JP5405363B2 - Method for producing osmium-supported catalyst composition - Google Patents

Description

  The present invention relates to a method for producing an osmium-supported catalyst composition with less leakage of an osmium catalyst from a support even after repeated use, and an osmium-supported catalyst composition obtained thereby.

  Recently, a catalyst composition in which a metal catalyst is supported on a polymer using microencapsulation has been developed, and a report of a catalyst composition in which a metal catalyst is physically supported on a polymer has been reported because of the advantage that the catalyst can be used repeatedly. (Patent Document 1).

  However, a catalyst composition in which a metal catalyst is physically supported on such a polymer has a problem that the activity of the catalyst is reduced by repeated use. Therefore, it has been reported that by using a cross-linked polymer as a carrier, the catalyst composition has little leakage of the metal catalyst and its activity does not decrease (Patent Document 2).

  However, even with such a catalyst composition, since the metal catalyst gradually leaks from the catalyst, there is a problem that the catalytic activity is lowered by repeated use of the catalyst multiple times. Therefore, it has been desired to develop a catalyst composition with almost no leakage of the metal catalyst.

JP 11-314038 JP 2002-66330

  The present invention is obtained by a method for synthesizing an osmium catalyst composition that can be recovered and reused after the reaction as in the case of the conventional catalyst composition, and almost no catalyst leaks from the catalyst composition, and the method. An object of the present invention is to provide an obtained osmium-supported catalyst composition.

［式中、Ｒ₁₀〜Ｒ₁₂は、それぞれ独立して水素原子又は炭素数１〜６のアルキル基を表し、Ｒ₁₃は、炭素数６〜１０のアリーレン基（その芳香環が炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基及び／又はハロゲン原子を置換基として有するものも含む）を表し、Ｒ₁₄は、下記一般式[31]で示される基

（式中、Ｒ₄₀は、炭素数１〜６のアルキレン基を表し、Ｒ₄₁は、酸素原子を鎖中に有する若しくは有さない炭素数１〜２０のアルキレン基を表す）である。］を共重合することにより得られるコポリマーを用いて、コポリマーそれぞれにオスミウム触媒を担持させ、次いで混合した後架橋反応に付すことにより、或いは、上記２種類のコポリマーの混合物にオスミウム触媒を担持させた後架橋反応に付すことにより、漏れが非常に少ないオスミウム触媒組成物が得られることを見出し、本発明を完成させるに至った。 As a result of diligent research to solve the above problems, the present inventors have found that there are two types of specific binary copolymers: (1) styrenic monomers and (2) aromatic groups having an epoxy group and polymerizable duplexes. A copolymer obtained by copolymerizing a monomer containing a bond, (1) a styrene monomer, and (2) a hydrophilic group-containing monomer represented by the following general formula [3]

[Wherein, R _{10 to} R ₁₂ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ₁₃ represents an arylene group having 6 to 10 carbon atoms (the aromatic ring having 1 to 6 carbon atoms). 4 alkyl groups, alkoxy groups having 1 to 4 carbon atoms and / or those having a halogen atom as a substituent, and R ₁₄ is a group represented by the following general formula [31]

(Wherein R ₄₀ represents an alkylene group having 1 to 6 carbon atoms, and R ₄₁ represents an alkylene group having 1 to 20 carbon atoms with or without an oxygen atom in the chain). The osmium catalyst is supported on each of the copolymers and then mixed and then subjected to a crosslinking reaction, or the mixture of the two types of copolymers is supported on the osmium catalyst. It has been found that an osmium catalyst composition with very little leakage can be obtained by post-crosslinking reaction, and the present invention has been completed.

  The osmium catalyst composition obtained by the method as described above has excellent solvent resistance regardless of the type of solvent, and can be reused without the problem of leakage of metal clusters depending on the type of reaction. .

（式中、Ｒ₁₀〜Ｒ₁₄は、上記と同じ）を共重合することにより得られるコポリマーのそれぞれにオスミウム触媒を担持させ、次いで混合した後、或いは、
（II）（1）スチレン系モノマー並びに（2）エポキシ基を有する芳香族基及び重合性二重結合を含有するモノマーを共重合することにより得られるコポリマーと、（1）スチレン系モノマー並びに（2）下記一般式[３]で示される親水性基含有モノマー

（式中、Ｒ₁₀〜Ｒ₁₄は、上記と同じ）を共重合することにより得られるコポリマーとの混合物にオスミウム触媒を担持させた後、得られたオスミウム担持ポリマーを架橋反応に付すことを特徴とする、オスミウム担持触媒組成物の製造方法、並びに該方法により得られるオスミウム触媒組成物に関する。 That is, the present invention relates to (I) (1) a styrene monomer and (2) a copolymer obtained by copolymerizing an aromatic group having an epoxy group and a monomer containing a polymerizable double bond, and (1) Styrene monomer and (2) hydrophilic group-containing monomer represented by the following general formula [3]

(Wherein R _{10 to} R ₁₄ are the same as above) each of the copolymers obtained by copolymerizing an osmium catalyst and then mixing, or
(II) a copolymer obtained by copolymerizing (1) a styrenic monomer and (2) a monomer containing an aromatic group having an epoxy group and a polymerizable double bond; and (1) a styrenic monomer and (2 ) Hydrophilic group-containing monomer represented by the following general formula [3]

(Wherein R _{10 to} R ₁₄ are the same as above), after a osmium catalyst is supported on a mixture with a copolymer obtained by copolymerization, the obtained osmium-supported polymer is subjected to a crosslinking reaction. And a method for producing an osmium-supported catalyst composition, and an osmium catalyst composition obtained by the method.

  According to the production method of the present invention, since two kinds of specific binary copolymers are used for the crosslinking reaction, the metal catalyst is firmly supported on the polymer, leakage of the metal catalyst is almost eliminated, and recovery and reuse are easy. It is possible to provide a catalyst composition. Further, the production method of the present invention using two types of binary copolymers has an effect that the production time can be shortened as compared with the conventional method of producing a osmium-supported catalyst composition using one type of ternary copolymer.

  In addition, when the osmium-supported catalyst composition of the present invention is used, the leakage of the metal catalyst can be suppressed to 2% or less regardless of the type of the solvent or the type of reaction, so the amount of the osmium catalyst leaked into the reaction solution As a result, there is an excellent effect that there is almost no decrease in catalytic activity.

（Ｒ₁〜Ｒ₃は、それぞれ独立して水素原子又は炭素数１〜６のアルキル基を表し、Ｒ_４は、炭素数６〜１０のアリール基を表し、これらアリール基は、その芳香環が、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基及び／又はハロゲン原子を置換基として有するものも含む。）で示されるモノマーが挙げられる。 [Styrene monomer according to the present invention]
As the styrenic monomer according to the present invention, for example, a monomer represented by the following general formula [1]

(R _{1 to} R ₃ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ₄ represents an aryl group having 6 to 10 carbon atoms, and these aryl groups have an aromatic ring. And those having an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and / or a halogen atom as a substituent.

The alkyl group represented by R _{1 to} R ₃ in the general formula [1] may be linear, branched or cyclic, and usually has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 4 carbon atoms. Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Examples include isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like.

Preferable specific examples of R _{1 to} R ₃ include a methyl group and a hydrogen atom, and a hydrogen atom is more preferable.

Examples of the aryl group represented by R ₄ in the general formula [1] include those usually having 6 to 10 carbon atoms, preferably 6 carbon atoms. Specific examples include a phenyl group and a naphthyl group. Groups are preferred.

When the aromatic ring of the aryl group represented by R ₄ in the general formula [1] has a substituent, the alkyl group as the substituent may be linear or branched, and usually has 1 to 4 carbon atoms. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc. Examples of the alkoxy group may be linear or branched, and usually include those having 1 to 4 carbon atoms. Specifically, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, An isobutoxy group, a sec-butoxy group, a tert-butoxy group and the like can be mentioned. Examples of the halogen atom as a substituent include a chlorine atom, a fluorine atom, a bromine atom and an iodine atom. In general, 1 to 5 and preferably 1 to 2 of the aromatic ring of the aryl group represented by R ₄ is substituted with such a substituent.

  Preferable specific examples of the styrene monomer according to the present invention include, for example, styrene, α-methylstyrene, β-methylstyrene, α-ethylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and the like. Of these, styrene and α-methylstyrene are preferable, and styrene is particularly preferable.

［Ｒ_５〜Ｒ_７は、それぞれ独立して水素原子又は炭素数１〜６のアルキル基を表し、Ｒ_８は、炭素数６〜１０のアリーレン基又は炭素数７〜１２のアリールアルキレン基（該アリーレン基及びアリールアルキレン基は、その芳香環が炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基及び／又はハロゲン原子を置換基として有するものも含む）を表し、Ｒ_９は、下記一般式［２１］又は［２２］で示されるエポキシ基を含有する基

（式中、Ｒ₂₁及びＲ₂₅は、炭素数１〜６のアルキレン基を表し、Ｒ₂₂及びＲ₂₆は、酸素原子を鎖中に有する若しくは有さない炭素数１〜２０のアルキレン基を表し、Ｒ₂₃、Ｒ₂₄、Ｒ₂₇及びＲ₂₈は夫々独立して水素原子又は炭素数１〜６のアルキル基、炭素数６〜１０のアリール基又は炭素数７〜１２のアラルキル基を表し、該アリール基及びアラルキル基は、その芳香環が、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基及び／又はハロゲン原子を有するものも含む。）］で示されるモノマーが挙げられる。 [Monomer containing an aromatic group having an epoxy group and a polymerizable double bond according to the present invention]
As a monomer containing an aromatic group having an epoxy group and a polymerizable double bond according to the present invention, for example, a monomer represented by the following general formula [2]

[R _{5 to} R ₇ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ₈ represents an arylene group having 6 to 10 carbon atoms or an arylalkylene group having 7 to 12 carbon atoms (this An arylene group and an arylalkylene group include those having an aromatic ring having an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms and / or a halogen atom as a substituent, and R ₉ is Group containing an epoxy group represented by the following general formula [21] or [22]

(In the formula, R ₂₁ and R ₂₅ represent an alkylene group having 1 to 6 carbon atoms, and R ₂₂ and R ₂₆ represent an alkylene group having 1 to 20 carbon atoms with or without an oxygen atom in the chain. , R ₂₃ , R ₂₄ , R ₂₇ and R ₂₈ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 12 carbon atoms, Examples of the aryl group and the aralkyl group include monomers having an aromatic ring having an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and / or a halogen atom.

In the general formula [2], the alkyl group represented by R _{5 to} R ₇ may be linear, branched or cyclic, and usually has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 4 carbon atoms. Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Examples include isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like.

Preferable specific examples of R _{5 to} R ₇ include a methyl group and a hydrogen atom, and a hydrogen atom is more preferable.

Examples of the arylene group represented by R ₈ in the general formula [2] include those having 6 to 10 carbon atoms, and preferably 6 carbon atoms. Specific examples include a p-phenylene group, an o-phenylene group, an m-phenylene group, and a naphthylene group.

Examples of the arylalkylene group represented by R ₈ in the general formula [2] usually include those having 7 to 12 carbon atoms. Specifically, for example, a phenylmethylene group, a phenylethylene group, a 1-phenylpropylene group, Examples include 2-phenylpropylene group, 1-phenylbutylene group, 2-phenylbutylene group, naphthylmethylene group, naphthylethylene group, and the like.

When the aromatic ring of the arylene group or arylalkylene group represented by R ₈ in the general formula [2] has a substituent, the alkyl group as the substituent may be linear or branched and usually has a carbon number. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. The alkoxy group as a substituent may be linear or branched, and usually includes one having 1 to 4 carbon atoms. Specific examples include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group. , Butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group and the like, and examples of the halogen atom as a substituent include a chlorine atom, a fluorine atom, a bromine atom and an iodine atom. That. Such an substituent is generally substituted with 1 to 5, preferably 1 to 2 on the aromatic ring of the arylene group or arylalkylene group represented by R ₄ .

In the general formula [2], R ₉ is represented by a group containing an epoxy group represented by the general formula [21] or [22], and a group containing an epoxy group represented by the general formula [21] is preferable.

The alkylene group represented by R ₂₁ and R ₂₅ in the general formula [21] or the general formula [22] may be linear, branched or cyclic, and usually has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. More preferably, those having 1 to 2 are mentioned, and specifically, for example, methylene group, ethylene group, trimethylene group, propylene group, methylmethylene group, methylethylene group, ethylmethylene group, tetramethylene group, pentamethylene group. , Hexamethylene group, cyclopropylene group, cyclopentylene group and cyclohexylene group, methylene group and ethylene group are preferable, and methylene group is preferable.

In general formula [21] or general formula [22], the alkylene group represented by R ₂₂ and R ₂₆ may be linear, branched or cyclic, and usually has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. More preferably, those having 1 to 3 are mentioned, and specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group , N-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, 3-methylpentyl, 2-methylpentyl Group, 1,2-dimethylbutyl group, n-heptyl group, isoheptyl group, sec-heptyl group, n-octyl group, isooctyl group, sec-octyl group, n-nonyl group, n-decyl group, n-undecyl group , N-dodecyl group, n-tridecyl group, n-te Tradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group , Cyclononyl group, cyclodecyl group, cyclododecyl group, cycloundecyl group, cyclotridecyl group, cyclotetradecyl group, cyclopentadecyl group, cyclohexadecyl group, cycloheptadecyl group, cyclooctadecyl group, cyclononadecyl group, cycloicosyl group Etc. When the alkylene group has an oxygen atom, the alkyl chain usually contains 1 to 20, preferably 1 to 10, more preferably 1 to 5 oxygen atoms.

In the general formula [21] or [22], the alkyl group represented by R ₂₃ , R ₂₄ , R ₂₇ and R ₂₈ may be linear, branched or cyclic, and usually has 1 to 6 carbon atoms. , Preferably 1-4, more preferably 1-2, specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl Group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, cyclopropyl group, A cyclopentyl group, a cyclohexyl group, etc. are mentioned.

Examples of the aryl group represented by R ₂₃ , R ₂₄ , R ₂₇ and R ₂₈ in the general formula [21] or the general formula [22] usually include those having 6 to 10 carbon atoms, preferably 6 carbon atoms. Examples thereof include a phenyl group and a naphthyl group.

In the general formula [21] or [22], the aralkyl group represented by R ₂₃ , R ₂₄ , R ₂₇ and R ₂₈ may be linear, branched or cyclic, and usually has 7 to 12 carbon atoms. 7 to 10 are preferable, and specific examples include a benzyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, and a phenylhexyl group.

When the aromatic ring of the aryl group or aralkyl group represented by R ₂₃ , R ₂₄ , R ₂₇ and R ₂₈ in the general formula [21] or [22] has a substituent, the alkyl group as the substituent is , Which may be linear or branched, and usually those having 1 to 4 carbon atoms. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl groups. , Sec-butyl group, tert-butyl group and the like, and the alkoxy group as the substituent may be linear or branched, and usually includes those having 1 to 4 carbon atoms, specifically For example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, and the like, and as a halogen atom as a substituent, for example, a chlorine atom, Fluorine atom, Atom, an iodine atom and the like. In general, 1 to 5 and preferably 1 to 2 such substituents are substituted on the aromatic ring of the aryl group or aralkyl group.

（式中、Ｒ₃₁は、炭素数１〜３のアルキレン基を表し、nは、１〜６を表す。Ｒ_21、Ｒ₂₃及びＲ₂₄は、上記と同じ。）が挙げられる。 As a preferred specific example of the group containing an epoxy group represented by the general formula [21], a group represented by the following general formula [23]

(Wherein R ₃₁ represents an alkylene group having 1 to 3 carbon atoms, and n represents 1 to 6. R _21, R _23, and R ₂₄ are the same as above).

As the alkylene group represented by R ₃₁ in the general formula [23], those having 1 to 3 carbon atoms are usually mentioned, and 1 to 2 are preferable, and specifically, methylene group, ethylene group, n-propylene group. , An isopropylene group, and the like. A methylene group and an ethylene group are preferable, and a methylene group is more preferable.

  N in general formula [23] is an integer of 1-6 normally, the integer of 1-4 is preferable and 1 is more preferable.

等が挙げられる。 As a preferable specific example of the general formula [23],

Etc.

（式中、Ｒ₃₂は、メチレン基又はエチレン基を表し、Ｒ₃₃は、炭素数１〜３のアルキレン基を表し、ｍは、１〜６を表す。Ｒ_25、Ｒ₂₇及びＲ₂₈は、上記と同じ。）が挙げられる。 As a preferred specific example of the group containing an epoxy group represented by the general formula [22], a group represented by the following general formula [24]

(In the formula, R ₃₂ represents a methylene group or an ethylene group, R ₃₃ represents an alkylene group having 1 to 3 carbon atoms, and m represents 1 to 6. R _25, R ₂₇ and R ₂₈ are The same as above).

In the general formula [24], R ₃₂ is a methylene group or an ethylene group, and a methylene group is preferable.

Examples of the alkylene group represented by R ₃₃ in the general formula [24] usually include those having 1 to 3 carbon atoms, preferably 1 to 2, and specifically include a methylene group, an ethylene group, and an n-propylene group. , An isopropylene group, and the like. A methylene group and an ethylene group are preferable, and a methylene group is more preferable.

  M in general formula [24] is an integer of 1-6 normally, the integer of 1-4 is preferable and 1 is more preferable.

等が挙げられる。 As a preferable specific example of the general formula [24],

Etc.

等が挙げられる。 As a preferred specific example of a monomer containing an aromatic group having an epoxy group and a polymerizable double bond according to the present invention,

Etc.

[Hydrophilic group-containing monomer represented by the general formula [3] according to the present invention]
In the general formula [3], the alkyl group represented by R _{10 to} R ₁₂ may be linear, branched or cyclic, and usually has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 4 carbon atoms. Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Examples include isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, cyclopropyl group, cyclopentyl group, and cyclohexyl group. Group and ethyl group are preferable, and methyl group is more preferable.

Preferable specific examples of R _{10 to} R ₁₂ include a methyl group and a hydrogen atom, and a hydrogen atom is more preferable.

In the general formula [3], the arylene group represented by R ₁₃ usually includes those having 6 to 10 carbon atoms, and preferably 6 carbon atoms. Specific examples include a p-phenylene group, an o-phenylene group, an m-phenylene group, and a naphthylene group.

When the aromatic ring of the arylene group represented by R ₁₃ in the general formula [3] has a substituent, the alkyl group as the substituent may be linear or branched, and usually has 1 to 4 carbon atoms. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc. Examples of the alkoxy group may be linear or branched, and usually include those having 1 to 4 carbon atoms. Specifically, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, An isobutoxy group, a sec-butoxy group, a tert-butoxy group and the like can be mentioned. Examples of the halogen atom as a substituent include a chlorine atom, a fluorine atom, a bromine atom and an iodine atom. In the arylene group represented by R ₁₃ , 1 to 5 and preferably 1 to 2 of such substituents are substituted on the aromatic ring.

In the general formula [31], the alkylene group represented by R ₄₀ may be linear, branched or cyclic, and usually has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms. Specifically, for example, methylene group, ethylene group, trimethylene group, propylene group, methylmethylene group, methylethylene group, ethylmethylene group, tetramethylene group, pentamethylene group, hexamethylene group, cyclopropylene group , Cyclopentylene group and cyclohexylene group, methylene group and ethylene group are preferable, and methylene group is preferable.

In the general formula [31], the alkylene group represented by R ₄₁ may be linear, branched or cyclic, and usually has 1 to 20, preferably 1 to 10, more preferably 1 to 8 carbon atoms. Specific examples thereof include, for example, methylene group, ethylene group, trimethylene group, propylene group, methylmethylene group, methylethylene group, ethylmethylene group, tetramethylene group, pentamethylene group, hexamethylene group. Group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, tetradecamethylene group, hexadecamethylene group, octadecamethylene group, icosalen group, cyclopropylene group , Cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclooctylene group Cyclononylene group, a cyclodecylene group, a cycloalkyl undecylenic group, cyclododecylene group, cyclotetrasiloxane decylene group, cyclohexadecen cyclohexylene group, a cycloalkyl octadecylene group, Shikuroikosaren group and the like. When the alkylene group has an oxygen atom, the chain usually contains 1 to 20 oxygen atoms, preferably 1 to 10 oxygen atoms, more preferably 1 to 5 oxygen atoms.

（式中、Ｒ₄₂は、炭素数１〜６のアルキレン基を表し、Ｒ₄₃、Ｒ₄₄及びＲ₄₅は、炭素数１〜３のアルキレン基を表し、ｐは１〜６の整数を、ｑは２〜６の整数を表す。）が挙げられるが、一般式［３２］で示される基が好ましい。 Preferred specific examples of the group represented by the general formula [31] are groups represented by the following general formula [32] or the general formula [33].

(Wherein R ₄₂ represents an alkylene group having 1 to 6 carbon atoms, R ₄₃ , R ₄₄ and R ₄₅ represent an alkylene group having 1 to 3 carbon atoms, and p represents an integer of 1 to 6, q Represents an integer of 2 to 6.), and a group represented by the general formula [32] is preferable.

The alkylene group represented by R ₄₂ in the general formula [32] may be linear, branched or cyclic, and usually has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms. Specifically, for example, methylene group, ethylene group, trimethylene group, propylene group, methylmethylene group, methylethylene group, ethylmethylene group, tetramethylene group, pentamethylene group, hexamethylene group, cyclopropylene group, Examples include a cyclopentylene group and a cyclohexylene group, a methylene group and an ethylene group are preferable, and a methylene group is preferable.

Examples of the alkylene group represented by R ₄₄ in the general formula [33] usually include those having 1 to 3 carbon atoms, preferably 1 to 2, and specifically include a methylene group, an ethylene group, and an n-propylene group. , An isopropylene group, and the like. A methylene group and an ethylene group are preferable, and a methylene group is more preferable.

Examples of the alkylene group represented by R ₄₃ and R ₄₅ in the general formula [32] or [33] usually include those having 1 to 3 carbon atoms, preferably 1 to 2, and specifically, a methylene group, Examples thereof include an ethylene group, an n-propylene group, and an isopropylene group. A methylene group and an ethylene group are preferable, and an ethylene group is more preferable.

  P in general formula [32] is an integer of 1-6, 1-4 are preferable, 3-4 are more preferable, and 4 is especially preferable.

  Q in the general formula [33] is an integer of 2 to 6, preferably 2 to 4, more preferably 3 to 4, and particularly preferably 4.

等が挙げられる。 As a more specific preferable example of the group represented by the general formula [31],

Etc.

等が挙げられる。 As preferable specific examples of the hydrophilic group-containing monomer represented by the general formula [3] according to the present invention, for example,

Etc.

[Styrenic monomer and copolymer obtained by copolymerizing an aromatic group having an epoxy group and a polymerizable double bond, a styrene monomer, and a hydrophilic group-containing monomer represented by the following general formula [3] Copolymers obtained by copolymerizing
A copolymer obtained by copolymerizing a styrenic monomer and a monomer containing an aromatic group having an epoxy group and a polymerizable double bond (hereinafter sometimes abbreviated as copolymer 1 according to the present invention), The styrenic monomer as described above and the monomer containing an aromatic group having an epoxy group and a polymerizable double bond as described above in a molar ratio of 60:40 to 95: 5, preferably 70:30 to 90:10. More preferably, it is obtained by copolymerization at 80:20 to 90:10. In the copolymer 1 according to the present invention, the constituent ratio of the monomer unit derived from a styrene monomer and the monomer unit derived from a monomer containing an aromatic group having an epoxy group and a polymerizable double bond is the same as the above ratio.

  A copolymer obtained by copolymerizing a styrenic monomer and a hydrophilic group-containing monomer represented by the general formula [3] (hereinafter sometimes abbreviated as copolymer 2 according to the present invention) is a styrenic monomer as described above. The monomer and the hydrophilic group-containing monomer represented by the general formula [3] as described above are used in a molar ratio of 60:40 to 95: 5, preferably 70:30 to 90:10, more preferably 80:20. Obtained by copolymerization at ~ 90: 10. In the copolymer 2 according to the present invention, the constituent ratio of the monomer unit derived from the styrenic monomer and the monomer unit derived from the hydrophilic group-containing monomer represented by the general formula [3] is the same as the above ratio.

The copolymer 1 and the copolymer 2 according to the present invention are polymerized according to a known method in which the above-mentioned various monomers are dissolved or suspended in an appropriate solvent in the above ratio, and an appropriate polymerization initiator is added, followed by stirring reaction while heating. Can be obtained.
Specifically, for example, various monomers as described above are mixed so as to have the ratio as described above, and an appropriate solvent having a volume of 1 to 10 times the monomer, such as toluene, ethanol, 1,4-dioxane, tetrahydrofuran, A polymerization initiator dissolved in isopropanol, methyl ethyl ketone, etc. and 0.1 to 30% by weight based on the monomer, such as azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2 ′ -Reaction at 50 to 150 ° C. for 1 to 20 hours in the presence of azobis (methyl 2-methylpropionate), 2,2′-azobis (2-methylbutyronitrile), benzoyl peroxide, lauroyl peroxide, etc. After the reaction, the desired copolymer is obtained by processing according to a conventional method for obtaining a polymer.

  The weight average molecular weight (Mw) of the copolymer 1 or 2 according to the present invention is not particularly limited as long as it is soluble in a suitable solvent, but is usually 2,000 to 1,000,000, preferably 10,000 to 100,000.

[Osmium catalyst]
The osmium catalyst according to the present invention is reduced in a reaction solvent as necessary in the production method of the present invention, and becomes a 0-hexavalent osmium catalyst in the osmium-supported catalyst composition of the present invention, preferably 4- Specific examples include hexavalent osmium catalysts, and specific examples include osmium inorganic acids such as osmium halides such as osmium chloride, osmium dioxide, osmium tetroxide, potassium osmate (VI), and potassium hexachloroosmate. Preferred are salts and the like, and among these, osmium tetroxide is more preferred. These osmium compounds can be easily obtained as commercial products.

[Method for producing osmium-supported catalyst composition of the present invention]
The production method of the osmium-supported catalyst composition of the present invention (hereinafter sometimes abbreviated as the production method of the present invention) comprises: (I) supporting the osmium catalyst on each of the copolymer 1 and the copolymer 2 according to the present invention; After mixing, the obtained osmium-supported polymer is subjected to a crosslinking reaction (this method may be abbreviated as the production method (I) of the present invention), or (II) the copolymer 1 according to the present invention. And an osmium catalyst supported on the mixture of copolymer 2 and then subjecting the obtained osmium-supported polymer to a crosslinking reaction (this method may be abbreviated as the production method (II) of the present invention).

[Production method (I) of the present invention]
The method for supporting the osmium catalyst on the copolymer 1 in the production method (I) of the present invention is, for example, by homogenizing the copolymer 1 and the osmium catalyst in a solvent in which the copolymer 1 is dissolved. The obtained copolymer carrying the osmium catalyst (hereinafter sometimes abbreviated as microencapsulated osmium catalyst) can be obtained by precipitation by adding a poor solvent for the copolymer 1 as necessary. .

  In the production method (I) of the present invention, the method for supporting the osmium catalyst on the copolymer 2 is the same as the method for supporting the osmium catalyst on the copolymer 1, for example, the copolymer 2 and the osmium catalyst are dissolved in the copolymer 2. The resulting microencapsulated osmium catalyst can be obtained by precipitation by adding a poor solvent for the copolymer 2 as necessary.

  Examples of the solvent for dissolving the copolymer 1 or the copolymer 2 according to the present invention include ethers such as tetrahydrofuran and dioxane, and halogenated hydrocarbons such as methylene chloride and chloroform. The amount used may be an amount that can dissolve the copolymer to be used, and is usually 1 to 100 ml, preferably 1 to 50 ml per 1 g of the copolymer. When an octavalent osmium catalyst such as osmium tetroxide is used as the osmium catalyst, alcohol such as methanol, ethanol, isopropanol, isobutyl alcohol, cyclohexanol or hydrazine is used in an amount of 10 to 40% of the above solvent. It is more preferable to add 10 to 30% volume, and still more preferably 20 to 30% volume.

  Examples of the poor solvent for the copolymer 1 or 2 include methanol, ethanol, isopropanol, t-butanol, diethyl ether, pentane, hexane, and cyclohexane. The amount used thereof may be an amount so that all of the obtained microencapsulated osmium catalyst is precipitated, and is usually 1 to 100 ml, preferably 1 to 50 ml with respect to 1 g of the copolymer as a starting material.

  The homogenization of the copolymer 1 or copolymer 2 and the osmium catalyst according to the present invention is usually carried out at 0 to 50 ° C., preferably 5 to 30 ° C. for 1 to 200 hours, preferably 1 to 100 hours.

  The amount of the osmium catalyst is usually 0.05 to 4.0 mmol, preferably 0.1 to 4.0 mmol, more preferably 0.2 to 2.0 mmol as metal osmium with respect to 1 g of copolymer 1 or copolymer 2, and the obtained microcapsules The amount of osmium supported on the osmium iodide catalyst (in terms of the amount of metal osmium) is usually 0.05 to 4.0 mmol, preferably 0.1 to 4.0 mmol, more preferably 0.2 to 2.0 mmol with respect to the microencapsulated osmium catalyst.

  In the production method (I) of the present invention, the microencapsulated osmium catalyst obtained by using each of the copolymer 1 and the copolymer 2 according to the present invention is mixed completely with two microencapsulated osmium catalysts. What is necessary is just to mix physically, but in order to mix more completely, it is more preferable to mix in a poor solvent as follows. That is, in a poor solvent for copolymers 1 and 2 according to the present invention such as methanol, ethanol, isopropanol, t-butanol, diethyl ether, hexane, pentane, cyclohexane, etc., usually 0 to 50 ° C., preferably 5 to 30 ° C. for 10 minutes to The two microencapsulated osmium catalysts are preferably mixed by stirring for 10 hours, preferably 30 minutes to 2 hours. The mixture thus obtained may be dried as necessary and subjected to a crosslinking reaction.

  The amount of the microencapsulated osmium catalyst by the copolymer 1 according to the present invention and the microencapsulated osmium catalyst by the copolymer 2 according to the present invention used in the mixing is usually 40:60 to 60:40 by weight ratio. Preferably, it is used in a ratio of 50:50.

  In the production method (I) of the present invention, the crosslinking reaction may be a heating method, a conventionally known method using a crosslinking agent, a method using a condensing agent, or a method using a radical polymerization catalyst such as a peroxide or an azo compound. And a method in which an acid or a base is added and heated, for example, a method in which a dehydrating condensing agent such as carbodiimide is combined with an appropriate crosslinking agent and a reaction is performed.

  The temperature for crosslinking by heating is usually 50 to 300 ° C, preferably 70 to 200 ° C, more preferably 100 to 180 ° C. The reaction time for the heat crosslinking reaction is usually 0.1 to 100 hours, preferably 1 to 50 hours, more preferably 3 to 10 hours. As a specific method of crosslinking by heating, for example, the above microencapsulated osmium catalyst may be heated at the above temperature for the above time without using a solvent, for example.

In the case of crosslinking using a crosslinking agent, as a crosslinking agent, when a copolymer obtained by copolymerizing a styrene monomer and an aromatic group having an epoxy group and a monomer containing a polymerizable double bond is crosslinked. Polyamine compounds such as hexamethylenediamine and hexamethylenetetramine, polyols such as ethylene glycol, propylene glycol and glycerin, such as polyacids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid and fumaric acid Crosslinking agents such as carboxylic acids and their anhydrides can be mentioned. When a copolymer obtained by copolymerizing a styrenic monomer and a hydrophilic group-containing monomer represented by the general formula [3] is crosslinked, for example, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, malein Examples include cross-linking agents such as polycarboxylic acids such as acid and fumaric acid and anhydrides thereof, for example, alkylene oxide compounds such as ethylene oxide and propylene oxide, and polyamine compounds such as hexamethylenediamine and hexamethylenetetramine.
The amount of the crosslinking agent is influenced by the reactivity of the crosslinking reaction, the molecular weight of the copolymer, the reaction conditions, etc. -10 equivalents, preferably 0.5-5 equivalents.

  Examples of the condensing agent used for crosslinking using a condensing agent include dehydrating agents such as carbodiimides such as dicyclohexylcarbodiimide in the case of a polymer having a carboxyl group as a crosslinkable functional group.

  The amount of the condensing agent is affected by the reactivity of the cross-linking reaction, the molecular weight of the copolymer, the reaction conditions, etc., but the reactive functional group of the cross-linking agent is usually 0.1% relative to the epoxy group or hydroxyl group, which is usually a cross-linking functional group. -20 equivalents, preferably 0.5-10 equivalents.

  In the production method of the present invention, among the crosslinking reactions, a crosslinking reaction by heating is preferable.

  The degree of crosslinking resulting from the crosslinking is not particularly limited as long as it does not interfere with the target catalytic action, but the crosslinked monomer units are usually 0.1 to 10%, preferably 0.5 to 5% of the total monomer units. More preferably, it is about 0.5 to 3%.

[Production method (II) of the present invention]
In the production method (II) of the present invention, the copolymer 1 and the copolymer 2 according to the present invention may be mixed by mixing them in a solvent that can dissolve both of these two types of copolymers. It is carried out at 50 ° C., preferably 5-30 ° C., usually for 1-200 hours, preferably 1-100 hours.

  Examples of the solvent used here include ethers such as tetrahydrofuran and dioxane, and halogenated hydrocarbons such as methylene chloride and chloroform. When the same solvent as the osmium catalyst in the next step is used, The mixing and the method of supporting the osmium catalyst on the copolymer may be performed simultaneously.

  The amount of the copolymer 1 and the copolymer 2 according to the present invention used in the mixing may be 40:60 to 60:40 by weight, and preferably 50:50.

  In the production method (II) of the present invention, for example, the mixed copolymer and the osmium catalyst are homogenized in a solvent in which the copolymers 1 and 2 according to the present invention are dissolved. Is made by The obtained microencapsulated osmium catalyst may be precipitated by adding a poor solvent for the copolymers 1 and 2 as necessary.

  Examples of the solvent for dissolving the copolymers 1 and 2 according to the present invention include ethers such as tetrahydrofuran and dioxane, and halogenated hydrocarbons such as methylene chloride and chloroform. The amount used may be an amount capable of dissolving both of the copolymers to be used, and is usually 1 to 100 ml, preferably 1 to 50 ml per 1 g of the copolymer. When an octavalent osmium catalyst such as osmium tetroxide is used as the osmium catalyst, alcohol such as methanol, ethanol, isopropanol, isobutyl alcohol, cyclohexanol or hydrazine is used in an amount of 10 to 40% of the above solvent. It is more preferable to add 10 to 30% volume, and still more preferably 20 to 30% volume.

  Examples of the poor solvent for the copolymers 1 and 2 according to the present invention include methanol, ethanol, isopropanol, t-butanol, diethyl ether, pentane, hexane, cyclohexane and the like. The amount used may be an amount so that all of the obtained microencapsulated osmium catalyst is precipitated, and is usually 1 to 100 ml, preferably 1 to 50 ml, based on the total amount of the starting copolymer.

  The homogenization of the mixed copolymer and the osmium catalyst is usually performed at 0 to 50 ° C., preferably 5 to 30 ° C. for 1 to 200 hours, preferably 1 to 100 hours.

  The amount of the osmium catalyst used is usually 0.05 to 4.0 mmol, preferably 0.1 to 4.0 mmol, more preferably 0.2 to 2.0 mmol as metal osmium with respect to 1 g of the mixed copolymer. The obtained microencapsulated osmium The amount of osmium supported on the catalyst (in terms of the amount of metal osmium) is usually 0.05 to 4.0 mmol, preferably 0.1 to 4.0 mmol, more preferably 0.2 to 2.0 mmol with respect to the microencapsulated osmium catalyst.

  For the crosslinking reaction in the production method (II) of the present invention, the same method as the crosslinking reaction in the production method (I) of the present invention can be used, and the resulting crosslinking degree is also the same.

[Reheating after crosslinking]
The osmium-supported catalyst composition of the present invention obtained by subjecting to a crosslinking reaction is preferably further heated. The heating reaction is usually 50 to 300 ° C, preferably 70 to 200 ° C, more preferably 100 to 180 ° C. The reaction time for the heat crosslinking reaction is usually 0.1 to 100 hours, preferably 1 to 50 hours, more preferably 1 to 10 hours. By performing such a heating reaction, an osmium-supported catalyst composition with less leakage of the osmium catalyst during the reaction can be obtained. This is considered to be because the osmium catalyst can be supported more firmly because the copolymer, which is the carrier, is further cross-linked by the heating reaction.

[Specific production method of the present invention]
The production method of the present invention is specifically performed as follows.

  For example, when the production method (I) of the present invention is used, it is performed as follows.

  That is, the copolymer 1 according to the present invention is dissolved in, for example, tetrahydrofuran-methanol (4: 1), and osmium tetroxide is usually 0.01 to 1.0 g, preferably 0.05 to 1.0 g, more preferably, to 1 g of the copolymer 11. Add to 0.05-0.5 g and stir at room temperature for 50-100 hours. Thereafter, for example, hexane which is a poor solvent for the copolymer 1 is added, and the mixture is further stirred for 10 to 30 hours, and the precipitate is collected and dried to obtain a microencapsulated osmium catalyst of the copolymer 1. Similarly, the copolymer 2 is dissolved in, for example, tetrahydrofuran-methanol (4: 1), and osmium tetroxide is usually 0.01 to 1.0 g, preferably 0.05 to 1.0 g, more preferably 0.05 to 1.0 g based on 1 g of the copolymer 21. Add to 0.5 g and allow to stir at room temperature for 50-100 hours. Thereafter, for example, hexane, which is a poor solvent for the copolymer 2, is added, and the mixture is further stirred for 10 to 30 hours, and the precipitate is collected to obtain a microencapsulated osmium catalyst based on the copolymer 2. Furthermore, the dried microencapsulated osmium catalyst according to the copolymer 1 according to the present invention and the microencapsulated osmium catalyst according to the copolymer 2 according to the present invention are used in the same amount of, for example, 30 minutes in a poor solvent for both copolymers such as hexane. Stir for 1 hour and mix. The obtained mixture is dried and then heated at 150 to 200 ° C. for 3 to 5 hours to cause a crosslinking reaction, whereby the osmium-supported catalyst composition of the present invention can be obtained.

  For example, when carrying out by the production method (II) of the present invention, it is carried out as follows.

  That is, the copolymer 1 according to the present invention and the copolymer 2 according to the present invention are dissolved in, for example, tetrahydrofuran-methanol (4: 1) using the same amount, for example. Thereafter, osmium tetroxide in an amount of usually 0.01 to 1.0% by weight, preferably 0.05 to 1% by weight, more preferably 0.05 to 0.5% by weight, based on the total amount of the copolymer 1 according to the invention and the copolymer 2 according to the invention. Add and let stir at room temperature for 50-100 hours. Thereafter, a poor solvent for both copolymers, such as hexane, is added and stirred for a further 10 to 30 hours to precipitate the target product, and the precipitate is collected, whereby the microencapsulated osmium according to the copolymers 1 and 2 according to the present invention is collected. A catalyst is obtained. Subsequently, after drying the microencapsulated osmium catalyst of the copolymers 1 and 2 according to the present invention, the osmium-supported catalyst composition of the present invention is obtained by heating at 150 to 200 ° C. for 3 to 5 hours to cause a crosslinking reaction. be able to.

  The osmium-supported catalyst composition of the present invention obtained as described above is further dried and further heated at 150 to 200 ° C. for 3 to 5 hours, thereby further reducing the osmium-catalyzed catalyst composition. Can be obtained.

[Osmium-supported catalyst composition of the present invention]
The osmium-supported catalyst composition of the present invention comprises (I) (1) a styrene monomer and (2) a copolymer obtained by copolymerizing an epoxy group-containing aromatic group and a monomer containing a polymerizable double bond. , (1) a styrene monomer and (2) a copolymer obtained by copolymerizing a hydrophilic group-containing monomer represented by the general formula [3], each of which was supported with an osmium catalyst and then mixed. An osmium-supported catalyst composition obtained by subjecting an osmium-supported polymer to a crosslinking reaction, or
(II) a copolymer obtained by copolymerizing (1) a styrenic monomer and (2) a monomer containing an aromatic group having an epoxy group and a polymerizable double bond; and (1) a styrenic monomer and (2 ) Obtained by supporting an osmium catalyst in a mixture with a copolymer obtained by copolymerizing a hydrophilic group-containing monomer represented by the general formula [3], and then subjecting the obtained osmium-supported polymer to a crosslinking reaction. The osmium-supported catalyst composition.

  The details of the monomer and copolymer, the production method, and the like are the same as the production method of the present invention.

  The ratio of the copolymer 1 and the copolymer 2 in the osmium-supported catalyst composition according to the present invention is 40:60 to 60:40 by weight, and 50:50 is preferable.

  The amount of osmium catalyst in the osmium-supported catalyst composition according to the present invention is usually 0.05 to 4.0 mmol, preferably 0.1 to 4.0 mmol, more preferably 0.2 to 2.0 mmol, and still more preferably 0.5 as the amount of osmium metal in 1 g of the catalyst composition. ~ 1 mmol.

  Such an osmium-supported catalyst composition of the present invention has excellent solvent resistance, and there is almost no leakage of the osmium catalyst supported on the osmium-supported catalyst composition even after repeated use. Very useful as a catalyst for the reaction. Because of such excellent characteristics, the catalyst composition of the present invention can be advantageously used industrially as a catalyst for various chemical reactions.

  For example, when used for the diolation reaction of an alkenyl compound, it may be performed as follows.

  That is, the reaction can be easily carried out in the presence of the osmium-supported catalyst composition of the present invention and a reoxidant in a suitable reaction solvent if necessary. Specifically, the alkenyl compound, the osmium-supported catalyst composition of the present invention and the reoxidant are added to an appropriate reaction solvent if necessary, and usually at −78 ° C. to 100 ° C., preferably at −10 ° C. to 50 ° C. The target diol compound is obtained by stirring and reacting for 0.5 to 50 hours, preferably 2 to 30 hours, and then isolation and purification by a conventional method. The osmium-supported catalyst composition of the present invention can be easily recovered by filtration or the like and can be used again for an oxidation reaction or the like.

  As the alkenyl compound, any compound can be used as long as it can be oxidized by a commonly used oxidation catalyst such as osmium tetroxide.

In the above oxidation method, the amount of the osmium-supported catalyst composition of the present invention used is usually 0.0001 to 1 mol, preferably 0.001 to 0.5 mol, more preferably 0.005 to 1 mol of the supported osmium catalyst with respect to 1 mol of the alkenyl compound. Used to be 0.2 mol.
As the reoxidant, a compound that can oxidize a metal that is usually used in this field may be appropriately set and used. Moreover, what is necessary is just to set and use the thing normally used in this field | area also suitably about the reaction solvent used as needed.

  Hereinafter, the present invention will be described in more detail with reference to Examples, Synthesis Examples, Experimental Examples, and Comparative Examples, but the present invention is not limited to these in any way.

Synthesis Example 1 Synthesis of ST-VBGE Copolymer Styrene (ST) 11.8g (113.4mmol), 4-vinylbenzylglycidyl ether (VBGE) 3.8g (20.0mmol), toluene 13mL and 2,2'-azobis (isobutyric acid) dimethyl (Wako Pure) 215 mg (0.9 mmol) manufactured by Yakuhin Kogyo Co., Ltd. (trade name: V-601) was mixed and polymerized by stirring at 80 ° C. for 7 hours. After completion of the polymerization, the polymerization solution was poured into 260 mL of methanol to crystallize the polymer. The crystallized polymer was separated and decanted by adding 100 ml of methanol. The obtained polymer was dissolved in 13 mL of chloroform, and the solution was poured into 260 mL of methanol to reprecipitate the polymer. The precipitated polymer was separated and decanted again, and then dried under reduced pressure at room temperature to obtain 11 g of a white powder polymer (Mn: 25951, Mw: 36754). This is polymer 1.

  In the synthesis of such a binary copolymer, since the polymerization reaction can be performed at a high temperature of 80 ° C., the polymerization can be completed in 7 hours. On the other hand, in the synthesis of the ternary copolymer, polymerization is performed at room temperature to prevent crosslinking. Therefore, a long polymerization reaction such as 72 hours is required as in Comparative Example 1 described later.

Synthesis Examples 2-6. Synthesis of ST-VBGE Copolymer A polymer was obtained in the same manner as in Example 1 except that the amount of each raw material charged was as shown in Table 1. Corresponding polymer compounds are designated as polymers 2-6. The amount of each raw material used (the lower part of ST and VBGE orchids represents the molar ratio), the yield of the obtained polymer compound and the molecular weight of the obtained polymer are also shown in Table 1. The result of Synthesis Example 1 is also shown.

Synthesis Example 7 Synthesis of ST-TEGVBE copolymer styrene (ST) 5.9 g (56.7 mmol), tetraethylene glycol mono (4-vinyl) benzyl ether (TEGVBE) 3.1 g (10.0 mmol), toluene 7 mL and 2,2′-azobis (isobutyric acid) ) 108 mg (0.5 mmol) of dimethyl (manufactured by Wako Pure Chemical Industries, Ltd .: trade name V-601) was mixed and polymerized with stirring at 80 ° C. for 7 hours. After completion of the polymerization, the polymerization solution was poured into 130 mL of methanol to crystallize the polymer. The crystallized polymer was separated and decanted by adding 50 ml of methanol. The obtained polymer was dissolved in 7 mL of chloroform, and the solution was poured into 130 mL of methanol for reprecipitation. Thereafter, the polymer was separated and decanted again, and then dried under reduced pressure at room temperature to obtain 6 g of a white powder polymer (Mn: 29609, Mw: 43092). This is designated as Polymer 7.

Synthesis Examples 8-12. Synthesis of ST-TEGVBE copolymer The amount of each raw material was adjusted to the amount shown in Table 2, and in Synthesis Example 12, except that diethyl ether was used instead of methanol as a poor solvent, the same as in Synthesis Example 7, A polymer compound was obtained. Corresponding polymer compounds are designated as polymers 8-12. The amount of monomer used (the lower part represents the molar ratio), the amount of V-601 used, the yield and molecular weight of the resulting polymer compound are also shown in Table 2. The result of Synthesis Example 7 is also shown.

Example 1. Synthesis of the osmium-supported catalyst composition (PI-Os-1) of the present invention [method for forming MC and crosslinking after mixing binary polymer]
13 g of polymer and 3 g of polymer 7 were dissolved in a mixed solvent of 96 mL of tetrahydrofuran and 24 mL of methanol, and 1.2 g of osmium tetroxide was added thereto, followed by stirring at room temperature for 72 hours. Thereafter, 180 mL of hexane was injected into the reaction solution, and the mixture was further stirred for 24 hours to precipitate a microencapsulated osmium catalyst (MC-Os) in which osmium was supported on a polymer. The supernatant was removed and dried under reduced pressure at room temperature for 1 hour to obtain 6.4 g of microencapsulated osmium catalyst. 1 g of the catalyst was taken out and crosslinked at 150 ° C. for 5 hours. It was washed with tetrahydrofuran and vacuum dried at room temperature to obtain 1 g of a target osmium-supported catalyst composition. The obtained osmium-supported catalyst composition was designated as PI-OS-1. The osmium content in the catalyst composition was measured by fluorescent X-ray.

Example 2 Synthesis of osmium-supported catalyst composition (PI-Os-2) of the present invention [Method of MC conversion and crosslinking after binary polymer mixing]
A microencapsulated osmium catalyst (6.6 g) was obtained in the same manner as in Example 1 except that polymer 2 and polymer 8 were used instead of polymer 1 and polymer 7. Thereafter, an experiment was conducted in the same manner as in Example 1 except that 6.6 g of the microencapsulated osmium catalyst was used, and 5.4 g of an osmium-supported catalyst composition was obtained. The obtained osmium catalyst was designated as PI-OS-2.

Example 3 Synthesis of the osmium-supported catalyst composition (PI-Os-3) of the present invention [Method of MC conversion and crosslinking after binary polymer mixing]
A microencapsulated osmium catalyst (7.1) as in Example 1 except that 3 g of polymer 3 and 3.2 g of polymer 9 were used instead of 3 g of polymer 13 and 3 g of polymer 7 and the amount of osmium tetroxide used was 1.3 g. Got. Then, it experimented like Example 1 except having used 3.1 g of microencapsulated osmium catalysts, and obtained 3.0 g of osmium carrying | support catalyst compositions. The obtained osmium catalyst was designated as PI-OS-3.
Regarding the results of Examples 1 to 3, the polymer compounds used in Examples 1 to 3 and the total amount thereof, the amount of osmium tetroxide used (OsO ₄ ), the amount of the obtained microencapsulated osmium catalyst (obtained MC- OS), the amount of microencapsulated osmium catalyst used (MC-Os used), the obtained osmium-supported catalyst composition (PI-Os), and the osmium content (Os content) in PI-Os of the catalyst. 3 shows.

Example 4 Synthesis of osmium-supported catalyst composition (PI-Os-4) of the present invention [PI-OS reheating]
An osmium catalyst obtained by reheating the osmium-supported catalyst composition (PI-Os-2) obtained in Example 2 at 150 ° C. for 3 hours was obtained as PI-OS-4.

Synthesis Example 13 Synthesis of microencapsulated osmium catalyst (MC-Os) 54.7 g of Polymer 5 was dissolved in a mixed solvent of 880 mL of tetrahydrofuran and 220 mL of methanol, and 10.5 g of osmium tetroxide was added thereto, followed by stirring at room temperature for 72 hours. did. Thereafter, 1650 mL of hexane was poured into the reaction solution, and the mixture was further stirred for 24 hours to precipitate a microencapsulated osmium catalyst (MC-Os) in which osmium was supported on a polymer. The supernatant was removed and dried under reduced pressure at room temperature for 1 hour to obtain 54.8 g of microencapsulated osmium catalyst.

Synthesis Examples 14 to 18 Synthesis of Microencapsulated Osmium Catalyst (MC-Os) Synthesis Example 13 except that the polymer compound used, the amount used, and the amount of osmium tetroxide used are shown in Table 4. In the same manner as in Example 1, a microencapsulated osmium catalyst (MC-Os) in which osmium was supported on a polymer was obtained. The amount of MC-Os obtained is also shown in Table 4.

Embodiment 5 FIG. Synthesis of Osmium-Supported Catalyst Composition (PI-Os-10) of the Present Invention [Method of Mixing and Crosslinking After Binary Polymer MC Conversion]
54.8 g of the microcapsules obtained in Synthesis Example 13 and 58.1 g of the microcapsules obtained in Synthesis Example 14 were stirred in 500 ml of hexane at room temperature for 30 minutes, filtered, and vacuum-dried at room temperature for 30 minutes. Thereafter, 112.3 g of two kinds of well-mixed microcapsules were cross-linked by heating at 150 ° C. for 5 hours. The obtained composition was washed with tetrahydrofuran and vacuum-dried at room temperature to obtain 101.4 g of an objective osmium-supported catalyst composition (osmium content 0.83 mmol / g). The obtained osmium-supported catalyst composition was designated as PI-OS-10.

Example 6 Synthesis of Osmium-Supported Catalyst Composition (PI-Os-11) of the Present Invention [Method of Mixing and Crosslinking After Binary Polymer MC Conversion]
The same experiment as in Example 5 was conducted except that 3.2 g of microcapsules obtained in Synthesis Example 15 and 3.2 g of microcapsules obtained in Synthesis Example 16 were used instead of the microcapsules obtained in Synthesis Examples 13 and 14. As a result, 5.7 g of the target osmium-supported catalyst composition was obtained (osmium content 0.83 mmol / g). The obtained osmium-supported catalyst composition was designated as PI-OS-11.

Example 7 Synthesis of Osmium-Supported Catalyst Composition (PI-Os-12) of the Present Invention [Method of Mixing and Crosslinking After Binary Polymer MC Conversion]
The experiment was conducted in the same manner as in Example 5 except that 3.0 g of the microcapsule obtained in Synthesis Example 17 and 3.0 g of the microcapsule obtained in Synthesis Example 18 were used instead of the microcapsule obtained in Synthesis Examples 13 and 14. Thus, 5.3 g of an objective osmium-supported catalyst composition was obtained (osmium content: 0.75 mmol / g). The obtained osmium-supported catalyst composition was designated as PI-OS-12.

Example 8 FIG. Synthesis of osmium-supported catalyst composition (PI-Os-13) of the present invention [PI-OS reheating]
An osmium-supported catalyst composition obtained by reheating the osmium-supported catalyst composition (PI-Os-10) obtained in Example 5 at 150 ° C. for 2 hours was obtained as PI-OS-13.

Example 9 Synthesis of osmium-supported catalyst composition (PI-Os-14) of the present invention [PI-OS reheating]
An osmium-supported catalyst composition obtained by reheating the osmium-supported catalyst composition (PI-Os-12) obtained in Example 6 at 150 ° C. for 2 hours was obtained as PI-OS-14.

Comparative Example 1.3 Synthesis of Osmium Catalyst Composition Supported on Original Polymer 25.0 g (240.0 mmol) of styrene (ST), 5.7 g (30.0 mmol) of 4-vinylbenzylglycidyl ether (VBGE), tetraethylene glycol mono (4 -Vinyl) benzyl ether (TEGVBE) 9.3 g (30.0 mmol), chloroform 38 mL and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd .: trade name V -70) 650 mg (2.1 mmol) was mixed and stirred and polymerized at room temperature for 72 hours. After completion of the polymerization, the polymerization solution was poured into 500 mL of methanol to crystallize the polymer. The crystallized polymer was separated and decanted by adding 100 ml of methanol. After removing the supernatant, the polymer was dissolved in 38 mL of chloroform. The solution was poured into 500 mL of methanol and reprecipitated. The polymer was separated and decanted again, and then dried under reduced pressure at room temperature to obtain 10 g (Mn: 24500, Mw: 33400) of a white powdered polymer.
1.0 g of the obtained polymer was dissolved in a mixed solvent of 16 mL of tetrahydrofuran and 4 mL of methanol, and 200 mg of osmium tetroxide was added thereto, followed by stirring at room temperature for 72 hours. Thereafter, 30 mL of hexane was injected into the reaction solution, and the mixture was further stirred for 24 hours to precipitate a microencapsulated catalyst (MC) in which osmium was supported on a polymer. After removing the supernatant and drying under reduced pressure at room temperature for 1 hour, it was crosslinked by heating at 120 ° C. for 1 hour and at 130 ° C. for 2 hours. After washing with tetrahydrofuran and vacuum drying at room temperature, 1.1 g of an objective osmium catalyst composition supported on a crosslinked polymer compound was obtained (Os content: 0.70 mmol / g).

Experimental Example 1 Diolation reaction of styrene using osmium-supported catalyst composition of the present invention
To 20 mL of t-butanol-water (1: 1) solvent, 0.21 g (2.0 mmol) of styrene, 0.83 g (6.0 mmol) of potassium carbonate, 1.98 g (6.0 mmol) of potassium hexacyanoferrate (III), (DHQD) ₂ PHAL (manufactured by Aldrich) 82 mg (0.1 mmol) and PI-OS-1 136 mg (0.1 mmol) were added, and the mixture was stirred at room temperature for 17 hours. After completion of the reaction, 0.63 g (4.0 mmol) of sodium thiosulfate and 8 ml of i-propanol-water (1: 3) were added to dissolve solids other than the osmium-supported catalyst composition. The osmium-supported catalyst composition (PI-OS-1) was collected by filtration and washed with i-propanol-water (1: 3). Next, the solution dissolved in i-propanol-water and the washing solution used for washing were combined and made up to 50 ml. Using this solution, leaching of osmium from the catalyst to the reaction solution was measured by fluorescent X-ray (EDX-800, manufactured by Shimadzu Corporation). As a result, the leak was 1%. After the measurement, the target product in the solution was extracted with 50 ml of ethyl acetate three times. The obtained organic layer was washed with 50 ml of water, concentrated, and purified by silica gel column chromatography (silica gel 60, manufactured by Merck & Co., Inc.) to obtain 0.25 g (1.8 mmol) of 1-phenyl-1,2-ethanediol. (Yield: 91%, optical yield: 96% ee).
Further, the osmium catalyst recovered above was reused to diolize styrene in the same manner as described above. As a result, the leakage of osmium was below the detection limit (1%), the yield of 1-phenyl-1,2-ethanediol was 84%, and the optical yield was 97% ee.

Experimental Example 2. Experiments were carried out in the same manner as in Experimental Example 1 except that α-methylstyrene was used as a substrate for the diolation reaction of α-methylstyrene using the osmium-supported catalyst composition of the present invention , and 2-phenyl-1,2-propane was used. Diol was obtained. (Yield 87%, 92% ee, Leakage: 1%)

Experimental Examples 3-9. Recovery and reuse of osmium-supported catalyst composition of the present invention PI-OS-3,4 and PI-OS-10 to 14 were used instead of PI-OS-1 as the osmium tetroxide catalyst composition of the present invention. In addition, an experiment was conducted in the same manner as in Experimental Example 1 except that α-methylstyrene was used as a substrate, and diol-formation of α-methylstyrene was performed. Further, in the same manner as in Experimental Example 1, an experiment for recovery and reuse of the osmium-supported catalyst composition was also conducted. Table 5 shows the diol yield%, optical yield (%), and leakage [%] for each reaction. The results of Experimental Examples 1 and 2 are also shown.
In the table, the substrate yield (optical yield) [leakage] is described in this order. When these are described in the table, the same applies hereinafter. Further, ND in the table indicates that it was below the detection limit, and so on.

Experimental Example 10 Diolation reaction of α-methylstyrene using the osmium-supported catalyst composition of the present invention (10 times scale of Experimental Example 6)
To 200 mL of a solvent of t-butanol-water (1: 1), α-methylstyrene 2.36 g (20 mmol), potassium carbonate 8.29 g (60 mmol), potassium hexacyanoferrate (III) 19.75 g (60 mmol), (DHQD) ₂ PHAL (manufactured by Aldrich) 0.82 g (1.0 mmol) and PI-OS-11 1.28 g (1.0 mmol) were added, and the mixture was stirred at room temperature for 38 hours. After completion of the reaction, 6.32 g (40 mmol) of sodium thiosulfate and 160 ml of i-propanol-water (1: 3) were added to dissolve solids other than the osmium-supported catalyst composition. The osmium-supported catalyst composition (PI-OS-11) was collected by filtration and washed with i-propanol-water (1: 3). Next, the solution dissolved in i-propanol-water and the washing solution used for washing were combined and made up to 500 ml. Using this solution, leaching of osmium from the catalyst to the reaction solution was measured by fluorescent X-ray (EDX-800, manufactured by Shimadzu Corporation). As a result, the leak was 1%. After the measurement, the target product in the solution was extracted three times with 200 ml of ethyl acetate. The obtained organic layer was washed with 200 ml of water, concentrated, and purified by silica gel column chromatography (silica gel 60, manufactured by Merck & Co., Inc.) to obtain 2.73 g (18 mmol) of 2-phenyl-1,2-propanediol. Obtained (yield 90%, 94% ee, leakage: 1%). The results are shown in Table 5 together with the results of Experimental Examples 1-9.

Comparative Example 2 Diolation of styrene with the osmium catalyst composition obtained in Comparative Example 1
In 5 mL of t-butanol-water (1: 1) solvent, 52 mg (0.5 mmol) of styrene, 207 mg (1.5 mmol) of potassium carbonate, 494 mg (1.5 mmol) of potassium hexacyanoferrate (III), (DHQD) ₂ PHAL (manufactured by Aldrich) 20 mg (0.025 mmol) and 36 mg (0.025 mmol) of the osmium catalyst composition obtained in Comparative Example 1 were added, and the mixture was stirred at room temperature for 12 hours. After completion of the reaction, 158 mg (1.0 mmol) of sodium thiosulfate and 4 ml of i-propanol-water (1: 3) were added to dissolve solids other than the osmium composition, and the mixture was stirred at room temperature for 10 minutes. The osmium composition of the present invention was collected by filtration and washed with i-propanol-water (1: 3), and then the reaction solution and the washing solution were combined to make up to 50 ml. Using this solution, leaching of osmium from the catalyst to the reaction solution was measured by X-ray fluorescence. After the measurement, the target product in the solution was extracted with ethyl acetate. The organic layer was washed with water, concentrated, and purified by column chromatography to obtain 55 mg (0.4 mmol) of 1-phenyl-1,2-ethanediol (yield 80%, 97% ee, leakage 6%). The results are shown in Table 5 together with the results of Experimental Examples 1-10.

From these results, when the osmium-supported catalyst composition of the present invention is used, the diolation reaction can proceed with a yield of 85% or more, and an asymmetric product with an optical yield of 90% or more in the asymmetric reaction. It turns out that you can get.
As for osmium leakage from the polymer, the osmium catalyst composition obtained by cross-linking the conventional ternary polymer after microencapsulation (MC conversion) was 6%, whereas the present invention When the osmium-supported catalyst composition was used, it was 2% or less. In particular, when the osmium-supported catalyst composition obtained by the method of Experimental Examples 5 to 10, ie, by mixing and crosslinking the osmium catalyst in the binary polymer after microencapsulation (MC conversion), the leakage is It could be suppressed to 1% or less. Furthermore, as a result of Experimental Examples 8 and 9, that is, an osmium-supported catalyst composition obtained by a method of microencapsulating (MC) an osmium catalyst in a binary polymer and then mixing and cross-linking was obtained by further heating. It has also been found that when a catalyst composition is used, it is possible to suppress leakage to below the detection limit.

Experimental Examples 11-13. Diolation reaction using various substrates
To 20 mL of t-butanol-water (1: 1) solvent, various substrates (2 mmol), potassium carbonate 0.83 g (6.0 mmol), potassium hexacyanoferrate (III) 1.98 g (6.0 mmol), (DHQD) ₂ PHAL ( Aldrich) 82 mg (0.1 mmol) and various osmium-supported catalyst compositions (0.1 mmol) were added and stirred at room temperature until the diolated substrate yield was 80% or more, and the reaction time and optics The yield was measured. Further, the leakage of osmium was measured in the same manner as in Experimental Example 1. The substrate used is styrene, trans-stilbene, trans-β-methylstyrene, 4-chlorostyrene, or 1-phenyl-1-cyclohexene, and the osmium-supported catalyst composition is PI-Os-3. , PI-Os-11 and PI-Os-13 were used, respectively.
Table 6 below shows the yield (%), optical yield (%), leakage (%), and reaction time of the diolated substrate.

From this result, when the osmium-supported catalyst composition of the present invention was used, the optical yield at that time was 95% or more although the dispersion of the reaction product was 80% or more, although time variation was observed. It was also found that leakage of the osmium catalyst can be suppressed to 2% or less. That is, it was found that the osmium-supported catalyst composition of the present invention was not affected by the substrate with respect to the reaction rate, optical yield, and leakage of the osmium catalyst.
The leakage of osmium catalyst is the method of mixing and cross-linking PI-Os-11 obtained by mixing and cross-linking osmium catalyst with bi-polymer, and then mixing and cross-linking osmium catalyst with bi-polymer. It was found that PI-Os-13 obtained by further heat-treating the osmium-supported catalyst composition obtained by the above method can be suppressed to 1% to the detection limit or less, and exhibits particularly excellent effects.

Experimental Example 14 Effect on leakage by reaction solvent (effect on solvent resistance)
To 20 mL of a solvent of t-butanol-water (1: 1), 0.24 g (2.0 mmol) of α-methylstyrene, 0.35 g (3.0 mmol) of N-methylmorpholine-N-oxide, and PI- 121 mg (0.1 mmol) of OS-10 was added and allowed to react with stirring at room temperature for 24 hours. Thereafter, PI-OS-10 was collected by filtration and washed with i-propanol-water (1: 3), and then the reaction solution and the washing solution were combined and made up to 50 ml. Using this solution, leaching of osmium from the catalyst to the reaction solution was measured by X-ray fluorescence. After the measurement, the target product in the solution was extracted with ethyl acetate. The organic layer was washed with water, concentrated, and purified by column chromatography to obtain 0.20 g (1.3 mmol) of 2-phenyl-1,2-propanediol. (Yield 66%, leakage ND)

Experimental Examples 15-17. Effect on leakage by reaction solvent (effect on solvent resistance)
2-Phenyl-1,2-propanediol was obtained in the same manner as in Experimental Example 14 except that the solvent and reaction time were as shown in Table 7. Yields and leaks are shown in Table 7.

Comparative Examples 3-6. Diolization reaction of styrene (various solvents)
In the same manner as in Experimental Example 14, except that the osmium-supported catalyst composition obtained in Comparative Example 1 was used instead of PI-OS-10, and the solvent and reaction time were as shown in Table 8, 2-phenyl- 1,2-propanediol was obtained. Yields and leaks are shown in Table 8.

  As a result of confirming leakage when using various solvents using the osmium-supported catalyst composition obtained in Reference 1, it is 4 to 20%, particularly in the case of acetone-water (1: 1), 20% I found out that it was melting. On the other hand, from the results of Experimental Examples 14 to 17, when the osmium-supported catalyst composition of the present invention was used, t-butanol-water (1: 1), acetone-water (1: 1), ethyl acetate-water ( 1: 1) and toluene-acetonitrile-water (1: 1: 1), the leakage was found to be 1% or below the detection limit. In particular, even when acetone-water (1: 1) was used, the leakage was 1% or less, indicating that the leakage rate of the osmium catalyst was greatly improved over the conventional one. . That is, it was found that the osmium-supported catalyst composition of the present invention has a high solvent resistance effect with respect to various solvents as compared with conventional osmium-supported catalyst compositions.

Claims (12)

(I) a copolymer obtained by copolymerizing (1) a styrene monomer and (2) a monomer containing an aromatic group having an epoxy group and a polymerizable double bond; and (1) a styrene monomer and (2 ) Hydrophilic group-containing monomer represented by the following general formula [3]

[Wherein, R _{10 to} R ₁₂ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ₁₃ represents an arylene group having 6 to 10 carbon atoms (the aromatic ring having 1 to 6 carbon atoms). 4 alkyl groups, alkoxy groups having 1 to 4 carbon atoms and / or those having a halogen atom as a substituent, and R ₁₄ is a group represented by the following general formula [31]

(Wherein R ₄₀ represents an alkylene group having 1 to 6 carbon atoms, and R ₄₁ represents an alkylene group having 1 to 20 carbon atoms with or without an oxygen atom in the chain). Each of the copolymers obtained by copolymerizing and supporting an osmium catalyst and then mixing, or
(II) a copolymer obtained by copolymerizing (1) a styrenic monomer and (2) a monomer containing an aromatic group having an epoxy group and a polymerizable double bond; and (1) a styrenic monomer and (2 ) Hydrophilic group-containing monomer represented by the following general formula [3]

[Wherein, R _{10 to} R ₁₂ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ₁₃ represents an arylene group having 6 to 10 carbon atoms (the aromatic ring having 1 to 6 carbon atoms). 4 alkyl groups, alkoxy groups having 1 to 4 carbon atoms, and / or those having a halogen atom as a substituent, and R ₁₄ is a group represented by the following general formula [31]

(Wherein R ₄₀ represents an alkylene group having 1 to 6 carbon atoms, and R ₄₁ represents an alkylene group having 1 to 20 carbon atoms with or without an oxygen atom in the chain). ], The mixture obtained with a copolymer obtained by copolymerizing an osmium catalyst, and then subjecting the obtained osmium-supported polymer to a crosslinking reaction, a method for producing an osmium-supported catalyst composition. The styrenic monomer is a monomer represented by the following general formula [1]

(R _{1 to} R ₃ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ₄ represents an aryl group having 6 to 10 carbon atoms, and these aryl groups have an aromatic ring. And those having an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms and / or a halogen atom as a substituent).
The monomer containing an aromatic group having an epoxy group and a polymerizable double bond is a monomer represented by the following general formula [2]

[R _{5 to} R ₇ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ₈ represents an arylene group having 6 to 10 carbon atoms or an arylalkylene group having 7 to 12 carbon atoms (this An arylene group and an arylalkylene group include those having an aromatic ring having an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms and / or a halogen atom as a substituent, and R ₉ is Group containing an epoxy group represented by the following general formula [21] or [22]

(In the formula, R ₂₁ and R ₂₅ represent an alkylene group having 1 to 6 carbon atoms, and R ₂₂ and R ₂₆ represent an alkylene group having 1 to 20 carbon atoms with or without an oxygen atom in the chain. , R ₂₃ , R ₂₄ , R ₂₇ and R ₂₈ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 12 carbon atoms, The aryl group and the aralkyl group include those having an aromatic ring having an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and / or a halogen atom. Production method. The production method according to claim 2, wherein R _{1 to} R ₃ , R _{5 to} R ₇ , and R _{10 to} R ₁₂ are a hydrogen atom or a methyl group. The production method according to claim 2, wherein R ₄ is a phenyl group. R ₈ is a phenylene group, and R ₉ is a group containing an epoxy group represented by the following general formula [23]

3 wherein R ₃₁ represents an alkylene group having 1 to 3 carbon atoms, n represents 1 to 6. R ₂₁ , R ₂₃ and R ₂₄ are the same as above. Manufacturing method. The production method according to claim 5, wherein R ₂₁ and R ₃₁ are methylene groups, and R ₂₃ and R ₂₄ are methyl groups. R ₁₄ is a group represented by the following general formula [32] or general formula [33]

(Wherein R ₄₂ represents an alkylene group having 1 to 6 carbon atoms, R ₄₃ , R ₄₄ and R ₄₅ represent an alkylene group having 1 to 3 carbon atoms, and p represents an integer of 1 to 6, q Represents an integer of 2 to 6.) The production method according to claim 1. The production method according to claim 7, wherein R ₁₃ is a phenylene group, and R ₁₄ is a group represented by the general formula [32]. R ₄₂ is methylene group, R ₄₃ is an ethylene group, a manufacturing method of claim 8. The molar polymerization ratio of (1) styrenic monomer and (2) monomer containing an aromatic group having an epoxy group and a polymerizable double bond is 60:40 to 95: 5, and (1) styrenic monomer and ( 2) The production method according to claim 1, wherein the molar polymerization ratio of the hydrophilic group-containing monomer represented by the general formula [3] is 60:40 to 95: 5. The molar polymerization ratio of (1) styrenic monomer and (2) monomer containing an aromatic group having an epoxy group and a polymerizable double bond is 70:30 to 90:10, and (1) styrenic monomer and ( 2) The production method according to claim 1, wherein the molar polymerization ratio of the hydrophilic group-containing monomer represented by the general formula [3] is 70:30 to 90:10. (I) a copolymer obtained by copolymerizing (1) a styrene monomer and (2) a monomer containing an aromatic group having an epoxy group and a polymerizable double bond; and (1) a styrene monomer and (2 ) Hydrophilic group-containing monomer represented by the following general formula [3]

[Wherein, R _{10 to} R ₁₂ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ₁₃ represents an arylene group having 6 to 10 carbon atoms (the aromatic ring having 1 to 6 carbon atoms). 4 alkyl groups, alkoxy groups having 1 to 4 carbon atoms and / or those having a halogen atom as a substituent, and R ₁₄ is a group represented by the following general formula [31]

(Wherein R ₄₀ represents an alkylene group having 1 to 6 carbon atoms, and R ₄₁ represents an alkylene group having 1 to 20 carbon atoms with or without an oxygen atom in the chain). Each of the copolymers obtained by copolymerizing and supporting an osmium catalyst and then mixing, or
(II) a copolymer obtained by copolymerizing (1) a styrenic monomer and (2) a monomer containing an aromatic group having an epoxy group and a polymerizable double bond; and (1) a styrenic monomer and (2 ) Hydrophilic group-containing monomer represented by the following general formula [3]

[Wherein, R _{10 to} R ₁₂ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ₁₃ represents an arylene group having 6 to 10 carbon atoms (the aromatic ring having 1 to 6 carbon atoms). 4 alkyl groups, alkoxy groups having 1 to 4 carbon atoms, and / or those having a halogen atom as a substituent, and R ₁₄ is a group represented by the following general formula [31]

(Wherein R ₄₀ represents an alkylene group having 1 to 6 carbon atoms, and R ₄₁ represents an alkylene group having 1 to 20 carbon atoms with or without an oxygen atom in the chain). ] An osmium-supported catalyst composition obtained by supporting an osmium catalyst in a mixture with a copolymer obtained by copolymerizing and then subjecting the obtained osmium-supported polymer to a crosslinking reaction.