JP2001116737A - Adsorption/separation method with use of porous particle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adsorption/separation method which can handle polar and nonpolar substances, or hydrophilic and hydrophobic substances to be adsorbed/separated. SOLUTION: The adsorption/separation method uses as an adsorption/ separation material porous particles having pores and formed of a crystalline organic inorganic composite material having a framework comprised of an organic group with one or more carbon atoms, two or more metal atoms bound to the same or different carbon atoms in the organic group, and one or more oxygen atoms bound to the metal atoms.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an adsorption separation method using porous particles made of a crystalline organic-inorganic composite material as an adsorption separation agent.

[0002]

2. Description of the Related Art Porous materials are widely used as various adsorbing / separating agents. Examples of uses of the porous material include oxygen production and carbon dioxide separation using pressure swing adsorption, wastewater and water treatment, purification of chemical intermediates and pharmaceuticals, chromatography, sustained-release pharmaceutical carriers, and the like. . Porous materials used in such applications can be broadly classified into inorganic porous materials and organic porous materials. Examples of the inorganic porous substance include activated carbon, zeolite, and silica gel. Examples of the organic porous substance include a polymer porous sintered body made of polypropylene, polytetrafluoroethylene, polycarbonate, polyamide, and the like.

Recently, in addition to the above-mentioned porous materials, a porous material made of an organometallic complex or a porous material made by reacting a surfactant with a silicon alkoxide (hereinafter, referred to as a porous material).
FSM) is known (JP-A-10-6871).
No. 9).

As a porous material composed of a metal oxide, a porous material having a spherical particle shape (S. Shio et a
l., Chem. Commun., p.2461, 1998; H. Yang et al.,
J. Mater. Chem., Vol. 8, p. 743, 1998), a porous material having a rod-like particle shape (S. Shio et al., Chem. Comm.
un., p.2461, 1998), a porous material having an octahedral particle shape (JM Kim et al., Chem. Commun., 259,
1998) is known.

Among the above porous materials, silica gel (hereinafter, referred to as SI) and silica gel whose surface is modified with an octadecyl group (hereinafter, referred to as ODS) are typical porous materials used as packing materials for liquid chromatography. Material. SI is suitable for separating relatively polar compounds, and is used in a normal phase system in which a weakly polar solvent is used as a mobile phase. On the other hand, ODS is suitable for separating a compound having a weak polarity, and is used in a reversed-phase system using a solvent having a strong polarity as a mobile phase. Liquid chromatography using these materials is a separation mechanism utilizing the difference in the partition coefficient of the target substance between the mobile phase and the stationary phase (filler).

[0006]

However, when the above-mentioned porous material is used as a packing material for liquid chromatography, there are the following problems.

That is, when SI is used as a filler, it is difficult to use a reverse phase system, and when ODS is used as a filler, it is difficult to use a normal phase system. When it is desired to perform separation of both a non-polar compound and a non-polar compound, there is a problem that both a column packed with SI and a column packed with ODS must be used. In particular, when ODS is used as a filler, a surface treating agent such as an octadecyl group is easily desorbed at the time of a separation operation.

When FSM is used as a packing material for liquid chromatography, the concentration of silanol groups on the surface of the FSM is lower than that of SI, so that the hydrophilicity is weak and the separation characteristics in a reversed phase system are exhibited. There is a problem that the separation performance in a reversed-phase system is inferior due to weakness. Also, FSM
Since water is easily adsorbed on the surface of, when the separation is performed in a system containing water, the hydrophobicity decreases with time. There is also an attempt to attach an organic group to the surface of the FSM to impart hydrophobicity, but since the surface is covered with the organic group, separation in a normal phase system becomes difficult as in the case of SI. Further, since this organic group is easily desorbed during the separation operation, there is a problem that this organic group is mixed into the separated product.

When the porous material having the above-mentioned specific shape is used as a filler for liquid chromatography, it is difficult to use it in a reversed-phase system as in the case of SI because it is made of a metal oxide. There's a problem.

The present invention has been made in view of such technical problems, and it is possible to make polar and non-polar substances, or hydrophilic and hydrophobic substances, the targets of adsorption and separation. An object of the present invention is to provide an adsorption separation method.

[0011]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a crystalline organic compound in which an organic group, a metal atom and an oxygen atom are bonded in a specific bonding manner. By the adsorption separation method using porous particles composed of inorganic composite material as the adsorption separation material, it is possible to target polar and non-polar substances or hydrophilic and hydrophobic substances for adsorption and separation. Heading, the present invention has been completed.

That is, the adsorption separation method of the present invention comprises an organic group having one or more carbon atoms, two or more metal atoms bonded to the same or different carbon atoms in the organic group, and one or more metal atoms bonded to the metal atom. The method is characterized in that porous particles having fine pores, which are made of a crystalline organic-inorganic composite material having a skeleton composed of the above oxygen atoms, are used as an adsorption separation material.

In the present invention, the value obtained by dividing the total volume of pores having a diameter within the range of ± 40% of the central pore diameter by the total volume of pores in the porous particles is 0.6 to 1%. It is preferable that the X-ray diffraction pattern of the porous particles has one or more peaks at a diffraction angle corresponding to a d value of 1 nm or more.

In the present invention, the porous particles preferably have a spherical, hexagonal or octahedral shape, and the skeleton is a structural unit represented by the following general formula (1). It is preferable that it is composed of at least one kind.

Embedded image (Wherein, R ¹ is an organic group having one or more carbon atoms, M is a metal atom, R ² is hydrogen, a hydroxyl group or a hydrocarbon group, x is an integer obtained by subtracting 1 from the valence of the metal M, and n is 1 or more. and an integer of x or less and m represents an integer of 2 or more, provided that carbons in R ¹ to which M is bonded may be the same or different.)

Further, in the present invention, it is preferable that the average particle diameter of the porous particles is 0.01 to 100 μm and the center pore diameter is 1 to 50 nm.

[0016]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below in more detail.

The adsorption separation method of the present invention comprises an organic group having one or more carbon atoms, two or more metal atoms bonded to the same or different carbon atoms in the organic group, and one or more metal atoms bonded to the metal atom. Porous particles made of a crystalline organic-inorganic composite material having a skeleton composed of oxygen atoms and having pores are used as an adsorption separation material.

First, the porous particles made of a crystalline organic-inorganic composite material used in the present invention will be described.

The organic-inorganic composite material constituting the porous material comprises an organic group, a metal atom and an oxygen atom. The organic group has at least one carbon atom, and the metal atom is contained in the organic group. Has two or more bonds to the same or different carbon atoms, and the oxygen atom has one or more bonds to the metal atom. The organic-inorganic composite material in the present invention has such a structure and has crystallinity. Here, a material having crystallinity means a material having at least one peak due to the regularity of constituent atoms in an X-ray diffraction pattern. The crystal structure is not particularly limited, but the crystal structure is preferably two-dimensional hexagonal, three-dimensional hexagonal, or cubic because symmetric particles can be obtained.

In the present invention, the organic group having one or more carbon atoms must have two or more valences in order to bond to two or more oxygen atoms. Examples of such organic groups include divalent or higher valent organic groups generated by removing two or more hydrogens from hydrocarbons such as alkanes, alkenes, alkynes, benzenes, and cycloalkanes, but are not limited thereto. is not. An organic group is one in which a part of the hydrogen atoms has been substituted with a substituent such as an amide group, an amino group, an imino group, a mercapto group, a sulfone group, a carboxyl group, an ether group, an acyl group, and a vinyl group. Is also good. Further, the organic-inorganic composite material constituting the porous particles used in the present invention has one of the above organic groups.
It may include only one type or two or more types.

In the present invention, a porous material having an appropriate degree of crosslinking is used.
Since particles are obtained, the valence of the organic group must be divalent.
Is preferred. As the divalent organic group, a methylene group (-
CH _Two-), Ethylene group (-CH_TwoCH_Two−), Trimethi
Len group (-CH_TwoCH_TwoCH_Two−), Tetramethylene group
(-CH_TwoCH_TwoCH_TwoCH_Two-), 1,2-butylene group
(-CH (C_TwoH_Five) CH-), 1,3-butylene group (-
CH (CH_Three) CH_TwoCH_Two-), Phenylene group (-C₆H
_Four-), Diethylphenylene group (-C_TwoH_Four-C₆H_Four-C_Two
H_Four-), Vinylene group (-CH = CH-), propenile
Group (-CH_Two-CH = CH_Two-), Butenylene group (-C
H_Two-CH = CH-CH_Two-), Amide group (-CO-NH
-), Dimethylamino group (-CH_Two-NH-CH_Two−),
Trimethylamine group (-CH_Two-N (CH_Three) -CH
_Two−) And the like. Among them, porous grains with high crystallinity
Methylene group, ethyl
A len group and a phenylene group are preferred.

Two or more metal atoms are bonded to the same or different carbon atoms in the above-mentioned organic group, but the kind of the metal is not particularly limited. For example, silicon, aluminum, titanium, magnesium, zirconium, tantalum,
Niobium, molybdenum, cobalt, nickel, gallium,
Examples include beryllium, yttrium, lanthanum, hafnium, tin, lead, vanadium, and boron. Among them, silicon, aluminum, and titanium are preferred because of their good binding to organic groups and oxygen. Note that the above metal bonds to an organic group and an oxygen atom to form an oxide. The oxide may be a composite oxide including two or more metal atoms.

The porous particles used in the present invention include:
It is made of a crystalline organic-inorganic composite material generated by the bonding of the above-mentioned organic group, metal atom and oxygen atom, but the type of this bond is not limited, and for example, a covalent bond, an ionic bond, etc. are possible. It is. In addition, an organic-inorganic composite material having a different skeleton (linear, ladder-like, mesh-like, branched, or the like) is generated depending on the number of metal atoms bonded to the organic group or the number of oxygen atoms bonded to the metal atom.

In the porous particles used in the present invention, the organic groups are bonded to two or more metal atoms and the metal atoms are bonded to one or more oxygen atoms. It is. That is, the skeleton has a metal oxide and an organic group. Therefore, when the porous particles are used as an adsorbing / separating material, it is possible to subject polar and nonpolar substances, or hydrophilic and hydrophobic substances, to a target of adsorption / separation. In addition, the above-mentioned O
Unlike porous materials such as DS and FSM having an organic group bonded to the surface, elimination of the organic group is reduced during the separation operation, so that deterioration of the performance over time can be suppressed. Furthermore, since the porous particles have crystallinity and the pores are regularly arranged, the adsorption / separation performance is improved.

The porous particles used in the present invention are:
The value obtained by dividing the total volume of pores having a diameter within the range of ± 40% of the central pore diameter by the total volume of pores is preferably 0.6 to 1. Here, the central pore diameter is a curve (pore diameter distribution curve) obtained by plotting a value (dV / dD) obtained by differentiating the pore volume (V) by the pore diameter (D) against the pore diameter (D). ) Is the pore diameter at the maximum peak.

The pore size distribution curve can be obtained by the following method. That is, the porous particles, which are adsorption and separation materials, are cooled to the temperature of liquid nitrogen (−196 ° C.), nitrogen gas is introduced, the amount of adsorption is determined by a constant volume method or a weight method, and then the pressure of the introduced nitrogen gas is determined. Is gradually increased, and the adsorption amount of nitrogen gas with respect to each equilibrium pressure is plotted to obtain an adsorption isotherm. Using this adsorption isotherm,
The pore size distribution curve can be obtained by a calculation method such as the anston-Inklay method, the Pollimore-Heal method, and the BJH method.

Therefore, "the value obtained by dividing the total volume of the pores having a diameter within the range of ± 40% of the central pore diameter by the total volume of the pores is 0.6 to 1" is, for example, as follows: When the central pore diameter is 3.00 nm, ± 3.0 of this 3.00 nm
0%, meaning that the sum of the pore volumes in the range of 1.80-4.20 nm occupies 60% or more of the total pore volume. Porous particles that satisfy this condition mean that the pore diameter is very uniform. Further, when such porous particles are used as an adsorption separation material,
The adsorption separation effect is improved due to the uniformity of the pore diameter.

The porous particles used in the present invention are:
The X-ray diffraction pattern preferably has one or more peaks at a diffraction angle corresponding to a d value of 1 nm or more. The X-ray diffraction peak means that a periodic structure having a d value corresponding to the peak angle is present in the sample. Therefore,
The presence of one or more peaks at a diffraction angle corresponding to a d value of 1 nm or more means that pores are regularly arranged at intervals of 1 nm or more. When such porous particles are used as an adsorption / separation material, the arrangement of the pores is regular, so that the adsorption / separation effect is improved.

In the porous particles used in the present invention, the skeleton comprising an organic group, a metal atom and an oxygen atom preferably comprises at least one of the structural units represented by the following general formula (1).

Embedded image

Here, R ¹ represents an organic group having at least one carbon atom. The type of the organic group is not particularly limited,
For example, a divalent or higher valent organic group generated by removing two or more hydrogen atoms from a hydrocarbon such as alkane, alkene, alkyne, benzene, and cycloalkane can be exemplified. In these organic groups, some of the hydrogen atoms are amide groups, amino groups,
It may be substituted with a substituent such as an imino group, a mercapto group, a sulfone group, a carboxyl group, an ether group, an acyl group, and a vinyl group. The organic group is preferably divalent, and examples of the divalent organic group include those described above. As the divalent organic group, a methylene group, an ethylene group, and a phenylene group are preferable since porous particles having high crystallinity can be obtained.

M in the general formula (1) represents a metal atom. Although the type of the metal atom is not particularly limited, for example, silicon, aluminum, titanium, magnesium, zirconium, tantalum, niobium, molybdenum, cobalt, nickel, gallium, beryllium, yttrium,
Lanthanum, hafnium, tin, lead, vanadium, boron can be mentioned. Among them, it is preferable to use silicon, aluminum, and titanium because of their good bondability with an organic group and oxygen.

R ² in the general formula (1) represents hydrogen, a hydroxyl group or a hydrocarbon group. When R ² is a hydrocarbon group, the type thereof is not limited. Examples of R ² include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, a phenyl group, and a substituted phenyl group. And the like. In the general formula (1), x is an integer obtained by subtracting 1 from the valence of the metal M, n is an integer of 1 to x, m
Represents an integer of 2 or more. The carbon atoms of R ¹ to which M is bonded may be the same or different. -O _1/2 -is
These represent a group which becomes -O- by bonding two of them.

In the above general formula (1), R ¹ , M,
When R ² , n, and m are an ethylene group, a silicon group, a methyl group, and 1, 2, respectively, the general formula (1) can be represented by the following chemical formula (2).

Embedded image

A skeleton in which two structural units of the chemical formula (2) are linked can be represented by the following chemical formula (3).

Embedded image

In the general formula (1), R ¹ , M,
When n and m are an ethylene group, silicon, 3, and 2, respectively, the general formula (1) can be represented by the following chemical formula (4).

Embedded image

When a plurality of structural units of the chemical formula (4) are connected, a network structure is formed. The following chemical formula (5) shows four structural units of chemical formula (4) in an example of the network structure.

Embedded image

The skeleton of the organic-inorganic composite material constituting the porous particles used in the present invention comprises a plurality of structural units having different R ¹ , M, R ² , n and m in the general formula (1). There may be. For example, it may be composed of a structural unit represented by the chemical formula (2) and a structural unit represented by the chemical formula (4). Further, the organic-inorganic composite material includes, for example, other than the structural unit represented by the general formula (1),
_{Si- (O 1/2) 4 -,} Ti- (O 1/2) 4 - may have a constitutional unit, and the like.

The porous particles used in the present invention are:
Crystalline particles having a spherical, hexagonal or octahedral shape composed of the above-described organic group, metal atom and oxygen atom are preferred.

The average particle size of the particles is 0.01 to 100 μm.
m, more preferably 0.01 to 50 μm. More preferably, the average particle size is 0.1
５０50 μm. When the average particle size is less than 0.01 μm, the particles are easily scattered and handling is difficult. On the other hand, when the average particle size exceeds 100 μm, the pores inside the particles tend to be insufficiently used. The average particle diameter of the particles having a spherical shape means the average of the diameter (longest diameter), and the average particle diameter of the particles having a hexagonal column shape is the diameter of a hexagonal cross section perpendicular to the longitudinal direction. (The length of the longest diagonal). The average particle diameter of the particles having an octahedral shape means the average of the diameters (the longest distance between the vertices).

On the other hand, the center pore diameter of the pores formed in the porous particles is preferably 1 to 50 nm, and 2 to 50 nm.
More preferably, it is 30 nm. More preferably,
The central pore diameter is between 2 and 10 nm. When the center pore diameter is less than 1 nm, the average pore size is often smaller than the size of the substance to be adsorbed, and thus the adsorption performance tends to decrease. On the other hand, when the center pore diameter exceeds 50 nm, the specific surface area tends to decrease and the adsorption characteristics tend to decrease.

The specific surface area of the porous particles used in the present invention is not particularly limited, but is 700 m ² /
g or more. The specific surface area can be calculated from the adsorption isotherm as a BET specific surface area using a BET isotherm adsorption equation.

The pores of the porous particles used in the present invention are formed not only on the surface of the particles but also inside the particles.
The shape of the pores is not particularly limited, but may be, for example, a tunnel-shaped one or a shape in which spherical or polygonal cavities are connected to each other.

Next, a method for producing porous particles made of a crystalline organic-inorganic composite material used in the present invention will be described.

The porous particles used in the present invention can be obtained, for example, by polycondensing at least one compound represented by the following general formula (6).

Embedded image

Here, R ¹ is an organic group having at least one carbon atom, and M is a metal atom. R ² represents hydrogen, a hydroxyl group or a hydrocarbon group. Note that R in the general formula (6)
^1, M, R ² is equal R ^1, M, and R ² in the general formula (1). A in the general formula (6) represents an alkoxyl group or a halogen atom, x represents an integer obtained by subtracting 1 from the valence of the metal M, n represents an integer of 1 or more and x or less, and m represents an integer of 1 or more. The carbon atoms of R ¹ to which M is bonded may be the same or different.

When A in the general formula (6) is an alkoxyl group, the type of the hydrocarbon group bonded to oxygen in the alkoxyl group is not particularly limited, and examples thereof include chain, cyclic and alicyclic hydrocarbon groups. Hydrogen may be mentioned. The hydrocarbon group is preferably a chain alkyl group having 1 to 5 carbon atoms,
More preferably, it is a methyl group or an ethyl group.

When A in the general formula (6) is a halogen atom, its type is not particularly limited. For example, chlorine, bromine,
Fluorine and iodine can be mentioned. Among them, chlorine and bromine are preferred.

In the general formula (6), R ¹ , M, A,
n and m are respectively an ethylene group, a silicon, a methoxy group,
When it is 3, 2, the general formula (6) is represented by (CH ₃ O) ₃
Represented by _{Si-CH 2 -CH 2 -Si (} OCH 3) 3 becomes 1,2-bis (trimethoxysilyl) ethane.

In the general formula (6), R ¹ , M,
A, n, and m are each an ethylene group, silicon, chlorine,
In the case of 3, 2, the general formula (6) is represented by Cl ₃ Si—C
1,2-bis (trichlorosilyl) ethane represented by H ₂ —CH ₂ —SiCl ₃ is obtained.

When the porous material used in the present invention is produced, the compound represented by the general formula (6) may be polycondensed by adding an alkoxysilane, a titanium alkoxide, an aluminum alkoxide or the like.

As the alkoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and the like can be used. Alternatively, an alkoxysilane having a functional group such as an amino group, a carboxyl group, a mercapto group, or an epoxy group can be used.

As the titanium alkoxide, for example, titanium butoxide, titanium isopropoxide, and titanium ethoxide can be used. As the aluminum alkoxide, for example, aluminum isopropoxide can be used. Various metal halides such as chlorinated silicon (SiCl ₄ ) can also be used.

By adding pseudo-boehmite, sodium aluminate, aluminum sulfate, dialkoxyaluminotrialkoxysilane and the like to the compound represented by the above general formula (6), alkoxysilane, etc.
_{A 2-} Al ₂ O ₃ skeleton can be introduced. In addition, V, B, and Mn can be introduced into the skeleton by adding vanadyl sulfate (VOSO ₄ ), boric acid (H ₃ BO ₃ ), manganese chloride (MnCl ₂ ), and the like to react.

In producing the porous particles used in the present invention, the compound represented by the above general formula (6) is
It is preferable that polycondensation is performed under acidic or alkaline conditions in addition to an aqueous solution containing a surfactant.

As the surfactant, any of cationic, anionic and nonionic surfactants can be used. Such surfactants, such as alkyl trimethyl ammonium _{[C n H 2n + 1 N} (CH 3)
₃ ], alkylammonium, dialkyldimethylammonium, benzylammonium chloride, bromide, iodide, hydroxide, etc., as well as fatty acid salts, alkyl sulfonates, alkyl phosphates, and polyethylene oxide nonionic surfactants And primary alkylamines.

Alkyltrimethylammonium [C _n H
_{2n + 1} N (CH ₃ ) ₃ ] has 8 to 9 carbon atoms of the alkyl group.
It is preferable to use 18 of them.

As the nonionic surfactant, a hydrophobic compound is used.
Having a hydrocarbon group as a component, and polyethylene as a hydrophilic component.
Polyethylene oxide having a lenoxide chain
Ionic surfactants. Such surface activity
As the agent, for example, C₁₆H ₃₃(OCH_TwoCH_Two)_TwoO
H, C₁₂H_{twenty five}(OCH_TwoCH_Two)_FourOH, C₁₆H₃₃(OC
H _TwoCH_Two)_TenOH, C₁₆H₃₃(OCH_TwoCH_Two)₂₀OH,
C₁₈H₃₇(OCH_TwoCH_Two) _TenOH, C₁₈H₃₅(OCH_Two
CH_Two)_TenOH, C₁₂H_{twenty five}(OCH_TwoCH_Two)_{twenty three}OH etc.
No.

Also, a surfactant having a sorbitan fatty acid ester component and a polyethylene oxide component can be used. Such surfactants include Tr
itonX-100 (Aldrich), polyethylene oxide (20) sorbitan monolaurate (Twe
en20, Aldrich), polyethylene oxide (20) sorbitan monopalmitate (Tween4
0), polyethylene oxide (20) sorbitan monostearate, polyethylene oxide (20) sorbitan monooliate (Tween 60), sorbitan monopalmitate (Span 40) and the like.

As the surfactant, a triblock copolymer composed of three polyalkylene oxide chains can also be used. Among them, polyethylene oxide (EO) chain-polypropylene oxide (PO) chain-
Triblock copolymers represented by polyethylene oxide (EO) chains are preferred. The number of repeating EO chains is x,
When the number of PO chain repeats is y, the triblock copolymer can be represented as (EO) x (PO) y (EO) x. Although x and y of the triblock copolymer used in the present invention are not particularly limited, x is 5 to 5.
110, y is preferably from 15 to 70, and x is 1
5-20 and y are more preferably 50-60.

Further, polypropylene oxide (PO)
A chain-polyethylene oxide (EO) chain-polypropylene oxide (PO) chain triblock copolymer ((PO) x (EO) y (PO) x) can also be preferably used. Here, x and y are not particularly limited, but x is 5 to 5.
110, y is preferably from 15 to 70, and x is 1
5-20 and y are more preferably 50-60.

As the above triblock copolymer,
(EO)_Five(PO)₇₀(EO)_Five, (EO)₁₃(PO)₃₀
(EO)₁₃, (EO)₂₀(PO)₃₀(EO)₂₀, (E
O)₂₆(PO)₃₉(EO)₂₆, (EO)₁₇(PO)
₅₆(EO)₁₇, (EO)₁₇(PO) ₅₈(EO)₁₇, (E
O)₂₀(PO)₇₀(EO)₂₀, (EO)₈₀(PO)
₃₀(EO)₈₀, (EO)₁₀₆(PO)₇₀(EO)₁₀₆,
(EO)₁₀₀(PO)₃₉(EO)₁₀₀, (EO)₁₉(P
O)₃₃(EO)₁₉, (EO)₂₆(PO)₃₆(EO)₂₆But
No. Among them, (EO)₁₇(PO)₅₆(E
O)₁₇, (EO)₁₇(PO)₅₈(EO)₁₇Using
Is preferred. These triblock copolymers are BAS
Available from company F, etc.
Obtain triblock copolymer with desired x and y values
Can be One of the above triblock copolymers
Or two or more can be used in combination
You.

Also, two nitrogen atoms of ethylenediamine
Each have two polyethylene oxide (EO) chains-
Star with polypropylene oxide (PO) chain attached
Diblock copolymers can also be used. this
As such a star diblock copolymer, ((E
O)₁₁₃(PO)_{twenty two})_TwoNCH_TwoCH_TwoN ((PO)_{twenty two}(E
O)₁₁₃)_Two, ((EO)_Three(PO)₁₈)_TwoNCH_TwoCH_TwoN
((PO)₁₈(EO) _Three)_Two, ((PO)₁₉(EO)₁₆)
_TwoNCH_TwoCH_TwoN ((EO)₁₆(PO)₁₉)_TwoEtc.
It is. There is one type of the above star die block copolymer
Alternatively, two or more kinds can be used in combination.

The porous particles used in the present invention are prepared by adding a compound represented by the above general formula (6) (and optionally an inorganic compound such as alkoxysilane) to an aqueous solution containing a surfactant, Although it can be obtained by polycondensation under alkaline conditions, the pH of the aqueous solution is preferably 7 or more.

An oligomer is formed by polycondensation of an organometallic compound (and, if necessary, an inorganic compound) under acidic or alkaline conditions in the absence of a surfactant,
A surfactant may be added to the aqueous solution containing the oligomer, and polycondensation may be further performed under acidic or alkaline conditions.

In the polycondensation in the presence of a surfactant, polycondensation under alkaline conditions and polycondensation under acidic conditions can be performed alternately. At this time, the order of the alkaline condition and the acidic condition is not particularly limited, but when the polycondensation is performed under the alkaline condition by performing the polycondensation under the acidic condition,
The degree of polymerization tends to increase. In the polycondensation reaction, it is preferable that stirring and standing are alternately performed.

The reaction temperature of the polycondensation is preferably in the range of 0 to 100 ° C., but the lower the temperature, the higher the regularity of the product structure. The preferred reaction temperature is 20 to 40 ° C. for increasing the regularity of the structure. On the other hand, when the reaction temperature is higher, the degree of polymerization tends to be higher and the stability of the structure tends to be higher. The preferred reaction temperature for increasing the degree of polymerization is 6
0-80 ° C.

After the polycondensation reaction, the precipitate or gel formed after aging is filtered, washed if necessary, and then dried to obtain a porous material with the surfactant filled in the pores. A particle precursor is obtained.

The precursor of the porous particles is used in an aqueous solution containing the same surfactant as used in the polycondensation reaction (typically, a surfactant concentration equal to or lower than that in the polycondensation reaction) or The precursor can be dispersed in a solvent such as water, and the precursor can be subjected to hydrothermal treatment at 50 to 200 ° C. In this case, the solution used in the polycondensation reaction can be heated as it is or after dilution. Heating temperature is 60 ~
The temperature is preferably 100 ° C, more preferably 70 to 80 ° C. Further, the pH at this time is preferably weakly alkaline, and the pH is preferably, for example, 8 to 8.5. The time of the hydrothermal treatment is not particularly limited, but is preferably 1 hour or more, and more preferably 3 to 8 hours.

After the hydrothermal treatment, the porous particle precursor is filtered and then dried to remove excess processing liquid. In addition, before the porous particle precursor is dispersed in the aqueous solution or the solvent and the pH is adjusted, and before the hydrothermal treatment is started, stirring may be performed at room temperature for several hours to several tens hours in advance.

Next, the surfactant is removed from the porous particle precursor. Examples of the method include a method of baking and a method of treating with a solvent such as water or alcohol.

In the firing method, the porous particle precursor is heated at 300 to 1000 ° C., preferably 400 to 700 ° C.
Heat at ° C. The heating time may be about 30 minutes, but it is preferable to heat for 1 hour or more to completely remove the surfactant component. Although calcination can be performed in the air, a large amount of combustion gas is generated, so that an inert gas such as nitrogen may be introduced.

When the surfactant is removed from the porous particle precursor using a solvent, for example, the porous material precursor is dispersed in a solvent having high solubility of the surfactant, and the solid content is recovered after stirring. I do. As the solvent, water, ethanol, methanol, acetone or the like can be used.

When a cationic surfactant is used,
The porous material precursor is dispersed in ethanol or water to which a small amount of hydrochloric acid has been added, and stirring is performed while heating at 50 to 70 ° C. Thereby, the cationic surfactant is ion-exchanged with the proton and extracted. When an anionic surfactant is used, the surfactant can be extracted in a solvent to which an anion has been added. When a nonionic surfactant is used, it is possible to extract with only a solvent. In addition, it is preferable to irradiate an ultrasonic wave at the time of extraction. Further, it is preferable to combine or repeat stirring and standing.

The shape of the porous particles used in the present invention can be controlled by the synthesis conditions. In addition,
The particle shape reflects the arrangement structure of the pores of the particles, and the crystal structure determines the particle shape. For example, the crystal structure of spherical porous particles is three-dimensional hexagonal, and the crystal structure of hexagonal columnar porous particles is two-dimensional hexagonal. The crystal structure of the octahedral porous particles is cubic.

The synthesis conditions that have the greatest influence on the particle shape (crystal structure) are the reaction temperature and the length of the surfactant (carbon number).
It is. For example, when alkyltrimethylammonium is used as a surfactant, the carbon number of the alkyl group and the reaction temperature affect the particle shape. For example, when the reaction temperature is 95 ° C. and the alkyl group has 18 carbon atoms,
Hexagonal particles are easily generated, and when the reaction temperature is 95 ° C. and the alkyl group has 16 carbon atoms, octahedral particles are easily generated. When the reaction temperature is 25 ° C.,
In both cases where the alkyl group has 18 or 16 carbon atoms, spherical particles are easily formed. On the other hand, when the reaction temperature is 2 ° C. and the number of carbon atoms of the alkyl group is 18, a layer structure is easily formed, and when the reaction temperature is 2 ° C. and the number of carbon atoms of the alkyl group is 16, spherical particles are easily generated. These are summarized in Table 1.

[Table 1] The respective particle shapes when the shape of the porous particles is spherical, hexagonal, and octahedral will be described in detail below.

FIG. 1 is a perspective view of an example of spherical porous particles suitably used in the present invention. FIG. 2 is an enlarged perspective view of a portion represented by A of the spherical porous particles shown in FIG. 1 and shows one mode of the shape of the pores of the porous particles. The spherical porous particles shown in FIG. 1 can be prepared, for example, under the conditions described in Example 1 (reaction temperature: 25 ° C., alkyl group of surfactant: 16), by 1,2-bis (trimethoxysilyl). ) It can be obtained by polycondensing ethane. The spherical porous particles obtained under the conditions described in Example 1 are formed by hexagonal close-packing of spherical units having a central pore diameter of 2.3 nm shown in FIG. The average diameter of the spherical porous particles is 5 μm.

FIG. 3 is a perspective view of an example of hexagonal columnar porous particles suitably used in the present invention. FIG. 4 is an enlarged perspective view of a portion indicated by B of the hexagonal columnar porous particles shown in FIG. 3 and shows one mode of the shape of the pores of the porous particles. The hexagonal columnar porous particles shown in FIG. 3 can be prepared, for example, under the conditions described in Example 6 below (reaction temperature: 95 ° C., surfactant: alkyl group having 18 carbon atoms) by 1,2-bis (trimethoxy). It can be obtained by polycondensing silyl) ethane. The hexagonal columnar porous particles obtained under the conditions described in Example 6 are formed by a honeycomb structure having pores having a central pore diameter of 3.1 nm shown in FIG. The average particle size of the hexagonal columnar porous particles is 1 μm, and the average length in the longitudinal direction is 10 μm.

FIG. 5 is a perspective view showing an example of octahedral porous particles suitably used in the present invention. FIG.
(A), (b), (c) is a front view, a side view, and a bottom view of the octahedral porous particles shown in FIG. 5, respectively. FIG. 7 is an enlarged perspective view of the portion represented by C of the octahedral porous particles shown in FIG. 5, and shows one mode of the shape of the pores of the porous particles. The octahedral porous particles shown in FIG. 5 can be prepared, for example, under the conditions described in Example 7 below (reaction temperature is 95 ° C., surfactant has 16 carbon atoms in the alkyl group), and 1,2-bis ( It can be obtained by polycondensation of (trimethoxysilyl) ethane. The octahedral porous particles obtained under the conditions described in Example 7 are formed by connecting units having pores having a central pore diameter of 2.9 nm shown in FIG. The average particle size of the octahedral porous particles is 5 μm.

In the present invention, when the above-mentioned inorganic compound such as alkoxysilane is polycondensed together with the compound of the general formula (6) to produce porous particles, the crystal structure can be controlled by the mixing ratio of these. It is possible. For example, when the number of moles of an inorganic compound such as alkoxysilane is X and the number of moles of the compound of the general formula (6) is Y, X
When / Y is in the range of 0/100 to 50/50, the crystal structure tends to be cubic, and when / Y is in the range of 80/20 to 100/0, the crystal structure tends to be hexagonal.

The pore size of the obtained porous particles can be controlled by changing the type of surfactant used or by adding a hydrophobic compound (for example, trimethylbenzene or tripropylbenzene) to the surfactant. can do. The ratio of surfactant (S) to water (H ₂ O) (S / H
_{When (} 2O: g / g) is 20 or more, a regular pore structure is easily formed. When this ratio is about 20, the crystal structure tends to be cubic, and when it is 23 or more, the crystal structure tends to be hexagonal.

Further, when the above-described hydrothermal treatment is performed, the strength and structural regularity of the porous particles after the removal of the surfactant are improved as compared with the case where the hydrothermal treatment is not performed. For example, by performing hydrothermal treatment on a porous particle precursor having a hexagonal crystal structure, ±
The pore diameter can be made uniform so that the value obtained by dividing the total volume of the pores having a diameter in the range of 40% by the total volume of the pores is 0.6 to 1.

Next, an adsorption separation method using the above-described porous particles as an adsorption separation material will be described.

The adsorption / separation method of the present invention may be any method as long as the above-mentioned porous particles are used as an adsorption / separation material. . For example, a liquid or gas from which the sample has been removed can be obtained by filling a column with the above-described porous material and adsorbing a liquid or gas containing a sample through the column and adsorbing the porous particles. In addition, the sample adsorbed on the porous particles can be collected and concentrated.

Further, the packed column in which the porous particles described above are packed in a column can be used for chromatography. That is, a mobile phase such as a solvent or a gas is allowed to flow through a packed column, a sample (mixture) is injected into the mobile phase, and the time required for each component in the sample to separate and flow is measured. Qualitative and quantitative analysis can be performed.

The porous material used in the present invention is suitable for use in this chromatography, and can be particularly preferably used for liquid chromatography in which the mobile phase is a liquid.

[0086] This liquid chromatography typically comprises a liquid sending pump, a packed column, a detector, a pipe connecting these, and an injection device for injecting a sample into a pipe before the packed column. . When the sample (mixture) to be analyzed is injected from the injection device while the mobile phase (liquid) flows into the packed column at a constant speed by the liquid sending pump, the sample flows into the packed column together with the mobile phase, and the sample Each component inside interacts with the porous particles in the packed column according to its polarity and size, so that the time for each component to flow out differs. The components that have flowed out in this way are detected by the detector and the sample is analyzed.

The type of the liquid sending pump used in this liquid chromatography is not limited. For example, a single plunger reciprocating pump, a dual plunger reciprocating pump, a tri-rotor pump, a non-pulsating constant-speed extrusion pump, a diaphragm A reciprocating pump or the like can be used.

The detection method of the liquid chromatography detector is not particularly limited. For example, a thermal detector, a radiation detector, an ionization detector, an electromagnetic analysis detector, an optical detector, an electric (chemical) detector A target detector or the like can be used. As the optical detector, an ultraviolet / visible photometer, a fluorometer, a refractometer, or the like can be used.

There is no particular limitation on the column filled with the porous material. A column of any size can be used depending on the target of adsorption / separation. Further, only one column may be used, or a plurality of columns may be used.

The mobile phase used in the liquid chromatography is not particularly limited, and examples thereof include methanol, a mixture of methanol and water, hexane, and a mixture of hexane and water.

[0091]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

(Example 1)Synthesis of 1,2-bis (trimethoxysilyl) ethane Under a reflux of nitrogen gas, 200
g of NaOCH_Three-HOCH_ThreeSolution (about 28% concentration)
102 g of anhydrous CH_ThreeAdd OH and shake under ice-water cooling.
While stirring, 1,2-bis (trichlorosilyl) ethane
50 g was dropped. The solvent methanol is removed by atmospheric distillation.
After that, the product was obtained by distillation under reduced pressure. In addition, generate
The material was purified by distillation under reduced pressure. The structure of the purified product
Gas chromatography mass spectrum (GC-MS)
When¹H-NMR,¹³C-NMR, ²⁹By Si-NMR
When identified (FIGS. 8-11), the product was 1,2-bi
(Trimethoxysilyl) ethane [(CH_ThreeO)_ThreeSi
-CH_Two-CH_Two-Si (OCH_Three)_Three] (Hereinafter, BT
Me (abbreviated as Me). By GC-MS
And the content of BTMe in the product is 95% or more, and the yield is
Was 84 mol%.

Synthesis of Porous Particle Precursor 0.432 g (1.35 mmol) was placed in a 100 mL beaker.
l) n-hexadecyltrimethylammonium chloride (surfactant), 30 g of ion-exchanged water and 1.5
g of a 6N NaOH aqueous solution (7.5 mmol of NaOH
) Was introduced. While stirring vigorously at room temperature, 2.03 g (7.5 mmol) of BTMe was added.
Stirred for hours. After standing at room temperature for 14 hours, the mixture was stirred for 12.5 hours, left again for 14 hours, stirred for 6.9 hours,
Filtered. The precipitate was washed twice with 300 mL of ion-exchanged water, and after air-drying, 1.90 g of a solid was obtained. This solid is a precursor of the porous particles, and has the above-mentioned surfactant in the pores.

Production of Porous Particles A surfactant was removed from a porous particle precursor by the following method to obtain porous particles. That is, 1.0 g of the porous particle precursor was added to a mixture of 150 mL of anhydrous ethanol and 3.8 g of concentrated hydrochloric acid, stirred at 50 ° C. for 6 hours, and filtered. The recovered precipitate was treated once more with a mixture of absolute ethanol and concentrated hydrochloric acid under the same conditions. The finally obtained precipitate was washed twice with 150 mL of absolute ethanol and air-dried to obtain porous particles.

Structural Analysis of Product Scanning electron micrographs (SEM) of the porous particles obtained in Example 1 are shown in FIGS. In addition, transmission electron micrographs (TEM) of the porous particles are shown in FIGS.
FIG. 17 shows an electron diffraction photograph measured on the observation surface of FIG.
FIG. 18 shows an electron beam diffraction photograph measured on the observation surface of FIG.
Shown in X-ray diffraction pattern, nitrogen adsorption isotherm, B
Pore size distribution curve determined by the JH method, ¹³ C-NMR, ²⁹
FIG. 1 shows the results of Si-NMR and thermogravimetric distribution, respectively.
9 to 24.

From the scanning electron micrographs shown in FIGS. 12 and 13, it was found that the obtained porous particles were spherical and had an average particle size of 5 μm. Further, from the electron beam diffraction photographs (FIGS. 17 and 18), it was inferred that the pore structure of the porous particles obtained in Example 1 was a three-dimensional hexagonal. The X-ray diffraction pattern in FIG. 19 confirmed that the structure of the porous particles was a three-dimensional hexagonal structure.

Further, the nitrogen adsorption isotherm in FIG.
From the pore diameter distribution curve of, the central pore diameter is 2.3 nm,
The value obtained by dividing the total volume of pores having a diameter within the range of ± 40% of the central pore diameter by the total volume of pores was 0.7, and it was confirmed that the pore diameter distribution was uniform. Was done.

The results of elemental analysis of the porous particles are as follows:
C: 14.5%, H: 4.4%, N: 0%, SiO ₂ :
It was 76.6%, indicating that the surfactant was completely removed, the molar ratio of C / Si was 1, and that carbon was taken into the skeleton of the porous particles as expected. This was also confirmed from the results of thermogravimetric analysis.

Liquid using column filled with porous particles
Chromatography The porous particles (hereinafter referred to as PESO) obtained in this example were packed in a column (φ4.6 mm × 250 mm) manufactured by Fuji Silysia. Shimadzu LC-9A pump, Shimadzu SPD-6AV
The above column packed with PESO was attached to a liquid chromatograph (HPLC) device manufactured by Shimadzu Corporation equipped with a UV-VIS detector and Shimadzu C-R6A recorder.

A sample obtained by dissolving uracil, naphthalene and anthracene in a 50% aqueous solution of methanol was used as a sample, and 25 μm was injected from the injection device of the liquid chromatograph.
1 was injected. The mobile phase was a 50% aqueous solution of methanol (reverse phase system), and the flow rate was 1.0 ml / min. UV (254 nm) was used as the detection method of the detector.

Comparative Example 1 Water (3.6) was added to 15.2 g of tetramethoxysilane (TMOS) as an alkoxysilane.
g and about 0.1 g of 2N hydrochloric acid were added, and the mixture was stirred at room temperature for 1 hour. Next, hexadecyltrimethylammonium chloride (C ₁₆ H ₃₃₎ as a surfactant was added to the obtained solution.
An additional 8.05 g of N (CH ₃ ) ₃ Cl) was added and the solution was vigorously stirred for several minutes to make the solution viscous.

Next, this solution was placed in a closed container for 2 to 2 hours.
Left for 3 days. As a result, the solution solidified to obtain a transparent and uniform solid. The solid was dried and then calcined at 550 ° C. for 6 hours in air to remove the surfactant, thereby obtaining porous particles (FSM). The average particle size of this FSM was 15 μm, and the central pore diameter was 4.4 nm.

The FSM thus obtained was packed in the same column as used in Example 1, and the same procedure as in Example 1 was carried out.
Separation of uracil, naphthalene and anthracene was performed in a reversed phase system.

Comparative Example 2 The same column as that used in Example 1 was packed with SI manufactured by Fuji Silysia Ltd. (average particle size: 15 μm, center pore diameter: 7.0 nm). Uracil, naphthalene and anthracene were separated in a reversed-phase system.

(Comparative Example 3) The same column as that used in Example 1 was filled with ODS (average particle size: 5 μm, center pore diameter: 10.0 nm) manufactured by Fuji Silysia Ltd. Uracil, naphthalene and anthracene were separated in a reversed-phase system.

The HPs obtained in Example 1 and Comparative Examples 1 to 3
The LC chromatogram is shown in FIG. Also, uracil,
Table 2 summarizes the retention times of naphthalene and anthracene.

[Table 2]

From FIG. 25, it was found that in the reversed phase system under the conditions of Comparative Example 2, uracil, naphthalene and anthracene could not be separated even using a column packed with SI. In addition, it was found that under the conditions of Comparative Example 1, when a column filled with FSM was used, naphthalene and anthracene were not sufficiently separated. On the other hand, when the column packed with ODS was used under the conditions of Comparative Example 3, and when the column packed with PESO which is the method of the present invention was used (Example 1), uracil, naphthalene and anthracene were separated. It turned out to be possible.

In the case where a column filled with ODS is used, the retention time of naphthalene and anthracene is extremely long, and the separation takes a long time, which may cause a practical problem. On the other hand, when a column packed with PESO is used, a relatively short
(Within 0 minutes).

Example 2 A column filled with PESO was prepared in the same manner as in Example 1 except that a 40% aqueous solution of methanol was used as a solution for dissolving uracil, naphthalene and anthracene and a mobile phase. , Naphthalene and anthracene were separated in a reversed-phase system.

Comparative Example 4 A column filled with FSM was prepared in the same manner as in Comparative Example 1 except that a 40% aqueous solution of methanol was used as a mobile phase and a solution for dissolving uracil, naphthalene and anthracene. , Naphthalene and anthracene were separated in a reversed-phase system.

(Comparative Example 5) A column filled with SI was used in the same manner as in Comparative Example 2 except that a 40% aqueous solution of methanol was used as a solution for dissolving uracil, naphthalene and anthracene and as a mobile phase. , Naphthalene and anthracene were separated in a reversed-phase system.

The HPs obtained in Example 2, Comparative Examples 4 and 5
The LC chromatogram is shown in FIG. Also, uracil,
Table 3 summarizes the retention times of naphthalene and anthracene.

[Table 3]

From FIG. 26, it was found that in the reverse phase system under the conditions of Comparative Example 5, uracil, naphthalene and anthracene could not be separated even using a column packed with SI. Also, under the conditions of Comparative Example 4, it was found that when a column packed with FSM was used, uracil, naphthalene and anthracene could be separated. It was also found that uracil, naphthalene and anthracene can be separated even when a column packed with PESO, which is the method of the present invention, is used (Example 2).

Example 3 PES was performed in the same manner as in Example 1.
O was obtained. Furthermore, a column filled with PESO was attached to a liquid chromatograph (HPLC) manufactured by Shimadzu Corporation in the same manner as in Example 1.

A sample obtained by dissolving benzene, dibutyl phthalate and dimethyl phthalate in a 1% hexane solution of methanol was used as a sample, and injected from the injection device of the above liquid chromatograph. The mobile phase is 1% of methanol
A hexane solution (normal phase system), and the flow rate was 1.0 ml / min. UV (254 nm) was used as the detection method of the detector.

(Comparative Example 6) FSM was prepared in the same manner as in Comparative Example 1.
I got This FSM was packed in the same column as that used in Example 3, and benzene, dibutyl phthalate and dimethyl phthalate were separated in a normal phase system in the same manner as in Example 3.

Comparative Example 7 The same column as that used in Example 3 was packed with SI manufactured by Fuji Silysia Ltd. (average particle size: 15 μm, center pore diameter: 7.0 nm). Then, benzene, dibutyl phthalate and dimethyl phthalate were separated in a normal phase system.

Comparative Example 8 The same column as that used in Example 3 was packed with ODS (average particle size: 5 μm, center pore diameter: 10.0 nm) manufactured by Fuji Silysia Ltd. Then, benzene, dibutyl phthalate and dimethyl phthalate were separated in a normal phase system.

HPL obtained in Example 3 and Comparative Examples 6 to 8
The C chromatogram is shown in FIG. Table 4 summarizes the retention times and the degrees of separation of benzene, dibutyl phthalate, and dimethyl phthalate.

[Table 4]

FIG. 27 shows that in the normal phase system under the conditions of Comparative Example 8, benzene,
It was found that separation of dibutyl phthalate and dimethyl phthalate was difficult. In addition, a case using a column filled with FSM (Comparative Example 6), a case using a column packed with SI (Comparative Example 7), and the method of the present invention, PE
In the case of using the column packed with SO (Example 3), it was found that separation of benzene, dibutyl phthalate and dimethyl phthalate was possible.

Example 4 PES was performed in the same manner as in Example 1.
O was obtained. Furthermore, a column filled with PESO was attached to a liquid chromatograph (HPLC) manufactured by Shimadzu Corporation in the same manner as in Example 1. Those fullerene C ₆₀ and fullerene C ₇₀ was dissolved in hexane was used as a sample was injected from the injection device of the liquid chromatograph. The mobile phase was hexane (normal phase system), and the flow rate was 1.0 ml /
Minutes. UV (350 nm) was used as the detection method of the detector.

(Comparative Example 9) FSM was prepared in the same manner as in Comparative Example 1.
I got This FSM was packed in the same column as that used in Example 4, and fullerene C ₆₀ and fullerene C ₇₀ were separated in a normal phase system in the same manner as in Example 4.

(Comparative Example 10) The same column as used in Example 4 was packed with SI manufactured by Fuji Silysia Ltd. (average particle size: 15 μm, center pore diameter: 7.0 nm). Te were separated fullerene C ₆₀ and fullerene C ₇₀ in normal phase.

(Comparative Example 11) ODS manufactured by Fuji Silysia Ltd.
(Average particle size: 5 μm, center pore diameter: 10.0 nm) was packed in the same column as used in Example 4, and
In the same manner as were separated fullerene C ₆₀ and fullerene C ₇₀ in normal phase.

The HPs obtained in Example 4 and Comparative Examples 9 to 11
The LC chromatogram is shown in FIG. Also, shown in Table 5 summarizes the retention times of the fullerene C ₆₀ and fullerene C _70.

[Table 5]

As shown in FIG. 28, it is difficult to separate fullerene C ₆₀ and fullerene C ₇₀ when the column packed with SI is used (Comparative Example 10) and when the column packed with FSM is used (Comparative Example 9). It turned out to be. When a column filled with ODS was used (Comparative Example 1
1) and in the case of using a column packed with PESO which is the method of the present invention (Example 4), fullerene C
₆₀ and was found to be possible to separate the fullerene C _70. The separation performance of fullerene C ₆₀ and fullerene C ₇₀ when a column packed with PESO was used was determined by ODS
Although inferior to the case of using a column packed with
Since a surface treating agent such as an octadecyl group of ODS tends to be desorbed with time, using a column packed with PESO has an advantage that a certain result can be obtained with time.

(Example 5) The flow rate of the moving bed was set to 0.5 ml /
Except that the fullerene C ₆₀ and the fullerene C ₇₀ were prepared using a column filled with PESO in the same manner as in Example 4.
Was performed in a normal phase system.

(Comparative Example 12) The flow rate of the moving bed was set to 0.5 ml.
/ Min, except that the fullerene C ₆₀ and the fullerene C ₇₀ were used in the same manner as in Comparative Example 9 using a column filled with FSM.
Was performed in a normal phase system.

(Comparative Example 13) The flow rate of the moving bed was 0.5 ml
/ Min, and using a column filled with SI, using the fullerene C ₆₀ and the fullerene C _{70 in the same} manner as in Comparative Example 10.
Was performed in a normal phase system.

(Comparative Example 14) The flow rate of the moving bed was 0.5 ml
Except that the / min, in the same manner as in Comparative Example 11, fullerene C ₆₀ and fullerene C using a column packed with ODS
Separation of ₇₀ was performed in a normal phase system.

H obtained in Example 5 and Comparative Examples 12 to 14
The PLC chromatogram is shown in FIG. Also, shown in Table 6 summarizes the retention times of the fullerene C ₆₀ and fullerene C _70.

[Table 6]

As shown in FIG. 29, it is difficult to separate fullerene C ₆₀ and fullerene C ₇₀ when the column packed with SI is used (Comparative Example 13) and when the column packed with FSM is used (Comparative Example 12). It turned out to be.
When a column filled with ODS was used (Comparative Example 1
4) and in the case of using a column packed with PESO which is the method of the present invention (Example 5), fullerene C
₆₀ and was found to be possible to separate the fullerene C _70. The separation performance of fullerene C ₆₀ and fullerene C ₇₀ when a column packed with PESO was used was determined by ODS
Although inferior to the case of using a column packed with
Since a surface treating agent such as an octadecyl group of ODS tends to be desorbed with time, using a column packed with PESO has an advantage that a certain result can be obtained with time.

Example 6 Synthesis of Porous Particle Precursor A mixed solution of n-octadecyltrimethylammonium chloride (ODTMA), sodium hydroxide (NaOH), and water (H ₂ O) was vigorously stirred at 25 ° C. BTMe was dropped therein. The mixing molar ratio of each raw material (BTMe: ODTMA: NaOH: H ₂ O) was 1: 0.57: 2.36: 353. When BTMe was added, no white precipitate was formed, but after stirring at 25 ° C. for 14 hours and heating to 95 ° C., a white precipitate was formed. After stirring this precipitation solution at 95 ° C. for 21 hours,
The precipitate was filtered, washed with a sufficient amount of water, and dried to obtain a porous particle precursor.

Production of Porous Particles 1 g of the porous particle precursor was taken and dispersed in 150 mL of water to which 3.8 g of a 36% hydrochloric acid aqueous solution had been added.
After stirring for an hour, the precipitate was filtered and washed with water. The obtained precipitate was again mixed with water 1 to which 3.8 g of a 36% hydrochloric acid aqueous solution was added.
The precipitate was dispersed in 50 mL and stirred at 50 ° C. for 6 hours. The precipitate was filtered, washed with water, and dried to obtain porous particles.

Structural Analysis of Product The X-ray diffraction pattern of the porous particles is shown in FIG. From this figure, it can be seen that the two-dimensional hexagonal structure (a = 57.0)
Six peaks indicating Å) were observed, indicating that the regularity of the structure was high. In addition, a scanning electron micrograph (FIG. 3)
1) showed that the porous particles had a hexagonal columnar particle shape reflecting the arrangement structure of the pores. Further, according to the transmission electron micrograph (see FIG. 32), pores regularly arranged in a hexagonal shape were observed.
From the electron beam diffraction pattern shown in the upper right corner of FIG. 32, high-order spots up to the sixth order were observed, indicating that the crystallinity was high. The center pore diameter of the porous particles was 31 °, and the specific surface area was 750 m ² / g. The average particle size of the porous particles was 1 μm, and the average length in the longitudinal direction was 10 μm.

From the measurement results of ²⁹ Si and ¹³ C-NMR,
The pore wall of the porous material has an ethylene group (—CH ₂ CH).
₂ -) that was confirmed to have a built-in chemical structures in the silicate framework combined with a covalent bond with Si.

Liquid using column packed with porous particles
Chromatography A separation experiment was carried out using the porous particles obtained in this example in the same manner as in Example 1 (reverse phase system) and Example 3 (normal phase system). It was found that the system exhibited good separation performance.

Example 7 Synthesis of Porous Particle Precursor In a beaker, 1.021 g of hexadecyltrimethylammonium chloride (HDTMA), 30 g of ion-exchanged water and 2.4 g of a 6N aqueous NaOH solution were mixed. While stirring vigorously at room temperature, 1.52 g of BTMe was added,
The mixture was further stirred at room temperature for 20 hours. Thereafter, the solution was heated to 95 ° C and left at 95 ° C for 17 hours. The resulting precipitate was washed with ion-exchanged water and air-dried to obtain a porous particle precursor.

Formation of Porous Particles 1 g of the porous particle precursor was added to a mixture of 150 ml of anhydrous ethanol and 3.8 g of concentrated hydrochloric acid, stirred at 50 ° C. for 6 hours, and filtered. The recovered precipitate was treated again with the same mixed solution of absolute ethanol and concentrated hydrochloric acid. Thereafter, the particles were air-dried to obtain porous particles.

Structural Analysis of Product The X-ray diffraction pattern of the porous particles obtained in this example is shown in FIG. Several peaks were observed at diffraction angles of 1 to 4 degrees, indicating that a regular structure was formed on the order of nanometers. 34 to 37,
A scanning electron micrograph of the porous particles is shown. All the porous particles had an octahedral particle shape, the particle size was small, and the average particle size was 5 μm.

Liquid using column packed with porous particles
Chromatography A separation experiment was carried out using the porous particles obtained in this example in the same manner as in Example 1 (reverse phase system) and Example 3 (normal phase system). It was found that the system exhibited good separation performance.

[0142]

As described above, according to the adsorption / separation method of the present invention, polar and non-polar substances or hydrophilic and hydrophobic substances can be subjected to adsorption / separation.

[Brief description of the drawings]

FIG. 1 is a perspective view of a spherical porous particle used in the present invention.

FIG. 2 is a perspective view of a main part of a spherical porous particle used in the present invention.

FIG. 3 is a perspective view of hexagonal columnar porous particles used in the present invention.

FIG. 4 is a perspective view of a main part of hexagonal columnar porous particles used in the present invention.

FIG. 5 is a perspective view of octahedral porous particles used in the present invention.

6 (a) is a front view of the octahedral porous particles used in the present invention, FIG. 6 (b) is a side view thereof, and FIG. 6 (c) is a bottom view thereof.

FIG. 7 is a perspective view of a main part of octahedral porous particles used in the present invention.

FIG. 8 is a diagram showing a GC spectrum of BTMe.

FIG. 9 is a diagram showing an MS spectrum of each peak of a GC spectrum of BTMe.

FIG. 10 shows a peak 3 of a GC spectrum of BTMe and an MS spectrum of a standard substance.

11A is a ¹³ C-NMR spectrum of BTMe, FIG. 11B is a ²⁹ Si spectrum of BTMe, and FIG.
It is a figure which shows the < ¹ > H-NMR spectrum of TMe.

FIG. 12 is a view showing a scanning electron micrograph (× 1000) of the porous particles obtained in Example 1.

FIG. 13 is a view showing a scanning electron micrograph (magnification: 5000) of the porous particles obtained in Example 1.

FIG. 14 is a transmission electron micrograph (magnification: 400,000 times) of a porous particle obtained in Example 1.

FIG. 15 is a transmission electron micrograph (magnification: 400,000 times) of the porous particles obtained in Example 1.

FIG. 16 is a transmission electron micrograph (magnification: 1,000,000 times) of the porous particles obtained in Example 1.

FIG. 17 is a diagram showing the porous particles obtained in Example 1.
FIG. 4 is a view showing an electron diffraction photograph of a cross section corresponding to No. 4;

FIG. 18 is a diagram showing the porous particles obtained in Example 1.
FIG. 5 is a view showing an electron diffraction photograph of a cross section corresponding to No. 5;

FIG. 19 is a view showing an X-ray diffraction pattern of the porous particles obtained in Example 1.

FIG. 20 is a diagram showing a nitrogen adsorption isotherm of the porous particles obtained in Example 1.

FIG. 21 is a view showing a pore size distribution curve of the porous particles obtained in Example 1.

FIG. 22 shows ¹³ C of the porous particles obtained in Example 1.
It is a figure which shows -NMR spectrum.

FIG. 23 shows ²⁹ S of the porous particles obtained in Example 1.
It is a figure which shows an i-NMR spectrum.

FIG. 24 is a view showing a thermogravimetric analysis result of the porous particles obtained in Example 1.

FIG. 25 shows HPLs obtained in Example 1 and Comparative Examples 1 to 3.
It is a figure which shows C chromatogram.

FIG. 26 shows HPLs obtained in Example 2, Comparative Examples 4 and 5.
It is a figure which shows C chromatogram.

FIG. 27 shows HPLs obtained in Example 3 and Comparative Examples 6 to 8.
It is a figure which shows C chromatogram.

FIG. 28 shows HPs obtained in Example 4 and Comparative Examples 9 to 11.
It is a figure which shows an LC chromatogram.

FIG. 29 shows H obtained in Example 5 and Comparative Examples 12 to 14.
It is a figure which shows a PLC chromatogram.

FIG. 30 is a view showing an X-ray diffraction pattern of the porous particles obtained in Example 6.

FIG. 31 is a view showing a scanning electron micrograph of the porous particles obtained in Example 6.

FIG. 32 is a view showing a transmission electron micrograph of the porous particles obtained in Example 6.

FIG. 33 is a view showing an X-ray diffraction pattern of the porous particles obtained in Example 7.

FIG. 34 is a diagram showing a scanning electron micrograph (magnification: 6000 times) of the porous particles obtained in Example 7.

FIG. 35 is a diagram showing a scanning electron micrograph (magnification: 14,000 times) of the porous particles obtained in Example 7.

36 is a diagram showing a scanning electron micrograph (magnification: 12,000 times) of the porous particles obtained in Example 7. FIG.

FIG. 37 is a diagram showing a scanning electron micrograph (magnification: 14,000 times) of the porous particles obtained in Example 7.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4D012 BA01 4D017 AA01 AA04 AA06 BA05 CA11 CA17 CB01 CB10 DA03 EB03 4G066 AB05B AB18A AB18B AB18C AB23B AB24B BA09 BA20 BA23 BA24 BA32 CA51 CA56 DA07 EA01 FA03 FA05 FA21 FA34 FA37

Claims (6)

[Claims] 1. A skeleton comprising an organic group having at least one carbon atom, two or more metal atoms bonded to the same or different carbon atoms in the organic group, and one or more oxygen atoms bonded to the metal atom. An adsorption separation method characterized by using porous particles having fine pores and comprising a crystalline organic-inorganic composite material having the following as an adsorption separation material. 2. In the porous particles, a value obtained by dividing the total volume of pores having a diameter within a range of ± 40% of the central pore diameter by the total volume of pores is 0.6 to 1. The adsorption separation method according to claim 1, wherein: 3. The adsorption separation method according to claim 1, wherein the X-ray diffraction pattern of the porous particles has one or more peaks at a diffraction angle corresponding to a d value of 1 nm or more. 4. The method according to claim 1, wherein the porous particles have a spherical, hexagonal or octahedral shape.
4. The adsorption separation method according to any one of the above items 3. 5. The adsorption separation method according to claim 1, wherein the skeleton comprises at least one of structural units represented by the following general formula (1). Embedded image (Wherein, R ¹ is an organic group having one or more carbon atoms, M is a metal atom, R ² is hydrogen, a hydroxyl group or a hydrocarbon group, x is an integer obtained by subtracting 1 from the valence of the metal M, and n is 1 or more. and an integer of x or less and m represents an integer of 2 or more, provided that carbons in R ¹ to which M is bonded may be the same or different.) 6. The porous particles having an average particle size of 0.01 to 0.01.
The adsorption separation method according to any one of claims 1 to 5, wherein the diameter is 100 µm and the center pore diameter is 1 to 50 nm.