JP2001055439A - Production of polyether - Google Patents

Abstract

PROBLEM TO BE SOLVED: To readily polymerize a substituted epoxide and efficiently produce a polyether having a high degree of polymerization by polymerizing a monomer component containing a specific epoxide in the presence of a specific rare earth metal compound and an organometallic compound. SOLUTION: A monomer component containing at least one kind of epoxide represented by formula II [R1 is H, a (substituted)1-50C hydrocarbon group or the like; R2 is a substituent group capable of binding to the epoxy ring or same as R1], formula III (R4 is H, a substituent group capable of binding to the epoxy ring or the like), formula IV or formula V in the presence of a rare earth metal compound represented by formula I (M is Sc, Y or a rare earth element selected from lanthanoids; L1 to L3 are each oxygen or a nitrogen- binding ligand and an organometallic compound (e.g. an organoaluminum compound such as trimethylaluminum).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a highly polymerized polyether useful in the cosmetics and chemicals fields, and to a novel polyether.

[0002]

2. Description of the Related Art
It is known that when a substituted epoxide is subjected to ring-opening polymerization, the molecular weight of the product is generally greatly reduced by chain transfer resulting from abstraction of atoms from the substituent. Exceptionally, propylene oxide and epihalohydrin do not show a significant decrease in polymerizability, and a molecular weight of about one million can be obtained by selecting a catalyst system, but other substituted epoxides can obtain a high degree of polymerization polyether with high yield. I couldn't do that.

In recent years, examples of using a composition containing a rare earth metal compound as a polymerization catalyst for ethylene oxide, propylene oxide or epichlorohydrin, for example, I
norg.Chim.Acta, Vol.155, 263 (1989), Polymer J.,
Vol.22, 326 (1990), Macromol.Chem.Phys., Vol.19
6, 2417 (1995). These are all obtained by polymerizing ethylene oxide, propylene oxide, and epichlorohydrin, and are said to have a molecular weight of about one million. However, this polymerization catalyst is comparable to conventional coordination anion catalysts, and polyethers with a high degree of polymerization can be obtained by using them or by polymerizing epoxides other than propylene oxide and epichlorohydrin. Taking into account the fact that no such catalyst was used, it was not expected that a rare earth metal compound, which had a performance comparable to that of a conventional catalyst, would be a useful catalyst for obtaining a highly polymerized polyether from a substituted epoxide.

An object of the present invention is to easily polymerize a substituted epoxide other than propylene oxide and epihalohydrin, which has been extremely difficult or impossible to obtain a high degree of polymerization, and to efficiently obtain a polyether having a high degree of polymerization. It is to provide a method.

[0005]

The present invention provides a compound represented by the general formula (I):

[0006]

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In the formula, R represents a rare earth element selected from M: Sc, Y or lanthanoid. L ¹ , L ² , L ³ : the same or different and represent oxygen or nitrogen binding ligands. ｝, In the presence of a rare earth metal compound and an organometallic compound, a method for producing a polyether for polymerizing a monomer component containing at least one of the epoxides represented by the general formulas (II) to (V), and a novel method. Provides polyether.

[0008]

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In the formula, R ¹ represents a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 50 carbon atoms, an acyl group having 1 to 30 carbon atoms, represents an alkyl sulfonyl group or arylsulfonyl group having 6 to 30 carbon atoms having 1 to 30 carbon atoms, or - a group represented by (AO) n-R ^3. Here, R ³ is a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent,
A -30 fluoroalkyl group, a C1-30 fluoroalkenyl group or a C6-30 fluoroaryl group, or a siloxysilyl group having 1 to 50 silicon atoms. A represents an alkylene group having 2 to 3 carbon atoms, and n represents an average value.
Indicates a number from 1 to 1000. The hydrocarbon group represented by R ¹
A part or all of the hydrogen atoms bonded to the carbon atoms of the acyl group, alkylsulfonyl group and arylsulfonyl group may be substituted by fluorine atoms. R ² represents a substituent capable of bonding to an epoxy ring (hereinafter referred to as a direct bonding substituent) or has the same meaning as R ¹
R ² may be the same or different. However, except that all of R ² are simultaneously hydrogen atoms. ｝

[0010]

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In the formula, R ⁴ represents a hydrogen atom, a direct bonding substituent, a hydrocarbon group having 1 to 50 carbon atoms which may have a substituent, or 1 carbon atom; or showing a 30 acyl group, or an alkyl sulfonyl group or arylsulfonyl group having 6 to 30 carbon atoms having from 1 to 30 carbon atoms ^{- (AO) n-R 3} (R 3, a and n are as above The same meaning), a hydrocarbon group, an acyl group, an alkylsulfonyl group, a part or all of the hydrogen atoms bonded to the carbon atoms of the arylsulfonyl group may be substituted with a fluorine atom And a plurality of R ⁴ may be the same or different. However, except that all of R ⁴ are hydrogen atoms at the same time. In addition, when three of R ⁴ are hydrogen atoms, the remaining one is a carbon atom having no substituent.
Excluding those having 1 to 50 hydrocarbon groups. ｝

[0012]

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(In the formula, R ⁴ has the same meaning as described above, and a plurality of R ⁴ may be the same or different.)

[0014]

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(In the formula, R ⁴ has the same meaning as described above, and a plurality of R ⁴ may be the same or different.)

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS <Epoxide> General formulas (II) to (V)
As a specific example of a hydrocarbon group which may have a substituent at R ¹ and R ⁴ of the epoxide represented by 1 to 50 carbon atoms
Alkyl or alkenyl group, or 6 to 50 carbon atoms
And further includes a hydrocarbon group obtained by combining them. As a substituent of a hydrocarbon group, a halogen atom, diazo group, hydroxyl group, nitrile group, ammonium group, nitro group, isocyanate group, amino group, mercapto group, carboxyl group, carboxylate group, aldehyde group, carbonyl group, ester group , An ether group, an amide group, a sulfide group, a sulfenyl group, a sulfonyl group, a phosphine group, a hypophosphite group, a phosphite group, a phosphate group, a phosphonium group, a silyl group, a siloxy group (hereinafter, referred to as “the present invention Substituent ") and the like.

Preferred examples of the acyl group include those having a total carbon number of 4
To 22 acyl groups, and the hydrocarbon group in this acyl group may be an alkenyl group. Preferred examples of the arylsulfonyl group include a benzenesulfonyl group, a toluenesulfonyl group, and a nitrobenzenesulfonyl group.

Specific examples of the direct bonding substituent for R ² and R ⁴ include the above-mentioned “substituent of the present invention” and the like.

Specific examples of the hydrocarbon group which may have a substituent for R ³ include an alkyl group or alkenyl group having 1 to 30 carbon atoms and an aryl group having 6 to 30 carbon atoms. Examples of the substituent of the group include the above “substituent of the present invention” and the like. Preferred examples of the fluoroalkyl or alkenyl group include trifluoromethyl, pentafluoroethyl, nonafluorobutyl, perfluorohexyl, perfluorooctyl, perfluorododecyl, perfluoro-3-methylbutyl, perfluoro-
5-methylhexyl, perfluoro-7-methyloctyl, perfluoro-9-methyldecyl, 1,1-difluoromethyl, 1,1,2,2-tetrafluoroethyl,
4H-octafluorobutyl, 5H-decafluoropentyl, 6H-dodecafluorohexyl, 8H-hexadecafluorooctyl, 10H-icosafluorodecyl,
Trifluoroethenyl is mentioned, and a preferred example of the fluoroaryl group is perfluorophenyl.

The epoxides represented by the general formulas (II) to (V) can copolymerize two or more kinds. Further, one or more of these can be copolymerized with another epoxide such as ethylene oxide, propylene oxide and / or epihalohydrin. Further, one or more of these can be copolymerized with an anionic polymerizable monomer. As anionic polymerizable monomers, styrene, vinyl naphthalene, 1,
3-butadiene, isoprene, ethylene, 2,3-dimethyl-
1,3-butadiene, 1,3-pentadiene, 1,3-cyclohexadiene, vinylpyridine, (meth) acrylates such as methyl (meth) acrylate, episulfide,
4- or 6- or 7-membered ring lactones, 5- or 6-membered ring carbonates, lactams, cyclic silicones such as D3 (hexamethylcyclotrisiloxane), D4 (octamethylcyclotetrasiloxane), etc., are preferred, but are preferred. Are styrene, 1,3-butadiene, isoprene, methyl methacrylate, β-lactone, and hexamethylcyclotrisiloxane.

<Rare earth metal compound> In the rare earth metal compound represented by the general formula (I), M, Sc, Y, La, C
e, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Y
b and Lu, but from the viewpoint of polymerization activity and economy, S
c, Y, La, Nd, Sm, Eu, Gd, Dy, Er, Yb, Lu are preferred.

L ¹ , L ² and L ³ are ligands having an oxygen or nitrogen bond, such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, butoxy group, allyloxy group, Methoxyethoxy group, phenoxy group, 2-methoxypropoxy group, trifluoroethoxy group, nitrile group, alkylamines (dimethylamine, diethylamine, t-
Butylamine, etc.), diphenylamine, pyridine derivatives (pyridine, di-2-pyridinylethylene, 2,2'-bipyridine, phenanthroline, etc.), pyridazine, trimethylsilylamine, ditrimethylsilylamine, dimethylpyrazolate, hydrazine, benzaldehydeazine, azobenzene, Porphyrins, 2,4-pentanedionate group (acetylacetonate group), trifluoropentanedionate group, hexafluoropentanedionate group, 6,
6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octandionate group, 2,2,6,6-tetramethyl-3,5-heptanedionate group, Thienoyl trifluoroacetate group,
Fluoryl trifluoroacetate group, benzoylacetonate group, benzoyl trifluoroacetate group, acetate group, trifluoroacetate group, methyl acetoacetate group, ethyl acetoacetate group, methyl (trimethyl) acetyl acetate group, 1,3-diphenyl-1 , 3-
Propanedionate group, methyl sulfonate group, trifluoromethyl sulfonate group, dimethyl carbamate group, diethyl carbamate group, nitrite group, hydroxamate group, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetrakismethylenephosphonic acid, hydroxyethylenediaminetriacetic acid, Azomethene H, citraconic acid, iminodiacetic acid, amino acids and the like.

L ¹ , L ² , and L ³ need not all be ligands represented by the same structural formula, and may have other ligands or form salts for charge adjustment. May be.

Among them, i-propoxy group, 2,4-pentanedionate group (acetylacetonate group), trifluoropentanedionate group and hexafluoropentanedionate group are preferred from the viewpoint of polymerization activity and economy. , 2,
A 2,6,6-tetramethyl-3,5-heptanedionate group, an acetate group and a trifluoroacetate group are preferred.

The rare earth metal compound can be easily synthesized, for example, by reacting a rare earth metal halide, oxide, hydroxide, or nitrate with a precursor compound that provides the ligand. These may be used after synthesizing and purifying in advance, or may be used by mixing a rare earth metal compound and a precursor compound that gives the ligand in a polymerization system.

The rare earth metal compound can be used by supporting it on a suitable carrier, if necessary. For example, inorganic oxide carriers, layered silicates such as clay minerals, activated carbon, metal chlorides, other inorganic carriers, organic carriers, etc. Any of the carriers may be used.
In addition, a known method can be appropriately used as the supporting method.

The amount of the rare earth metal compound to be used may be appropriately determined according to the polymerization ability of the compound, the polymerization ability and the amount of the monomer used, and the desired degree of polymerization and the total amount of the polymerization inhibitor present in the polymerization system. For example, based on the number of moles of the monomer, preferably 0.000001 to 10 equivalents, more preferably
It is 0.0001 to 5 equivalents, more preferably 0.002 to 2 equivalents.
When the amount is 0.000001 equivalent or more, a high polymerization activity is obtained, and when the amount is 10 equivalents or less, formation of a low molecular weight polymer can be suppressed.

<Organometallic Compound> The organometallic compound reacts with all or a part of the rare earth metal compound represented by the general formula (I) and generates any rare earth metal species having extremely high polymerization activity. Often, (i) an organoaluminum compound such as trimethylaluminum, triethylaluminum, triisobutylaluminum, or a binary catalyst of these and water, or a ternary catalyst obtained by adding an alcohol or a chelate compound thereto; Alkoxide, (iii) dialkylaluminum alkoxide, (i
v) dialkylaluminum hydride, (v) alkylaluminum dialkoxide, (vi) methylaluminoxane,
(vii) organoaluminum sulfate, (viii) dimethyl zinc,
A binary catalyst of an organic zinc compound such as diethyl zinc and water,
Or a ternary catalyst to which an alcohol or a chelate compound is added, (ix) a zinc alkoxide, (x) an organolithium compound such as an alkyllithium, and a mixture thereof with water,
(xi) Organic magnesium compounds such as alkylmagnesium, and mixtures thereof with water, (xii) other organic or inorganic compounds having reactivity can be used. Among them, (i), (vi), (viii) and (xi) are preferable.

These organometallic compounds may be used after being mixed and reacted with a rare earth metal compound in advance, or may be used after being mixed in a polymerization system. When used after mixing and reacting in advance, keep at an appropriate temperature,
It may be used after aging, and the aging operation can further increase the polymerization activity.

The amount of the organometallic compound used depends on its reactivity,
What is necessary is just to determine suitably according to the kind and use amount of a rare earth metal compound. Organometallic compounds, aluminum, zinc,
In the case of a compound containing a metal such as lithium and magnesium, the number of moles of the metal species is preferably 0.001 to 200 equivalents, more preferably 0.01 to 100 equivalents, based on the number of moles of rare earth metal species used. And 0.1 to 50 equivalents is particularly preferred. When the amount is 0.001 equivalent or more, high polymerization activity is obtained, and when the amount is 200 equivalents or less, formation of a low molecular weight polymer can be suppressed.

<Epoxide Ring-Opening Polymerization> In carrying out the present invention, the polymerization temperature is -78 to 220 ° C., particularly -30 to 160 ° C.
C. is preferred. The polymerization of epoxide in the molten state in the polymerization temperature range can be performed without solvent,
Usually, it is desirable to carry out the reaction in an inert solvent. Examples of such a solvent include hydrocarbons such as benzene, toluene, xylene, ethylbenzene, n-pentane, n-hexane, n-heptane, isooctane, and cyclohexane, and ethers such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, and dioxane. And halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, N, N-dimethylsulfoxide, and mixtures thereof. These polymerization solvents are preferably used after being sufficiently dehydrated and degassed. Further, the polymerization of the epoxide in a gaseous state in the polymerization temperature range can be performed in an epoxide gas stream.

The polymerization reaction of the present invention is desirably carried out under conditions excluding oxygen. Specifically, it is desirable to carry out the reaction under an atmosphere of an inert gas such as nitrogen, helium, argon, etc., under a reduced pressure of deaeration, a sealed vapor of a deaeration solvent, or an epoxide stream. The polymerization pressure may be any of normal pressure, pressurization and reduced pressure.

The polymerization reaction of the present invention can be carried out by any mixing method. The epoxide, the rare earth metal compound and the organometallic compound may be mixed at once, or one or two of them may be mixed in advance. The remaining two or one may be added to the system containing

In practicing the present invention, one or more epoxides of the general formulas (II) to (V) can be used. These can be used in combination with other epoxides such as ethylene oxide, propylene oxide and epichlorohydrin. When two or more epoxides are used, they may be mixed and used simultaneously, or may be sequentially introduced into a polymerization system.

Further, in carrying out the present invention, one or more of the epoxides of the general formulas (II) to (V) and one or more of the anionic polymerizable monomers other than the epoxide can be used in combination. These may be used by mixing at the same time, or may be sequentially introduced into the polymerization system.

<Polyether> The polyether obtained by the production method of the present invention is represented by, for example, general formulas (VI) to (X).

[0037]

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[0038] {wherein, R ^1, R ^2: the same meanings as R ^1, R ² in the general formula (II). However, at least one of R ² is a direct bonding substituent or a hydrocarbon group having 6 or more carbon atoms. a: The average value is a number of 10 or more, preferably 50 or more, more preferably 150 to 1,000,000. ｝

[0039]

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[0040] {wherein, R ^4: the same meaning as R ⁴ in the general formula (III). However, at least one of R ⁴ is a direct bonding substituent or a hydrocarbon group having 6 or more carbon atoms. b: The average value indicates a number of 10 or more, preferably 50 or more, more preferably 150 to 1,000,000. ｝

[0041]

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[0042] {wherein, R ^4: the same meaning as R ⁴ in the general formula (IV). However, at least one of R ⁴ is a direct bonding substituent or a hydrocarbon group having 6 or more carbon atoms. d: The average value is a number of 10 or more, preferably 50 or more, more preferably 150 to 1,000,000. ｝

[0043]

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[0044] {wherein, R ^4: the same meaning as R ⁴ in the general formula (V). However, at least one of R ⁴ is a direct bonding substituent or a hydrocarbon group having 6 or more carbon atoms. e: The average value indicates a number of 10 or more, preferably 50 or more, more preferably 150 to 1,000,000. ｝

[0045]

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In the formula, X and Y represent any two of the structural units represented by the general formulas (VI) to (IX) and other epoxide or other anionic polymerizable structural units. However, at least one of X and Y has a structural unit represented by any of the general formulas (VI) to (IX), except that X and Y are the same. f, g: the average value indicates a number of 10 or more, preferably
It is 50 or more, more preferably 150 to 1,000,000. ｝ Here, specific examples of other epoxides include ethylene oxide, propylene oxide, epihalohydrin, etc., and specific examples of anionic polymerizable structural units include styrene, methyl methacrylate, methyl acrylate, ethylene, isoprene, butadiene, D3, D4, Examples include structural units derived from lactone and the like.

The copolymer represented by the general formula (X) is a binary or higher copolymer. In the general formula (X), X and Y may be of a random type or a block type.

[0048]

EXAMPLES <Catalyst preparation and polymerization>
The test was performed under a dry nitrogen atmosphere. Various solvents used were dried, distilled and degassed after drying. As the rare earth metal compound and other inorganic compounds, commercially available high-purity products were used as they were. Methylalumoxane (hereinafter referred to as MAO) solution (the toluene solution used here has an aluminum concentration of 1
0.2% by weight) and diethylzinc used were commercial products as they were.

Catalyst Preparation Example 1 0.9296 g of samarium triisopropoxide was weighed, and 23.83 ml of toluene was added and stirred. MAO at room temperature with stirring
5.06 ml (6 equivalents) of the solution was added dropwise, and catalyst A (Sm / Al (molar ratio)
= 1/6) was adjusted.

Catalyst Preparation Example 2 Samarium tris (tetramethylheptane dionate)
0.5192 g was weighed, 7.20 ml of toluene was added, and the mixture was heated and stirred. After cooling to room temperature, 0.22 ml (1 equivalent) of a MAO solution was added dropwise with stirring to prepare catalyst B (Sm / Al (molar ratio) = 1/1).

Example 1 Poly (2-methylglycidyl-4-nitrobenzoate): In the general formula (VI), R ¹ = 4-nitrobenzoyl, R ² = methyl, hydrogen atom × 2 2-methylglycidyl-4- 4 g of nitrobenzoate was placed in a vessel purged with nitrogen, and 5.7 ml of toluene was added and dissolved.
After 1.00 ml of Catalyst A was added thereto, the vessel was sealed and polymerized at 130 ° C. with stirring. After completion of the polymerization, the reaction solution was added to acetone to which a small amount of dilute hydrochloric acid was added. The precipitated white solid was dried under reduced pressure at 80 ° C. for 24 hours to obtain poly (2-methylglycidyl-4-nitrobenzoate). 80% yield.

According to GPC analysis (130 ° C., o-dichlorobenzene, molecular weight in terms of polystyrene), number average molecular weight (Mn) = 5
10,000, weight average molecular weight (Mw) = 1.05 million. The measurement was performed using a Waters 150C model, and the column was a Showa Denko Sh
One odexHT-806M and two ShodexHT-803 were used. In the following Examples and Comparative Examples, measurement was performed at 130 ° C. under these conditions.

Example 2 Poly (2-methylglycidyl-4-nitrobenzoate): In the general formula (VI), R ¹ = 4-nitrobenzoyl, R ² = methyl, hydrogen atom × 2. A polyether was obtained in the same manner as in Example 1 except that was used. 95% yield. G
According to PC analysis (130 ° C.), Mn was 120,000 and Mw was 1.5 million.

Example 3 Poly (2,3-epoxybutane): In the general formula (VII), R ⁴ = methyl × 2, hydrogen atom × 2 2,4-epoxybutane 4 g was placed in a container purged with nitrogen, and toluene was added. 5.7 ml was added and dissolved. After adding 1.50 ml of catalyst B, the vessel was sealed and polymerized at 130 ° C. with stirring. After the polymerization was completed, the container was opened, and the reaction solution was added to acetone to which a small amount of dilute hydrochloric acid was added. 80 ° C of the precipitated white solid
And dried under reduced pressure for 24 hours to obtain poly (2,3-epoxybutane). 80% yield. According to GPC analysis (130 ° C.), Mn = 12,000, Mw =
150,000.

Example 4 Poly (diethyl epoxysuccinate): In the general formula (VII), R ⁴ = COOC ₂ H ₄ × 2, hydrogen atom × 2, 4 g of diethyl epoxysuccinate was polymerized in the same manner as in Example 3. Thus, poly (diethyl epoxy succinate) was obtained. yield
88%. According to GPC analysis (130 ° C.), Mn was 12,000 and Mw was 150,000.

Example 5 Poly (2-methylglycidyl-4-nitrobenzoate / methylglycidylether): In the general formula (X),

[0057]

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3 g of 2-methylglycidyl-4-nitrobenzoate and 2 g of methyl glycidyl ether were placed in a container purged with nitrogen, and 5.7 ml of toluene was added to dissolve. After adding 1.50 ml of catalyst B to this, the container is sealed, and while stirring,
Polymerized at 130 ° C. After the polymerization was completed, the container was opened, and the reaction solution was added to acetone to which a small amount of dilute hydrochloric acid was added. The precipitated white solid was dried under reduced pressure at 80 ° C. for 24 hours to obtain a copolymer.
Yield 92%. According to GPC analysis (130 ° C.), Mn was 12,000 and Mw was 150,000. According to NMR analysis, the composition of the copolymer was 2-methylglycidyl-4-nitrobenzoate: methylglycidylether = 40: 60.

Example 6 Poly (2-methylglycidyl-4-nitrobenzoate / 2,3
-Epoxybutane): In the general formula (X),

[0060]

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3 g of 2-methylglycidyl-4-nitrobenzoate and 2 g of 2,3-epoxybutane were copolymerized in the same manner as in Example 5 to obtain a copolymer. According to GPC analysis, Mn = 2
10,000, Mw = 200,000. According to NMR analysis, the composition of the copolymer was 2-methylglycidyl-4-nitrobenzoate: 2,3
-Epoxybutane = 30: 70.

Example 7 Poly (bischloromethyloxetane): In the general formula (VIII), R ⁴ = hydrogen atom × 4, chloromethyl × 2 Bischloromethyloxetane 4 g was placed in a vessel purged with nitrogen, and 5.7 ml of toluene was added. It was added and dissolved. This is followed by catalyst B1.
After adding 50 ml, seal the container and stir at 130 ° C.
Was polymerized. After the polymerization was completed, the container was opened, and the reaction solution was added to acetone to which a small amount of dilute hydrochloric acid was added. The precipitated white solid was dried under reduced pressure at 80 ° C. for 24 hours to obtain poly (bischloromethyloxetane). Yield 70%. According to GPC analysis (130 ° C.), Mn = 8,000 and Mw = 20,000.

Example 8 Poly (2,5-dimethyltetrahydrofuran): General formula (IX)
R ⁴ = methyl × 2, hydrogen atom × 6 2,5-dimethyltetrahydrofuran 4 g was polymerized in the same manner as in Example 7 to obtain poly (2,5-dimethyltetrahydrofuran).
2.2 g were obtained. According to GPC analysis (130 ° C.), Mn = 3,000, Mw = 1.2
It was 10,000.

Comparative Example 1 A catalyst obtained by mixing triethylaluminum / water / acetylacetone in a molar ratio of 1 / 0.5 / 1 instead of catalyst A
2-Methylglycidyl-4-nitrobenzoate was polymerized by the method described in Example 1 except that a 0.1 M toluene solution was used. Yield 3%. According to GPC analysis (130 ° C.), the polymer had Mn = 5000 and Mw = 20,000.

Comparative Example 2 The procedure of Example 1 was repeated except that a 0.1M toluene solution of a catalyst obtained by mixing diethylzinc / 1-methoxy-2-propanol at a molar ratio of 1 / 0.5 was used instead of the catalyst A. Was used to polymerize 2-methylglycidyl-4-nitrobenzoate. Yield 35%. According to GPC analysis (130 ° C.), the polymer had Mn =
It was 15,000 and Mw = 60,000.

Comparative Example 3 2-methylglycidyl was prepared in the same manner as in Example 1 except that 0.75 g of cesium hydroxide was used instead of Catalyst A.
-4-Nitrobenzoate was polymerized. After the reprecipitation operation,
No solids were obtained. 0% yield

Comparative Example 4 A catalyst obtained by mixing triethylaluminum / water / acetylacetone in a molar ratio of 1 / 0.5 / 1 instead of catalyst B
Diethyl epoxysuccinate was polymerized by the method described in Example 4 except that a 0.1 M toluene solution was used. After the reprecipitation operation, no solid was obtained. 0% yield

Comparative Example 5 A catalyst obtained by mixing triethylaluminum / water / acetylacetone in a molar ratio of 1 / 0.5 / 1 instead of catalyst B
2-Methylglycidyl-4-nitrobenzoate and methylglycidylether were copolymerized by the method described in Example 5 except that a 0.1 M toluene solution was used. Yield 12%. GP
According to C analysis (130 ° C.), Mn was 12,000 and Mw was 150,000. N
According to the MR analysis, the composition of the copolymer was 2-methylglycidyl-4-nitrobenzoate: methylglycidyl ether = 0: 100, and no copolymer was obtained.

Comparative Example 6 A catalyst obtained by mixing triethylaluminum / water / acetylacetone in a molar ratio of 1 / 0.5 / 1 instead of catalyst B
Bischloromethyloxetane was polymerized by the method described in Example 7 except that a 0.1 M toluene solution was used. Yield 5%. According to GPC analysis (130 ° C.), Mn = 5,000 and Mw = 15,000.

Comparative Example 7 A catalyst obtained by mixing triethylaluminum / water / acetylacetone in a molar ratio of 1 / 0.5 / 1 instead of catalyst B
2,5-Dimethyltetrahydrofuran was polymerized by the method described in Example 8 except that a 0.1 M toluene solution was used.
After the reprecipitation operation, no solid was obtained. 0% yield

[0071]

According to the present invention, a highly polymerized polyether useful in the fields of cosmetics and chemicals can be easily provided in good yield.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Taku Oda 1334 Minato, Wakayama-shi, Wakayama F-term in Kao Research Institute (reference) 4J005 AA09 BB04

Claims (3)

[Claims] 1. A compound of the general formula (I) In the formula, a rare earth element selected from M: Sc, Y or lanthanoid is shown. L ¹ , L ² , L ³ : the same or different and represent oxygen or nitrogen binding ligands. A method for producing a polyether, which comprises polymerizing a monomer component containing at least one of the epoxides represented by the general formulas (II) to (V) in the presence of the rare earth metal compound represented by｝ and the organometallic compound. Embedded image In the formula, R ¹ represents a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 50 carbon atoms, an acyl group having 1 to 30 carbon atoms, or 1 carbon atom. or showing a 30 alkylsulfonyl group or an arylsulfonyl group having 6 to 30 carbon atoms, or - a group represented by (AO) n-R ^3. Here, R ³ is a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent,
A -30 fluoroalkyl group, a C1-30 fluoroalkenyl group or a C6-30 fluoroaryl group, or a siloxysilyl group having 1 to 50 silicon atoms. A represents an alkylene group having 2 to 3 carbon atoms, and n represents an average value.
Indicates a number from 1 to 1000. The hydrocarbon group represented by R ¹
A part or all of the hydrogen atoms bonded to the carbon atoms of the acyl group, alkylsulfonyl group and arylsulfonyl group may be substituted by fluorine atoms. R ² represents a substituent capable of bonding to the epoxy ring or has the same meaning as R ^1, and three R ^{2 s} may be the same or different.
However, except that all of R ² are simultaneously hydrogen atoms. ｝ (3) In the formula, R ⁴ represents a hydrogen atom, a substituent capable of bonding to an epoxy ring, a hydrocarbon group having 1 to 50 carbon atoms which may have a substituent, or 1 carbon atom. Showing ~ 30 acyl groups,
C1-C30 alkylsulfonyl group or C6-C6
Or shows a 30 arylsulfonyl group ^{- (AO) n-R 3} (R
³ , A and n have the same meanings as described above), and part or all of the hydrogen atoms bonded to carbon atoms of the hydrocarbon group, the acyl group, the alkylsulfonyl group, and the arylsulfonyl group are fluorine. It may be substituted with an atom, and a plurality of R ⁴ may be the same or different. However, except that all of R ⁴ are hydrogen atoms at the same time. Also out of R ⁴
When three are hydrogen atoms, the other one is a hydrocarbon group having 1 to 50 carbon atoms which has no substituent. ｝ (In the formula, R ⁴ has the same meaning as described above, and a plurality of R ⁴ may be the same or different.) (In the formula, R ⁴ has the same meaning as described above, and a plurality of R ⁴ may be the same or different.) 2. A polyether represented by any one of formulas (VI) to (IX). Embedded image {Wherein, R ^1, R ^2: the same meanings as R ^1, R ² in the general formula (II). However, at least one of R ² is a substituent capable of bonding to an epoxy ring or a hydrocarbon group having 6 or more carbon atoms. a: The number whose average value is 10 or more is shown. ｝ {Wherein, R ^4: the same meaning as R ⁴ in the general formula (III). However, at least one of R ⁴ is a substituent capable of bonding to the epoxy ring or a hydrocarbon group having 6 or more carbon atoms. b: The number whose average value is 10 or more. ｝ {Wherein, R ^4: the same meaning as R ⁴ in the general formula (IV). However, at least one of R ⁴ is a substituent capable of bonding to the epoxy ring or a hydrocarbon group having 6 or more carbon atoms. d: The number whose average value is 10 or more is shown. ｝ {Wherein, R ^4: the same meaning as R ⁴ in the general formula (V). However, at least one of R ⁴ is a substituent capable of bonding to the epoxy ring or a hydrocarbon group having 6 or more carbon atoms. e: The number whose average value is 10 or more is shown. ｝ 3. A polyether represented by the general formula (X). Embedded image In the formula, X, Y: arbitrary two of the structural units represented by the general formulas (VI) to (IX) and other epoxide or other anionic polymerizable structural units. However, at least one of X and Y has a structural unit represented by any of the general formulas (VI) to (IX), except that X and Y are the same. f, g: The average values indicate numbers of 10 or more, respectively. ｝