JP2005298463A - Ring-opening polymerization method - Google Patents

Abstract

An object of the present invention is to provide a method for adding a ring-opening epoxide to an alcohol and polymerizing it, without having to consider the step of activating the catalyst in advance, and having a high catalytic activity and narrowing the molecular weight distribution of the product. With the goal.
As a result of intensive investigations, the present inventors have made it possible to produce a product with high catalytic activity without the need to pre-activate a catalyst in a method of ring-opening addition and polymerization of epoxides to alcohols. A method for narrowing the molecular weight distribution of a product has been developed and the present invention has been achieved. Specifically, by adding an epoxide to an alcohol and polymerizing it in the presence of a metallocene complex and a Lewis base. The product obtained by the method of the present invention has a narrow molecular weight distribution and can reduce the residual amount of free (unreacted) alcohols.
[Selection figure] None.

Description

The present invention relates to a method for producing an epoxide derivative used for a surfactant, a chemical derivative or the like. Specifically, it relates to a method for ring-opening polymerization of epoxides to alcohols.

Alkoxylates obtained by ring-opening alkylene oxides such as ethylene oxide and propylene oxide to compounds having active hydrogen such as alcohols, phenols, and amines and used for addition polymerization are widely used as surfactants, solvents, and organic intermediates. . Particularly, alkoxylates of alcohols are used in a large amount throughout the world as surfactants, emulsifiers, cleaning agents and the like.

In order to obtain such an alkoxylate, a catalyst is added to the active hydrogen-containing compound, and the reaction is carried out by adding alkylene oxide under atmospheric pressure or pressure under heating. Epoxides other than alkoxylates can be reacted in a similar manner.

The catalyst used in these reactions is generally carried out with an acidic or basic catalyst. Conventionally used catalysts include alkali metals such as lithium, sodium and potassium, basic compounds such as hydroxides, oxides, carbonates and alkoxides, Lewis acids such as boron trifluoride diethyl ether complex, and antimony. And halides such as tin and acidic substances such as sulfuric acid and heteropolyacid.

However, all of these catalysts have drawbacks. For example, when an acidic substance is used as a catalyst, an epoxide cyclic dimer (for example, 1,4-dioxane, for example), a derivative thereof, a homopolymer of epoxide is produced as a by-product, or an acid corrodes a metal. It is often unsuitable as a production catalyst. On the other hand, when a basic compound is used as a catalyst, there are problems that only compounds having a wide distribution of addition polymerization products can be obtained, and that many free (unreacted) active hydrogen-containing compounds remain. In particular, if a large amount of free active hydrogen-containing compound remains, the remaining alcohol smells (Japanese Examined Patent Publication No. 51-43483), and there is a problem in temperature change, especially when it is blended with it. Often occurs.

In order to solve these problems, attempts have been made to narrow the molecular weight distribution of the addition polymer. U.S. Pat. No. 4,239,917 discloses an ethoxylation process using barium oxide as a catalyst. Further, US Pat. No. 4,835,321 and US Pat. No. 4,775,653 disclose alkoxylation methods using a calcium-based mixed catalyst system. J. et al. Chem. Soc. , Chem. Commun. 1985, p. 1148, Macromolecules, 1988, vol. 21, p. 1195, discloses a method for alkoxylation of aluminum with a porphyrin complex. Japanese Patent Laid-Open No. 4-28717 discloses a double metal cyanide complex catalyst. These reports do not satisfy the effect of narrowing the distribution, it is difficult to obtain a catalyst at an industrial level with a porphyrin complex, and it is difficult to use cyanide with a cyanide catalyst from the viewpoint of safety and environment. I can't say that.

In recent years, studies using a composite oxide catalyst or a natural or synthetic mineral as a catalyst have been actively conducted, and Japanese Patent No. 3322587, Japanese Patent No. 3174479, Japanese Patent No. 2784622, Japanese Patent Laid-Open No. There are many reports such as JP-A-505986, JP-A-2-71841, JP-A-6-182206, JP-A-6-198169, JP-B-6-15038, JP-A-11-114417. All of these can be said to be excellent methods for producing alkoxylates having a narrow molecular weight distribution. However, according to Japanese Patent No. 2784622, hydrotalcite calcined as disclosed in Japanese Patent Laid-Open No. 2-71841, that is, complex oxide, needs to be calcined at a high temperature in order to impart catalytic activity. Problems such as complicated processes and unnecessary energy have been pointed out. Even Japanese Patent No. 2784622 using a mineral requires a step of activating the mineral in advance, and it is difficult to say that the above problem has been solved.

That is, there is a need for a method of narrowing the molecular weight distribution of a product in the method of adding an epoxide to an active hydrogen-containing compound, adding and polymerizing the compound, without considering the step of activating the catalyst in advance.

The present inventors have previously proposed a method for narrowing the molecular weight distribution of a product in the method of adding an epoxide to an active hydrogen-containing compound and adding and polymerizing it, without having to take into account the step of activating the catalyst in advance. (Japanese Patent Application No. 2003-413954). This was a catalyst using a metallocene complex and a Lewis acid as a catalyst, but the catalyst activity was low and a long reaction time was required. Therefore, in industrial use, it was disadvantageous from the viewpoint of productivity.

Let me add up. As described above, the reaction between an active hydrogen-containing compound and an epoxide has been actively studied with great interest, and a characteristic compound has been obtained. It is very interesting to narrow the molecular weight distribution of the addition polymer, but not only this kind of research has been conducted, but in order to obtain a characteristic reaction product, as disclosed in JP-A-2002-187951. In addition, studies have been made to improve the primary ratio of the terminal hetero atom group of the heterocyclic compound.
U.S. Pat. No. 4,239,917 U.S. Pat. No. 4,835,321 U.S. Pat. No. 4,775,653 JP-A-4-28717 Japanese Patent No. 3322587 Japanese Patent No. 3174479 Japanese Patent No. 2784622 JP-T 6-505986 JP-A-2-71841 JP-A-6-182206 Japanese Patent Application Laid-Open No. 6-198169 Japanese Examined Patent Publication No. 6-15038 Japanese Patent Laid-Open No. 11-114417 Japanese Patent Application No. 2003-413554 JP 2002-187951 A J. et al. Chem. Soc. , Chem. Commun. 1985, 1148, Macromolecules, 1988, 21: 1195.

An object of the present invention is to provide a method of narrowing the molecular weight distribution of a product with high catalytic activity, without the need to consider the step of activating the catalyst in advance in the method of adding an epoxide by ring-opening to an alcohol and polymerizing it. To do.

As a result of intensive studies, the inventors of the present invention do not need to consider the step of pre-activating the catalyst in the method of ring-opening epoxide to alcohols and adding and polymerizing, and have high catalytic activity and molecular weight distribution of the product. A method of narrowing the width has been developed and the present invention has been achieved.
That is, the ring-opening polymerization method of the present invention is based on the addition and polymerization of epoxides to alcohols in the presence of a metallocene complex and a Lewis base. The product obtained by the method of the present invention has a narrow molecular weight distribution and can reduce the residual amount of free (unreacted) alcohols.

The aforementioned JP-A-2002-187951 also exemplifies titanocene chloride and has similarities to the present invention, but the effects of the present invention cannot be obtained in this publication system. That is, although this publication has similarities to the present invention, it is for obtaining the effects of the publication and not for obtaining the effects of the present invention. In order to obtain the effects of the present invention, the requirements described in detail later are required. It is necessary to satisfy.

According to the present invention, in the method of adding an epoxide by ring-opening to an alcohol and adding and polymerizing it, it is not necessary to consider the step of activating the catalyst in advance, and the molecular weight distribution of the product can be narrowed with high catalytic activity.

The present invention provides a method of reacting an alcohol with an epoxide, characterized by using a metallocene complex and a Lewis base as a catalyst for reacting an epoxide with an alcohol to obtain a polyether compound. That is, a method for ring-opening polymerization of epoxides to alcohols catalyzed by a metallocene complex and a Lewis base. More particularly, the ring-opening polymerization method according to claim 1, wherein the metallocene-type catalyst has a tetravalent metal, and the metallocene-type catalyst is titanium (IV) and / or zirconium. (IV) The ring-opening polymerization method according to claim 1 for epoxides to alcohols having ions, aliphatic amines, aromatic amines and alicyclic amines whose Lewis base does not have active hydrogen The ring-opening polymerization method according to claim 1, wherein the epoxide to an alcohol is selected from one or more of the above, wherein the reaction temperature is 40 ° C to 250 ° C. The ring-opening polymerization method according to claim 1, wherein the reaction is carried out under normal pressure or under pressure. The ring-opening polymerization method according to claim 1, wherein the epoxide is an epoxide to an alcohol whose epoxide is an alkylene oxide and / or glycidol having 2 to 4 carbon atoms, and the metallocene-type catalyst is titanium (IV) and / or zirconium (IV) ion And the Lewis base has no active hydrogen and is an aliphatic amine and / or aromatic amine and / or alicyclic amine, and the epoxide is an alkylene oxide having 2 to 4 carbon atoms and / or glycidol. The ring-opening polymerization method according to claim 1, wherein the metallocene catalyst is titanocene dichloride and / or zirconocene dichloride, and the Lewis base has no active hydrogen, and / or aromatics. Aromatic amines and / or alicyclic amines whose epoxide has carbon number A ring-opening polymerization process of claim 1 wherein the epoxide to alcohol, which is a to 4 alkylene oxide and / or glycidol.

The alcohols used in the present invention may be monovalent or polyvalent. As the alcohols, linear or branched or cyclic saturated or unsaturated alcohols having 2 to 24 carbon atoms are preferable, and alcohols having 8 to 24 carbon atoms are more preferable. Specifically, 1-butanol, 2-butanol, 1-hexanol, 1-octanol, 1-decanol, 1-dodecanol, 1-tetradecanol, 1-hexadecanol, 1-octadecanol, 2-ethyl Monohydric alcohols such as hexanol, 2-octylhexanol, isotridecanol, 2-octyldodecanol, oleyl alcohol, palm alcohol, isostearyl alcohol, isocetyl alcohol, oxo alcohol, ethylene glycol, propylene glycol, glycerin, tri Methylolpropane, sorbitol, hexanetriol, sorbit, diethylene glycol, triethylene glycol, diglycerin, polyglycerin, pentaerythritol, 1,3-butylene glycol, 1,4-butylene Polyhydric alcohols such as recall, 2-ethyl-1,3-hexanediol, 1,5-pentanediol, 2,4-diethylpentanediol, 2-butyl-2-ethyl-1,3-propanediol It is done. These 1 type (s) or 2 or more types are used.

The epoxide used in the present invention is not limited as long as it is an epoxide compound capable of ring-opening polymerization, but reactive active alkylene oxides having 2 to 4 carbon atoms and glycidol are preferable. In addition, α-olefin oxide, epichlorohydrin, glycidyl ethers, glycidyl esters, styrene oxide and the like can be mentioned. In the case of epoxides having low reactivity, a long reaction time is required. These single or 2 or more types of mixtures are used.

As the catalyst used in the present invention, a mixed system of a metallocene complex and a Lewis base is used. As the metallocene type complex, tetravalent metal complexes such as titanocene and zirconocene are preferable. These complexes are composed of a metal ion, a cyclopentadienyl anion, and other ligands, but the biscyclopentadienyl type represented by Chemical Formula 1 and the monocyclopentadienyl type complex represented by Chemical Formula 2 are Illustrated. The cyclopentadienyl ring and other ligands represented by X in these complexes may or may not have a substituent. Other substituents represented by X in the chemical formulas 1 and 2 may be chelate ligands. Specifically, titanocene dichloride (biscyclopentadienyl titanium dichloride), zirconocene dichloride (biscyclopentadienyl zirconium dichloride), cyclopentadienyl titanium trichloride, cyclopentadienyl zirconium trichloride, chloride water Biscyclopentadienyl titanium oxide, biscyclopentadienyl chlorinated chloride, alkoxy biscyclopentadienyl titanium chloride, alkoxy biscyclopentadienyl zirconium chloride, dialkoxy biscyclopentadienyl titanium, dialkoxy biscyclopenta Dienyl zirconium, dimethylaminobiscyclopentadienyl titanium chloride, dimethylaminobiscyclopentadienyl zirconium chloride, cyclopentadienyl rhenium tricarbonyl, biscyclopentadichloride dichloride Etc. Le hafnium are exemplified. Preferably titanocene dichloride, zirconocene dichloride, cyclopentadienyl titanium trichloride, cyclopentadienyl zirconium trichloride, alkoxy biscyclopentadienyl titanium chloride, alkoxy biscyclopentadienyl zirconium chloride, dialkoxy biscyclopentadi Among them, there are enil titanium and dialkoxybiscyclopentadienyl zirconium, and particularly preferred are titanocene dichloride, zirconocene dichloride, alkoxybiscyclopentadienyl titanium chloride, and alkoxybiscyclopentadienyl zirconium chloride. In addition to these, a dimer of a metallocene type complex such as μ-oxobis {chlorobis (cyclopentadienyl) zirconium} may be used, and the structure is not particularly limited as long as it is a metallocene type catalyst. The dimer may be recognized in the catalyst as an impurity or decomposition product of a metallocene catalyst without intentional use.

As the Lewis base, there is no particular problem as long as it is an aliphatic amine, aromatic amine or alicyclic amine having no active hydrogen. Tri-n-octylamine, tributylamine, N, N, N ′, N′-tetramethylethylenediamine, N-methylimidazole, N-methylpyrrole, N-methylpyrazole, 1,3-oxazole, isoxazole, 1, 3-thiazole, isothiazole, pyridine, pyridazine, pyrimidine, pyrazine, N-ethylpyrrolidine, N, N-dimethylpyrazolidine, N, N-dimethylimidazolidine, N-methylisoxazolidine, N-methylisothiazolidine, N -Methylpiperidine, N-morpholine, N, N-dimethylpiperazine, N-methylthiomorpholine, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, dianopyrazine, cyanopyridy , Collidine, quinoline, etc. 1,8-diazabicyclo [5,4,0] undecene -7. Preferred are high boiling point amines such as tri-n-octylamine, N-methylimidazole, 1,8-diazabicyclo [5,4,0] undecene-7.

The use ratio of the metallocene complex to the Lewis base varies depending on the alcohol used and is not particularly limited. Usually, in the case of a monovalent Lewis base with respect to the metallocene type complex, it is desirable to use it at 2 molar equivalents or less. In the case of a divalent Lewis base, it cannot be generally stated due to its molecular structure, but it is preferably used in an amount of 1 molar equivalent or less if there is no steric restriction. The amount of the catalyst used varies depending on the type of alcohol and epoxide, the molar ratio of the two, reaction conditions such as reaction temperature and reaction pressure, but is usually 0.1 to 30% by weight of the alcohol, preferably 1 to 20%. % By weight, more preferably 1 to 10% by weight.

The polymerization method of the present invention can be synthesized by any of batch, semi-batch and continuous methods, but batch and semi-batch methods are preferred.

The reaction temperature is 40 ° C to 250 ° C, preferably 100 ° C to 230 ° C, more preferably 120 ° C to 200 ° C. If the reaction temperature is low, the reaction rate is slow, and if it is too high, decomposition of the product and side reactions are likely to occur and should be avoided.

The reaction pressure is normal pressure or under pressure. When low boiling point ethylene oxide, propylene oxide or the like is used, it is necessary to pressurize. Conversely, when high boiling glycidol, glycidyl ether, long chain α-olefin oxide, or the like is used, pressurization is not necessarily required. Although it is not always necessary, it may dissipate little by little due to the vapor pressure, and it is desirable to be performed under pressure. Specifically, it is desirable that the gauge pressure be 0 to 3.0 MPa, preferably 0 to 1.0 MPa.

These reactions proceed appropriately without using a solvent, but a solvent may be used. It is important that the solvent to be used is not reactive with alcohols, catalysts or epoxides. Of course, you may make it react without using a solvent.

In the method of the present invention, when the number of moles of epoxide added is low, the reaction rate is not improved. However, as exemplified in the examples described later, the reaction rate increases rapidly from the middle of the reaction, resulting in a state of high catalytic activity. In the examples, the case where the epoxide is ethylene oxide is exemplified, and the present invention and an example (Japanese Patent Application No. 2003-413954) using a metallocene type complex and a Lewis acid reported by the present inventors as a catalyst are described. In comparison, when the amount of the catalyst was the same, the reaction rate of the former was improved over the latter when 3 mol of ethylene oxide was added. When an ethylene oxide adduct is substantially industrially utilized, an epoxide adduct of 3 moles or more occupies a large amount, and a high mole number of epoxide adduct is often required. That is, the initial reaction rate is not important, and overall, the reaction needs to be performed with high catalytic activity. The present invention is commensurate with it.

In the method of the present invention, an antioxidant, an anti-coloring agent and the like can be added. It can also be added before or during the reaction. This leads to prevention of oxidation and coloring during the reaction. In addition, if added after the reaction, it leads to stability of the polymer over time.

Examples, comparative examples and reference examples are shown below. The present invention is not limited to these examples.

A stainless steel autoclave with stirring, temperature control mechanism, exhaust pipe, nitrogen inlet, and dropping pipe was charged with 150 g of lauryl alcohol, 5 g of titanocene dichloride and 2.5 g of N-methylimidazole, and thoroughly replaced with nitrogen gas. Oxygen was removed. Under stirring, ethylene oxide was added dropwise at 160 ° C., and 141.7 g of ethylene oxide was reacted while adjusting the reaction temperature to be 170 ± 5 ° C. and the reaction pressure to be 0.3 MPa (gauge pressure). After completion of the dropping, the mixture was kept at the same temperature for about 1 hour and sufficiently aged to confirm that the pressure was sufficiently lowered, and then cooled to obtain polyoxyethylene (4) lauryl ether. The reaction time required about 2 hours. FIG. 1 shows the change over time in the amount of ethylene oxide introduced (drop amount). The reaction time is the time from the start of dropping ethylene oxide to the end of aging after the end of dropping. The obtained polyoxyethylene (4) lauryl ether was subjected to gas chromatography to determine the content for each mole number of ethylene oxide added. For gas chromatography, a sample was subjected to silylation treatment with a silylating agent, and the content was determined by the area ratio of each peak. The measurement results are shown in FIG. In this reaction, even when a stainless steel autoclave was used, corrosion of stainless steel was not observed.

Polyoxyethylene (4) lauryl ether was synthesized under the same conditions as in Example 1 except that the catalyst used was 2 g of titanocene dichloride and 1 g of N-methylimidazole. The reaction time required 5.5 hours. FIG. 1 shows the change over time in the amount of ethylene oxide introduced (drop amount). In addition, the content rate for each number of moles of ethylene oxide added is almost the same as that in the example, and is omitted for simplification in FIG.

Comparative Example 1

A stainless steel autoclave with stirring, temperature control mechanism, exhaust pipe, nitrogen inlet, and dropping pipe was charged with 150 g of lauryl alcohol, 5 g of titanocene dichloride, and 2.5 g of boron trifluoride diethyl ether complex, and nitrogen gas was sufficient. The oxygen was removed by substitution. Under stirring, ethylene oxide was added dropwise at 160 ° C., and 141.7 g of ethylene oxide was reacted while adjusting the reaction temperature to be 170 ± 5 ° C. and the reaction pressure to be 0.3 MPa (gauge pressure). After completion of the dropping, the mixture was kept at the same temperature for about 1 hour and sufficiently aged to confirm that the pressure was sufficiently lowered, and then cooled to obtain polyoxyethylene (4) lauryl ether. The reaction time required about 4 hours. FIG. 1 shows the change over time in the amount of ethylene oxide introduced (drop amount). The obtained polyoxyethylene (4) lauryl ether was allowed to stand, a small amount of sediment was decanted and separated, and the content for each number of moles of ethylene oxide added was determined by gas chromatography. For gas chromatography, a sample was subjected to silylation treatment with a silylating agent, and the content was determined by the area ratio of each peak. The measurement results are shown in FIG. In this reaction, corrosion of stainless steel was not observed even when a stainless steel autoclave was used.

Comparative Example 2

The catalyst used was changed to 5 g of zirconocene dichloride and 2.5 g of boron trifluoride diethyl ether complex, and polyoxyethylene (4) lauryl ether was synthesized under the same conditions as in Comparative Example 1. The reaction time required 5.5 hours. FIG. 1 shows the change over time in the amount of ethylene oxide introduced (drop amount). The measurement result of the content rate for each number of moles of ethylene oxide added by gas chromatography is shown in FIG.

Comparative Example 3

150 g of lauryl alcohol and 0.3 g of potassium hydroxide were charged into a stainless steel autoclave equipped with stirring, a temperature control mechanism, an exhaust pipe, a nitrogen introduction part, and a dropping pipe, and oxygen was removed by thorough substitution with nitrogen gas. Under stirring, ethylene oxide was added dropwise at 160 ° C., and 141.7 g of ethylene oxide was reacted while adjusting the reaction temperature to be 165 ± 5 ° C. and the reaction pressure to be 0.3 MPa (gauge pressure). After completion of dropping, the mixture was kept at the same temperature for 0.5 hours and sufficiently aged, and then cooled to obtain polyoxyethylene (4) lauryl ether. The time required for the reaction was 1.5 hours. After neutralizing with 0.32 g of acetic acid, the content of each mole of ethylene oxide added was determined by gas chromatography. For gas chromatography, a sample was subjected to silylation treatment with a silylating agent, and the content was determined by the area ratio of each peak. The measurement results are shown in FIG.

To a four-necked flask equipped with stirring, temperature control mechanism, reflux tube, nitrogen inlet, and dropping tube, 100 g of 2-butyl-2-ethyl-1,3-propanediol and 5 g of titanocene dichloride, 1,8- While charging 2.5 g of diazabicyclo [5,4,0] undecene-7, starting dropwise addition of glycidol at 140 ° C. with stirring under a nitrogen gas stream, adjusting the reaction temperature to maintain 155 ± 5 ° C., 184.9 g of glycidol was reacted. The dripping took 1.5 hours. After completion of the dropwise addition, the mixture was kept at the same temperature for 1 hour and sufficiently aged, and then cooled to obtain polyglyceryl ether of 2-butyl-2-ethyl-1,3-propanediol (average polymerization degree 4). The molecular weight distribution was determined by gel permeation chromatography. The measurement results are shown in FIG.

Comparative Example 4

In a four-necked flask equipped with stirring, a temperature control mechanism, a reflux tube, a nitrogen inlet, and a dropping tube, 100 g of 2-butyl-2-ethyl-1,3-propanediol and 0.36 g of potassium hydroxide were charged. Glycidol was started to drop at 140 ° C. under stirring in a nitrogen gas stream, and 184.9 g of glycidol was reacted while adjusting the reaction temperature to maintain 150 ± 5 ° C. The dripping took 1.5 hours. After completion of dropping, the mixture was kept at the same temperature for 1 hour and sufficiently aged, then cooled to 90 ° C., neutralized with 0.39 g of acetic acid, and polyglyceryl ether of 2-butyl-2-ethyl-1,3-propanediol (Average polymerization degree 4) was obtained. The molecular weight distribution was determined by gel permeation chromatography. The measurement results are shown in FIG.

A stainless steel autoclave with stirring, temperature control mechanism, exhaust pipe, nitrogen inlet, and dropping pipe was charged with 150 g of lauryl alcohol, 7.4 g of titanocene dichloride, and 3.7 g of N-methylimidazole, and sufficiently replaced with nitrogen gas. Then oxygen was removed. Under stirring, ethylene oxide was added dropwise at 160 ° C., and 283.4 g of ethylene oxide was reacted while adjusting the reaction temperature to be 170 ± 5 ° C. and the reaction pressure to be 0.3 MPa (gauge pressure). After completion of dropping, the mixture was kept at the same temperature for about 1 hour and sufficiently aged to confirm that the pressure was sufficiently lowered, and then cooled to obtain polyoxyethylene (8) lauryl ether. The reaction time required about 2 hours.

A stainless steel autoclave equipped with stirring, temperature control mechanism, exhaust pipe, nitrogen inlet, and dropping pipe was charged with 150 g of lauryl alcohol, 7.4 g of zirconocene dichloride and 3.7 g of N-methylimidazole, and sufficiently replaced with nitrogen gas. Then oxygen was removed. Under stirring, ethylene oxide was added dropwise at 160 ° C., and 283.4 g of ethylene oxide was reacted while adjusting the reaction temperature to be 170 ± 5 ° C. and the reaction pressure to be 0.3 MPa (gauge pressure). After completion of dropping, the mixture was kept at the same temperature for about 1 hour and sufficiently aged to confirm that the pressure was sufficiently lowered, and then cooled to obtain polyoxyethylene (8) lauryl ether. The reaction time required about 3 hours.

The compounds obtained by the present invention can be used as other surfactant raw materials, detergent raw materials, cosmetic raw materials, emulsifiers, solubilizers, and the like. The technique of the present invention can also be applied to addition polymerization reactions of epoxides with active hydrogen compounds other than alcohols.

FIG. 1 is a time change of the amount of ethylene oxide introduced into the reaction system (drop amount) during the reactions of Examples 1 and 2 and Comparative Examples 1 and 2. The horizontal axis represents time, and the vertical axis represents the cumulative amount of ethylene oxide introduced into the reaction system (drop amount). The larger the slope, the faster the reaction and the higher the catalytic activity. In Example 1, it is difficult to say that the catalyst has high catalytic activity in the initial stage of the reaction, but the reaction rate rapidly increases from the middle of the reaction, and the catalyst is in a highly catalytically active state. Example 2 is obtained by reducing the amount of catalyst of Example 1, but has the same tendency as Example 1. The amount of ethylene oxide introduced overtakes Comparative Examples 1 and 2 in which the amount of catalyst is large during the reaction (reaction time). Becomes shorter and becomes highly catalytically active). FIG. 2 is an addition mole number distribution of ethylene oxide of polyoxyethylene (4) lauryl ether obtained in Example 1 and Comparative Examples 1 to 3. The horizontal axis represents the degree of ethoxylation, and the vertical axis represents the area ratio of components at each degree of ethoxylation by gas chromatography. It can be seen that the molecular weight distribution in Example 1 is narrower than that in Comparative Example 3 as in Comparative Examples 1 and 2. FIG. 3 is a gel permeation chromatograph of polyglyceryl ether (average polymerization degree 4) of 2-butyl-2-ethyl-1,3-propanediol obtained in Example 3. The horizontal axis is the retention time, and the vertical axis is the detection intensity. Compared to FIG. 4, it can be seen that Example 3 has a narrower molecular weight distribution than Comparative Example 4. 4 is a gel permeation chromatograph of polyglyceryl ether (average polymerization degree 4) of 2-butyl-2-ethyl-1,3-propanediol obtained in Comparative Example 4. FIG. The horizontal axis is the retention time, and the vertical axis is the detection intensity. Compared to FIG. 3, it can be seen that Comparative Example 4 has a broader molecular weight distribution than Example 3.

Claims (9)

A method of ring-opening polymerization of epoxides to alcohols catalyzed by a metallocene complex and a Lewis base. The ring-opening polymerization method according to claim 1, wherein the metallocene-type catalyst has a tetravalent metal. The ring-opening polymerization method according to claim 1, wherein the metallocene-type catalyst has titanium (IV) and / or zirconium (IV) ions. The epoxide to alcohols according to claim 1, wherein the Lewis base is selected from one or more of aliphatic amines, aromatic amines, and alicyclic amines having no active hydrogen. Ring-opening polymerization method. The ring-opening polymerization method according to claim 1, wherein the reaction temperature is 40 ° C to 250 ° C. The ring-opening polymerization method according to claim 1, wherein the reaction is carried out at normal pressure or under pressure. The ring-opening polymerization method according to claim 1, wherein the epoxide is converted to an alcohol whose epoxide is an alkylene oxide having 2 to 4 carbon atoms and / or glycidol. The metallocene-type catalyst is an aliphatic amine and / or an aromatic amine and / or an alicyclic amine having a titanium (IV) and / or zirconium (IV) ion and a Lewis base having no active hydrogen; The ring-opening polymerization method according to claim 1, wherein the epoxide is an alkylene oxide having 2 to 4 carbon atoms and / or glycidol. The metallocene-type catalyst is titanocene dichloride and / or zirconocene dichloride, the Lewis base is an aliphatic amine and / or aromatic amine and / or alicyclic amine having no active hydrogen, and the epoxide has a carbon number The ring-opening polymerization method according to claim 1, wherein the epoxide to an alcohol is an alkylene oxide and / or glycidol.

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