes. The reaction was allowed to proceed at 150 °C for four hours. After completion of reaction, dimethyl sulfoxide was distilled off under reduced pressure at 80- 100 ^°C . The product was determined by HPLC and Ή-NMR analysis. The conversion of alkyl glycidyl ether was 98% or more, and the dialkyl ether content was 14.8%.

as catalyst)

[0046] A 250 ml four-necked flask was charged with 0.5mol polyglycerol having an average of three glycerol units per molecule and 5.0 mmol Samarium(III) triflate under nitrogen atmosphere, and the solution was heated to 150- 180 ^°C while stirring under a nitrogen flow. Then n-dodecyl glycidyl ether (O.Smol) was added drop by drop to the solution over 60 minutes. The reaction was permitted to continue for four hours at 150-180 ^°C , after which 5 the reactor was permitted to cool. The product was determined by HPLC and Ή-NMR analysis. The conversion of alkyl glycidyl ether was 100%, there is no unreacted alkyl glycidyl ether by NMR analysis, and the dialkyl ether content was 15.9%, i o Example 5: (lanthanum trisidodecylbenzenesulfonate as catalyst)

[0047] A 250 ml four-necked flask was charged with 0.5mol polyglycerol having an average of three glycerol unites and 5.0 mmol lanthanum tris(dodecylbenzenesulfonate) under nitrogen atmosphere, and the solution was heated to 180 °C while stirring under a nitrogen flow. Then n-dodecyl

1 5 glycidyl ether (0.5mol) was added drop by drop to the solution over 60 minutes. The reaction was permitted to continue for four hours at 180 °C , after completion of reaction, the reactor was permitted to cool. The product was confirmed by HPLC and Ή-NMR analysis. The conversion of alkyl glycidyl ether was 100%, there is no unreacted alkyl glycidyl ether by NMR0 analysis, and the dialkyl ether content was 10.8%.

Example 6: (polyglycerol having average of twenty glycerol unites)

[0048] A 250 ml four-necked flask was charged with 0.5mol polyglycerol having average of 20 glycerol unites and 5,0 mmol lanthanum triflate under5 nitrogen atmosphere, and the solution was heated to 180 ^°C while stirring under a nitrogen flow. Then alkyl (C 12-14) glycidyl ether (0.5mol) was added drop by drop to the solution over 60 minutes. The reaction was permitted to continue for four hours at 180 °C , after completion of reaction, the reactor was permitted to cool. As a result, the product was confirmed by HPLC and0 Ή-NMR analysis. The result showed that the conversion of alkyl glycidyl ether was 98% or more, and the dialkyl ether content was 19%. Example 7: (n-butyl Glycidyl ether)

[0049] A 250 ml four-necked flask was charged with 0.5mol polyglvcerol having average of three glycerol unites and 5.0 mmol lanthanum triflate under nitrogen atmosphere, and the solution was heated to 125 ^°C while stirring under a nitrogen flow. Then n-butyl glycidyl ether (0.5mol) was added drop by drop to the solution over 60 minutes. The reaction was permitted to continue for four hours at 125 ^°C . After the completion of reaction, the product was confirmed by gas chromatography and ¹ H-NMR analysis. As a result, the conversion of alkyl glycidyl ether was 100%, there is no unreacted alkyl glycidyl ether, and the dialkyl ether content was 2.5%.

Example 8: CCis-alkyl Glycidyl ether

[0050] A 250 ml four-necked flask was charged with 0.5mol polyglycerol having average of three glycerol unites and 5.0 mmol lanthanum triflate under nitrogen atmosphere, and the solution was heated to 180 °C while stirring under a nitrogen flow. Then alkyl (Cjg) glycidyl ether (0.5mol) was added drop by drop to the solution over 60 minutes. The reaction was permitted to continue for four hours at 180 °C . After completion of reaction, the product was confirmed by HPLC and ¹ H-NMR analysis. The result showed that the conversion of alkyl glycidyl ether was 97% or more, and the dialkyl ether content was 1 1 .2%.

Example 9: (2-dodecyloxirane with polyglycerol)

[0051] A 250 mL four-necked flask was charged with 0.5mol polyglycerol having an average of three glycerol units per molecule and 5.0 mmol lanthanum triflate under nitrogen atmosphere, and the solution was heated to 1 80 °C while stirring under a nitrogen flow. 2-Dodecyloxirane (0.5mol) was added drop by drop to the solution over 60 minutes. The reaction was permitted to continue for four hours at 180 °C . After completion of reaction, the product was confirmed by HPLC and ¹ H-NMR analysis. The result showed that the conversion of alkyl epoxide was 100%, there is no unreacted alkyl glycidyl ether, and the dialkyl ether content was 9.1 %.

INDUSTRIAL APPLICABILITY [0052] By the process for producing the epoxide derivatives (especially, alkyl glycidyl ether) according to the present invention, it is possible to realize a highly selective addition reaction of an alcohol and alkyl glycidyl ether, and increase a conversion rate of the alcohol,

[0053] In addition, the obtained epoxide derivatives (especially, polyglyceryl ether derivatives) are useful as a solvent, an emulsifier, a dispersant, a cleaning agent, a foaming agent etc. Particularly, the polyglycerol ether derivatives are very useful materials for anionic surfactant, such as sulfate product.

Claims

1. A process for producing an epoxide derivative, comprising reacting an alcohol of formula (I)

R^!(OH)p

I,

wherein R¹ represents the skeleton moiety of the alcohol, p is an integer ranging from 1 to 100, with an epoxide of formula (II)

II, wherein R^" represents a linear or branched alkyl group, q is 0 or 1 , in the presence of a simple metal salt of rare earth element as a catalyst.

2. The process according to claim 1 , wherein q is 1.

3. The process according to claim 1 or 2, wherein the alcohol is a polyol.

4. The process according to claim 1 or 2, wherein the alcohol is selected from the group consisting of glycerol, polyglycerol, or mixtures thereof.

5. The process according to claim 4, wherein the alcohol is a polyglycerol.

6. The process according to claim 5, wherein the polyglycerol contains 2 to 30 glycerol units.

7. The process according to claim 6, wherein the polyglycerol contains 2 to 20 glycerol units.

8. The process according to claim 7, wherein the polyglycerol contains 2 to 10 glycerol units.

9. The process according to claim 8, wherein the polyglycerol contains 3 to 4 glycerol units.

10. The process according to claim 1 or 2, wherein R represents a linear or branched alkyl.

1 1. The process according to claim 10, wherein R² represents a linear or branched C_4-24 alkyl.

12. The process according to claim 1 1 , wherein R represents a linear or branched C₆.2o alkyl.

13. The process according to claim 12, wherein R² represents a linear Cg-is alkyl.

14. The process according to claim 1 or 2, wherein m is an integer ranging from 2 to 10.

15. The process according to claim 1 or 2, wherein the rare earth element is a lanthanide series metal.

16. The process according to claim 1 or 2, wherein the simple metal salt of the rare earth element is in the form of an inorganic acid salt and/or an organic acid salt.

17. The process according to claim 16, wherein the inorganic acid salt of the rare earth element is a perchloric acid salt thereof.

18. The process according to claim 16, wherein the organic acid salt of the rare earth element is a sulfonic acid salt thereof.

19. The process according to claim 1 or 2, wherein the simple metal salt of the rare earth element is used in an amount of from 0.001 to 0.2 mol per 1 mol of the epoxide.

20. The process according to any one of claims 1 to 19, wherein the rare earth element is lanthanum and/or samarium,

21. The process according to claim 1 or 2, wherein the simple metal salt of the rare earth element is lanthanum triflate.

22. The process according to any one of claims 1 , 2 and 4-8, wherein the reaction is carried out in a solvent.

23. The process according to claim 22, wherein the solvent is a polar solvent.

24. The process according to claim 22, wherein the solvent is selected from the group consisting of hexane, diethyl ether, tetrahydrofuran, dichloromethane, acetonitrile, nitromethane, benzene, toluene, xylene, chloroform, dioxane, cyclohexane, dimethyl sulfoxide, dimethylformamide and dimethylacetamide.

25. The process according to claim 24, wherein the solvent is dimethyl sulfoxide.

26. The process according to claim 1 or 2, wherein the reaction is carried out in the absence of solvent.

27. The process according to claim 1 or 2, wherein the reaction is carried out at a temperature of 60 to 300 °C .

28. The process according to claim 1 or 2, wherein the reaction is carried out at a temperature of 120 to 200°C .

29. The process accordmg to claim 1 or 2, wherein the molar ratio of the alcohol to the glycidyl ether is in a range from 0.1 to 40.

30. The process according to claim 1 or 2, wherein the molar ratio of the alcohol to the glycidyl ether is in a range from 0.5 to 20.

31. The process according to claim 1 or 2, wherein the molar ratio of the catalyst to the alcohol is in a range from 0.002 to 0.5.

32. The process according to claim 1 or 2, wherein the reaction is carried out in the absence of solvent and the alcohol is glycerol and/or polyglycerol.

33. A process for preparing a sulfation product of epoxide derivative, comprising a step of sulfating the epoxide derivative obtained by the process according to any one of claims 1 to 32.