JP2003337125A - Adsorption separating medium, packing material for chromatograph, column therefor, and liquid chromatography - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adsorption separating medium with excellent separative power, a packing material for a chromatograph, a column therefor, and liquid chromatography. <P>SOLUTION: A vinyl pyridine homopolymer including a vinyl pyridine compound or a material consisting of a copolymer modified with vinyl pyridine and a monomer polymerizable is employed to a carrier consisting of the particle of an inorganic compound including an OH group as the adsorption separating medium. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adsorption separating agent, a chromatographic packing material, a chromatographic column and a liquid chromatograph which are useful for pretreatment of samples or separation of organic compounds.

[0002]

2. Description of the Related Art It is necessary to dissolve or disperse a mixture of organic compounds in a solvent and then pass through a layer of a separating agent to separate the mixture due to a difference in affinity for the separating agent in industrial production or in liquid chromatography. It is widely used in laboratories that handle organic compounds as graphs.

The separating agent used for such a purpose is a powder of an inorganic compound having a functional group on the surface, or a powder of an inorganic compound whose surface is modified with a specific organic compound according to the characteristics of the organic compound to be separated. It is used.

[0004]

[Problems of the prior art] Particularly in high performance liquid chromatography, a column packed with silica in which an organic phase is immobilized is the mainstream. However, since a silica carrier has a hydroxyl group, it is unfavorable. Adsorption and abnormal retention of basic substances are observed. Therefore, in order to improve the separation performance of liquid chromatography, it is essential to reduce the influence of residual hydroxyl groups.

[0005]

Therefore, an object of the present invention is to provide a useful adsorptive separating agent which can reduce the influence of the hydroxyl groups of the carrier, suppress the adsorption of basic substances, and have excellent retention during the separation operation. To provide. Another object of the present invention is to provide a chromatographic packing material, a chromatographic column, and a liquid which impart a molecular structure selectivity exceeding the performance of conventional column packing materials and enable stable and high-performance liquid chromatography. It is intended to provide a chromatograph.

[0006]

That is, the present invention is an adsorption / separation agent in which a carrier is modified with a vinylpyridine polymer containing 10 mol% or more of vinylpyridine.

The vinyl pyridine polymer is preferably a polymer (1) having a structure satisfying the following general formula (1).

[Chemical 7] (However, X ₁ is a telogen having a terminal group capable of reacting with a hydroxyl group, X ₂ is hydrogen or a group forming an end point of the reaction, X ₃ is a heteroaromatic ring group, and a is 2 to 100.
Average polymerization degree)

The polymer (1) is preferably produced by the following reaction formula (1).

[Chemical 8] (However, X ₁ is a telogen having a terminal group capable of reacting with a hydroxyl group, X ₂ is hydrogen or a group forming an end point of the reaction, X ₃ is a heteroaromatic ring group, and a is 2 to 100.
Average polymerization degree, A'is the same integer as a)

The vinyl pyridine polymer is preferably a polymer (2) having a structure satisfying the following general formula (2).

[Chemical 9] (However, X ₁ is a telogen having a terminal group capable of reacting with a hydroxyl group, X ₂ is hydrogen or a group terminating the reaction, X ₃ is a heteroaromatic ring group, and X ₄ is hydrogen or methyl. Group, X ₅ is NH or O, and a and b are 2 to
Average degree of polymerization of 100, n is 1 to 24)

The polymer (2) is preferably produced by the following reaction formula (2).

[Chemical 10] (However, X ₁ is a telogen having a terminal group capable of reacting with a hydroxyl group, X ₂ is hydrogen or a group terminating the reaction, X ₃ is a heteroaromatic ring group, and X ₄ is hydrogen or methyl. Group, X ₅ is NH or O, and a and b are 2 to
Average degree of polymerization of 100, n is 1 to 24)

The vinyl pyridine polymer is preferably a polymer (3) having a structure satisfying the following general formula (3).

[Chemical 11] (However, X ₁ is a telogen having a terminal group capable of reacting with a hydroxyl group, X ₂ is hydrogen or a group terminating the reaction, X ₃ is a heteroaromatic ring group, and X ₄ is hydrogen or methyl. Group, X ₅ is NH or O, X ₆ is a functional group capable of reacting with a hydroxyl group, a, b and c are an average degree of polymerization of 2 to 100, and n is 1 to 24).

The polymer (3) is preferably produced by the following reaction formula (3).

[Chemical 12] (However, X ₁ is a telogen having a terminal group capable of reacting with a hydroxyl group, X ₂ is hydrogen or a group terminating the reaction, X ₃ is a heteroaromatic ring group, and X ₄ is hydrogen or methyl. Group, X ₅ is NH or O, X ₆ is a functional group capable of reacting with a hydroxyl group, a, b and c are an average degree of polymerization of 2 to 100, and n is 1 to 24).

The carrier is preferably an inorganic porous powder. Further, the inorganic porous powder is preferably a powder having a hydroxyl group on the surface of at least one selected from silica, zeolite, titania, and alumina.

The weight ratio of the vinylpyridine polymer to the carrier is preferably in the range of 1/20 to 5/1.

A second aspect of the present invention is a packing material for a chromatograph, which is obtained by chemically modifying a carrier with a vinylpyridine polymer having a vinylpyridine content of 10 mol% or more.

A third invention of the present invention is a chromatographic column packed with the above-mentioned chromatographic packing material.

A fourth invention of the present invention is a liquid chromatograph comprising the above-mentioned chromatographic column, a pump for feeding the mobile phase to the column, and a detector for detecting the separated liquid from the column.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
Examples of the carrier used in the present invention include silica, zeolite, titania, and inorganic compound carriers such as alumina, glass, carbon, diatomaceous earth, organic compound carriers such as polyethylene, polypropylene, cellulose, and organic polymers such as polyvinyl alcohol. Can be mentioned. Among these, zeolite having many hydroxyl groups on the surface, titania, alumina, or silica is preferable. Of these, silica is particularly preferable.

The particle size of the carrier differs depending on whether it is used industrially or chromatographically in a laboratory, but generally the particle size is 0.5 μm to 10 mm, preferably 1 μm to 30 μm.
It is 0 μm. The carrier is preferably porous, and the average pore size thereof is preferably 10Å to 1 μm,
Å to 0.5 μm is more preferable.

In the present invention, a vinylpyridine polymer containing 10 mol% or more of vinylpyridine compound is used as the stationary phase for modifying the carrier.

Examples of the vinyl pyridine compound used in the present invention include compounds having weak basicity such as 4-vinyl pyridine, 2-vinyl pyridine and 2-vinyl pyrimidine. Of these, 4-vinylpyridine is most preferable because it is easily available.

In the vinyl pyridine type polymer used in the present invention, the amount of the vinyl pyridine type compound is 10 mol% or more, preferably in the range of 30 to 100 mol%. An excellent separating agent is obtained.

The structure of the vinylpyridine polymer modified with the carrier in the present invention can be classified into the following (1) to (3).

<< Vinylpyridine Polymer (1) >> The vinylpyridine polymer (1) is a polymer having a structure in which most of the monomers constituting the polymer (other than telogen) are vinylpyridine compounds. This vinylpyridine polymer can be represented by the following general formula (1).

[Chemical 13] (However, X ₁ is a telogen having a terminal group capable of reacting with a hydroxyl group, X ₂ is hydrogen or a group forming an end point of the reaction, X ₃ is a heteroaromatic ring group, and a is 2 to 100.
Average polymerization degree)

The telogen in the present invention is a compound capable of stopping a radical reaction, and particularly a compound having an end group capable of reacting with a hydroxyl group. Specific examples of such a telogen include silane coupling agents such as 5-isocyanatopentyltriethoxysilane and 3-mercaptopropyltrimethoxysilane. Of these, 3-mercaptopropyltrimethoxysilane is preferable because it is easy to handle.

In the general formula (1), X ₃ is a group consisting of a heteroaromatic ring which constitutes the pyridine compound. The average degree of polymerization (a) of the pyridine polymer is 2
The range is ˜200, preferably 2 to 100, and particularly 10 to 50. In this range, the polymerization is easy and the separation ability is the highest. The molecular weight distribution (Mw / Mn) of the vinyl pyridine-based polymer in the present invention is preferably 1 to 10,
More preferably, it is 1 to 3.

<< Vinylpyridine-based Polymer (2) >> The vinylpyridine-based polymer (2) is a copolymer of the vinylpyridine-based compound and other radical-copolymerizable monomer except the telogen. It is a polymer. Such a vinylpyridine-based polymer can be represented by the following general formula (2).

[Chemical 14] (However, X ₁ is a telogen having a terminal group capable of reacting with a hydroxyl group, X ₂ is hydrogen or a group terminating the reaction, X ₃ is a heteroaromatic ring group, and X ₄ is hydrogen or methyl. Group, X ₅ is NH or O, and a and b are 2 to
Average degree of polymerization of 100, n is 1 to 24)

The vinyl pyridine compound and the other radically copolymerizable monomer are, for example, methyl methacrylate,
Methacrylic acid such as ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate having an alkyl group with a carbon number (n) of 1 to 22. Alkyl ester; methyl acrylate,
For example, an alkyl acrylate having an alkyl group having 2 to 24 carbon atoms, such as ethyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate. Unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile, and copolymerizable with them,
Examples thereof include maleic anhydride, methacrylic acid, acrylic acid, methacrylamide, acrylamide, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, hydroxyethyl methacrylate and hydroxyethyl acrylate. These alone or 2
A mixture of two or more species can be used.

In the general formula (2), X _{1 to} X ₄ are the same as in the vinylpyridine polymer (1). X ₅ is NH or O. The average degree of polymerization a of the vinyl pyridine-based polymer and the average degree of polymerization b of the vinyl pyridine-based compound and other monomer capable of radical copolymerization are 2 to 1,000, preferably 2
The average degree of polymerization is -100. The vinylpyridine-based polymer (2) may be a block copolymer of a vinylpyridine-based compound and another monomer or a random copolymer.

When X ₄ is hydrogen, it is an acrylic acid type compound, and when X ₄ is a methyl group, it is a methacrylic acid type compound.

Another monomer which is radically copolymerizable with the vinylpyridine compound is an acid ester when X ₅ is O and an acid amide when X ₅ is NH.

<< Vinylpyridine-based Polymer (3) >> The vinylpyridine-based polymer (3) is a functional group in which a monomer constituting the polymer reacts with other monomer capable of radical copolymerization with a vinylpyridine-based compound and a hydroxyl group. It is a terpolymer with a vinyl monomer having Such a vinylpyridine polymer can be represented by the general formula (3).

[0033]

[Chemical 15]

In the general formula (3), X _{1 to} X ₆ are the same as those described for the vinyl pyridine polymer (2). The average degree of polymerization a of the vinyl pyridine-based polymer, the average degree of polymerization b of the vinyl pyridine-based compound and other monomer capable of radical copolymerization, and the average degree of polymerization c of the vinyl monomer having a functional group that reacts with a hydroxyl group are 2 to 1,000. , Preferably 2 to 1
The average degree of polymerization is 00.

In the vinylpyridine polymer (3), the polymer composed of the vinylpyridine compound, another monomer and a vinyl monomer having a functional group capable of reacting with a hydroxyl group may be a block copolymer or a random copolymer. Although it may be a copolymer, it is preferably a random copolymer from the viewpoint of easy radical polymerization.

<< Production of Vinyl Pyridine Polymer (1) >>
The vinylpyridine polymer (1) can be produced, for example, by the reaction formula (1). That is, a vinylpyridine compound is reacted in the presence of a radical initiator,
Polymerize.

[0037]

[Chemical 16]

In the reaction formula (1), X _{1 to} X ₃ and the degree of polymerization a are the same as those described for the vinylpyridine polymer (1). The blending amount A ′ of the vinylpyridine compound is the degree of polymerization a
Is the same integer as.

Examples of the radical polymerization initiator which can be used in the present invention include acetyl peroxide, succinic acid peroxide, t-butyl peroctoate, benzyl peroxide, t-butyl peroxymaleic acid, 1
-Hydroxy-1-hydroperoxydicyclohexyl peroxide, 1,1-bis (t-butylperoxy)
-3,3,5-Trimethylcyclohexane, t-butylperoxycrotonate, 2,2-bis (t-butylperoxybutane), t-butylperoxyisopropyl carbonate, t-butylperoxybivalate, lauroylper Oxide, t-butyl peroxyisobutyrate, di-t-butyl peroxide, 1,1,3,3-
Tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 2,5-dimethyl-
2,5-bis (benzoylperoxy) hexane, t-
Butyl peracetate, 2,5-dimethyl-di (hydroperoxy) hexane, t-butyl hydroperoxide, t-butyl cumyl peroxide, p-menthane hydroperoxide, methyl ethyl ketone peroxide, di-t-butyl peroxy. Phthalate, t-butylperbenzoate, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,
4-pentanedione peroxide, azobisisobutyronitrile and the like can be mentioned, and these can be used alone or in admixture of two or more.

The amount of the radical polymerization initiator (c) compounded is 0.01 to 100 parts by weight of the vinyl monomer.
10 parts, preferably 1-10 parts, more preferably 1-
5 copies.

As a method for producing the above vinyl pyridine type polymer, for example, vinyl pyridine and, if necessary, other solvents may be used in the presence or absence of a solvent such as benzene, methanol, chloroform or toluene in a polymerization vessel. It can be produced by charging the above-mentioned comonomer and heating and stirring at a temperature not lower than the decomposition temperature of the initiator.

The vinyl pyridine type polymer (2) can be produced by the reaction formula (2).

[0043]

[Chemical 17]

The vinylpyridine polymer (2) is produced by
The other conditions are almost the same except that the method for producing the vinyl pyridine polymer (1) is different from the compounding monomer.

The vinylpyridine polymer (3) can be produced by the reaction formula (3).

[0046]

[Chemical 18]

The vinyl pyridine polymer (3) is produced by
The other conditions are almost the same except that the method for producing the vinyl pyridine polymer (1) is different from the compounding monomer.

<< Modification of Vinyl Pyridine Polymer to Carrier >> To modify the carrier of the vinyl pyridine polymer obtained by the above method, the end substituents of the silane coupling residue of the vinyl pyridine polymer are It can be easily produced by reacting with a porous carrier having a hydroxyl group.

As a specific method for modifying the carrier with the vinylpyridine polymer, for example, chloroform,
The vinylpyridine polymer is dispersed in a solvent such as N, N-dimethylformamide, and then reacted at 60 to 90 ° C. for 2 to 6 hours in an inert gas atmosphere such as nitrogen. Then, the reaction solution is filtered, and the reaction product is post-treated by a usual method to obtain the adsorption separating agent of the present invention in which the vinyl pyridine polymer is chemically modified on the silica carrier.

In the adsorption / separation agent of the present invention, the weight ratio of the vinylpyridine polymer to the carrier is in the range of 1/20 to 5/1, preferably 1/10 to 1/1. .

The adsorptive separating agent of the present invention can be used as a packing material for chromatography, which is the second invention of the present invention for packing a column.

The chromatographic packing material of the present invention can be packed in a column and used as the chromatographic column of the third aspect of the present invention.

A fourth invention of the present invention is a liquid chromatograph comprising the above-mentioned chromatographic column, a pump for feeding the mobile phase to this column, and a detector for detecting the separated liquid from the column. Then, the organic mixture can be separated by such a device.

Examples of the organic compound which can be separated by the adsorption / separation agent, the chromatographic packing material, the chromatographic column, and the liquid chromatograph of the present invention include aromatic hydrocarbons, amino acids, amines, carboxylic acids, hydroxycarboxylic acids, Alcohol, glucose, mannose,
Examples thereof include sugar compounds such as fructose, proteins and the like.

[0055]

EFFECTS OF THE INVENTION Since a vinylpyridine polymer is used as a modifying compound in the present invention, the influence of the hydroxyl group of the carrier can be reduced and the adsorption of basic substances can be suppressed. As a result, the theoretical plate number in the separation operation can be reduced. And the separation factor is excellent. In addition, the adsorptive separation agent of the present invention provides molecular structure selectivity exceeding the performance of conventional column packing materials. This enables stable and high-performance liquid chromatography in the field of separation and analysis.

[0056]

The present invention will be described in more detail below with reference to comparative examples and examples, but the present invention is not limited to these examples.

[0057]

Example 1 << Synthesis of 4-vinylpyridine polymer (P4VP) >> 4-vinylpyridine (4VP) 10 ml (92.8 mm) was placed in a two-necked flask equipped with a nitrogen introducing device and a reflux condenser.
Ol) and 0.91 ml (4.64 mmol) of 3-mercaptopropyltrimethoxysilane, and the mixture was stirred and mixed for 20 minutes while introducing nitrogen gas. Then, azobisisobutyronitrile (AIBN) was added as a polymerization initiator, and the mixture was stirred and mixed at 60 ° C. for 6 hours under a nitrogen atmosphere. After cooling the obtained solution to room temperature, 10 ml of chloroform
Was added, and the mixture was poured into 150 ml of n-hexane for reprecipitation to obtain a pale yellow viscous precipitate. The same reprecipitation operation was performed twice, and the obtained pale yellow precipitate was dried under reduced pressure with a vacuum desiccator to obtain a pale yellow powder. The obtained compound was ¹ H-NMR.
Propyl group around 0.7ppm and 8.5p in the spectrum
The average degree of polymerization is 2 depending on the integration ratio of the pyridyl group near pm.
It was confirmed to be 1.

<< Immobilization of P4VP on silica gel >> Silica gel (brand YMC120-5, manufactured by Yamamura Chemical Co., Ltd., average particle diameter 4.4 μm, average pore diameter 126Å,
2.5g of specific surface area 333m ^{2 /} g) and 3.0g of P4VP
Then, 30 ml of chloroform was added as a solvent. After stirring and mixing at 60 ° C. for 8 days, the mixture was collected by a filter and washed with 20 ml each of chloroform and methanol to collect the target product (P4VP-Si). P4VP-
The yield of Si was 2.75 g. P4 by elemental analysis
It was confirmed that the amount of P4VP immobilized in VP-Si was 29.4% by weight.

<< Effect as Column Chromatographic Packing Material >> 4-vinylpyridine polymer-immobilized silica (P4VP-Si) produced by the above method was used, having an inner diameter of 4.6 mm and a length of 1
It was packed in a 00 mm stainless steel column to prepare a cartridge column.

This column was placed in a constant temperature column holder, and a mixture of pyridine and benzene was separated under the following conditions by a liquid chromatograph consisting of a liquid feed pump, a detector and an injector. Developing agent: Water: Methanol = 9: 1 Flow rate: 1 ml / mim Temperature: 25 ° C

The results are shown in FIG. In addition, in FIG.
TR indicates the time (minute) when the elution of the specific compound was maximized.

[0062]

Example 2 Example 1 was repeated except that the separated sample was a mixture of cis-stilbene and trans-stilbene. The results are shown in Figure 2. In addition, in FIG. 2, k represents a holding coefficient and α represents a separation coefficient.

[0063]

[Comparative Example 1] A commercially available separating agent (ODS, GL)
Cis) under the same conditions as in Example 2
Separation of the mixture of stilbene and trans-stilbene was carried out. The results are shown in Figure 2.

[0064]

Example 3 The procedure of Example 1 was repeated, except that the separated sample was a mixture of o-terphenyl, m-terphenyl, and triphenylene. The result is shown in Figure 3.
Shown in.

[0065]

[Comparative Example 2] Commercially available separating agents (ODS, GL)
(Manufactured by Science Co., Ltd.) was used to separate a mixture of o-terphenyl, m-terphenyl, and triphenylene under the same conditions as in Example 3. The results are shown in Fig. 3.

[0066]

Example 4 << 2-Vinylpyridine Polymer (P2V
Synthesis of P) >> 2-vinylpyridine (2VP) 10 ml in a two-necked flask equipped with a nitrogen introducing device and a reflux condenser.
(92.8 mmol) and 2.4 ml (12.4 mmol) of 3-mercaptopropyltrimethoxysilane were added,
The mixture was stirred and mixed for 20 minutes while introducing nitrogen gas. After that, azobicisobutyronitrile (A
IBN) was added, and the mixture was stirred and mixed at 60 ° C. for 6 hours under a nitrogen atmosphere. The obtained solution was cooled to room temperature, 10 ml of chloroform was added, and the mixture was reprecipitated by pouring into 150 ml of n-hexane to obtain a pale yellow viscous precipitate. The same reprecipitation operation was performed twice, and the obtained pale yellow precipitate was dried under reduced pressure with a vacuum desiccator to obtain a pale yellow powder. The obtained compound is ¹ H-
From the NMR spectrum, it was confirmed that the average degree of polymerization was 23 by the integral ratio of the propyl group near 0.7 ppm and the pyridyl group near 8.5 ppm.

<< Fixation of P2VP on silica gel >> Silica gel (brand YMC120-5, manufactured by Yamamura Chemical Co., Ltd., average particle size 4.4 μm, average pore size 126Å,
Specific surface area 333 m ^{2 /} g) 2.5 g and P2VP 3.0 g
Then, 30 ml of chloroform was added as a solvent. After stirring and mixing at 60 ° C. for 8 days, the mixture was separated by a filter and washed with 20 ml each of chloroform and methanol to recover the target product (Si-P2VP). Si-P2
The VP yield was 3.23 g. Si by elemental analysis
It was confirmed that the immobilized amount of P2VP in -P2VP was 39.4% by weight.

[Brief description of drawings]

FIG. 1 is a diagram showing the results of separating a mixture of pyridine and benzene by liquid chromatography using the separating agent of the present invention.

FIG. 2 is a diagram showing the results of separating a mixture of cis-stilbene and trans-stilbene by liquid chromatography using the separating agent of the present invention.

FIG. 3 is a diagram showing the results of separating a mixture of o-terphenyl, m-terphenyl, and triphenylene by liquid chromatography using the separating agent of the present invention.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // G01N 30/26 G01N 30/26 A 30/74 30/74 E 30/88 30/88 C

Claims (13)

[Claims] 1. An adsorption / separation agent in which a carrier is modified with a vinylpyridine polymer containing 10 mol% or more of a vinylpyridine compound. 2. The adsorptive separation agent according to claim 1, wherein the vinylpyridine polymer is a polymer (1) having a structure satisfying the following general formula (1). [Chemical 1] (However, X ₁ is a telogen having a terminal group capable of reacting with a hydroxyl group, X ₂ is hydrogen or a group forming an end point of the reaction, X ₃ is a heteroaromatic ring group, and a is 2 to 100.
Average polymerization degree) 3. The adsorptive separating agent according to claim 2, wherein the polymer (1) is produced by the following reaction formula (1). [Chemical 2] (However, X ₁ is a telogen having a terminal group capable of reacting with a hydroxyl group, X ₂ is hydrogen or a group forming an end point of the reaction, X ₃ is a heteroaromatic ring group, and a is 2 to 100.
Average polymerization degree, A'is the same integer as a) 4. The adsorptive separating agent according to claim 1, wherein the vinylpyridine polymer is a polymer (2) having a structure satisfying the following general formula (2). [Chemical 3] (However, X ₁ is a telogen having a terminal group capable of reacting with a hydroxyl group, X ₂ is hydrogen or a group terminating the reaction, X ₃ is a heteroaromatic ring group, and X ₄ is hydrogen or methyl. Group, X ₅ is NH or O, and a and b are 2 to
Average degree of polymerization of 100, n is 1 to 24) 5. The adsorptive separating agent according to claim 4, wherein the polymer (2) is produced by the following reaction formula (2). [Chemical 4] (However, X ₁ is a telogen having a terminal group capable of reacting with a hydroxyl group, X ₂ is hydrogen or a group terminating the reaction, X ₃ is a heteroaromatic ring group, and X ₄ is hydrogen or methyl. Group, X ₅ is NH or O, and a and b are 2 to
Average degree of polymerization of 100, n is 1 to 24) 6. The adsorptive separating agent according to claim 1, wherein the vinylpyridine polymer is a polymer (3) having a structure satisfying the following general formula (3). [Chemical 5] (However, X ₁ is a telogen having a terminal group capable of reacting with a hydroxyl group, X ₂ is hydrogen or a group terminating the reaction, X ₃ is a heteroaromatic ring group, and X ₄ is hydrogen or methyl. Group, X ₅ is NH or O, X ₆ is a functional group capable of reacting with a hydroxyl group, a, b and c are an average degree of polymerization of 2 to 100, and n is 1 to 24). 7. The adsorptive separating agent according to claim 6, wherein the polymer (3) is produced by the following reaction formula (3). [Chemical 6] (However, X ₁ is a telogen having a terminal group capable of reacting with a hydroxyl group, X ₂ is hydrogen or a group terminating the reaction, X ₃ is a heteroaromatic ring group, and X ₄ is hydrogen or methyl. Group, X ₅ is NH or O, X ₆ is a functional group capable of reacting with a hydroxyl group, a, b and c are 2-100 average polymerization degree, n is 1-24) 8. The adsorptive separating agent according to claim 1, wherein the carrier is an inorganic porous powder. 9. The adsorptive separating agent according to claim 8, wherein the inorganic porous powder is one or more kinds of powder selected from silica, zeolite, titania, and alumina. 10. The adsorptive separating agent according to claim 1, wherein the weight ratio of the vinylpyridine polymer to the carrier is in the range of 1/20 to 5/1. 11. A packing material for a chromatograph, which is obtained by chemically modifying a carrier with a vinylpyridine polymer containing 10 mol% or more of vinylpyridine. 12. A chromatographic column filled with the chromatographic packing material according to claim 11. 13. A chromatographic column according to claim 12,
A liquid chromatograph comprising a pump for feeding a mobile phase to the column, and a detector for detecting a separated liquid from the column.