JP3042556B2 - Method for immobilizing cyclodextrin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for immobilizing cyclodextrin, and more particularly, to a method for immobilizing cyclodextrin on an inorganic substance, particularly carbon black.

[0002]

2. Description of the Related Art Cyclodextrin (hereinafter abbreviated as CD) incorporates various organic compounds into its annular cavity to form an inclusion compound, and these compounds have recently been used as adsorption / separation agents. However, since CD itself is water-soluble and is soluble only in a specific organic solvent, it is difficult to include and isolate a compound from various systems.

As one method for solving such a problem, there has been proposed a method in which CD is chemically bonded to an inorganic substance to make it insoluble and used as an easy-to-handle adsorption / separation agent.

[0004]

The use of silica as the above-mentioned inorganic substance is generally known, but the chemical bonding between other inorganic substances and CD has not yet been sufficiently studied. In particular, carbon black has many uses due to its huge surface area and unique surface, and it is not hard to imagine that combining it with CD would provide more effects than expected.

Accordingly, an object of the present invention is to provide a CD-immobilized carbon black in which a CD is chemically bonded to carbon black, and to provide a method for immobilizing a CD on carbon black.

[0006]

Means for Solving the Problems In view of the above problems, the present inventors have conducted intensive studies, and as a result, the above object of the present invention was to chlorinate the carboxyl group of carbon black and then react it with a diamine. Then, a method for immobilizing cyclodextrin, characterized by reacting with a cyclodextrin derivative, a method for immobilizing cyclodextrin, comprising reacting carbon black with a diisocyanate, and then reacting with cyclodextrin or a cyclodextrin derivative. A method for immobilizing cyclodextrin, comprising reacting carbon black with a dicarboxylic acid halide, or reacting the carbon black with a cyclodextrin or a cyclodextrin derivative after further converting the carbon black to an azide group; Reaction with halide And then reacting the compound obtained as a carboxylic acid with a cyclodextrin or a cyclodextrin derivative, or reacting an alkali metal salt of the compound obtained as a carboxylic acid with a cyclodextrin derivative. Dextrin immobilization method, after reacting carbon black with alkyl oxirane halide, cyclodextrin immobilization method characterized by reacting with cyclodextrin or cyclodextrin derivative, or carbon black with alkyl oxirane halide It has been found that this is achieved by a method for immobilizing cyclodextrin, which comprises reacting the epoxy group, opening the epoxy group, and reacting with cyclodextrin or a cyclodextrin derivative.

Hereinafter, the present invention will be described more specifically.

As the CD used in the present invention, any of α, β and γ-cyclodextrin having 6, 7, and 8 glucose units can be used.

The following are examples of CD derivatives. (1) A CD derivative which can be used for the reaction of a reaction product of carbon black and a diisocyanate, or a product obtained by reacting carbon black with a dicarboxylic acid halide and substituting this with a carboxylic acid. CD derivatives that can be used in the reaction of A CD derivative having at least one -OH group.

[0010]

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A CD derivative having an arm extended with ethylene or an ethyleneoxy chain and having at least one —OH group at a terminal.

[0012]

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(2) A compound obtained by reacting a dicarboxylic acid halide with carbon black and then converting the compound obtained into carboxylic acid into an alkali metal salt, or chlorinating a carboxyl group of carbon black and then diamines CD derivatives that can be used in the reaction with the product obtained by the reaction, and include the following: A CD derivative having at least one TsO- or halogen group (for example, I- group) which is a leaving group.

[0014]

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A CD derivative having an arm extended with ethylene or an ethyleneoxy chain and having at least one leaving group at a terminal.

[0016]

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(3) A reaction product obtained by substituting a reaction product of carbon black and a dicarboxylic acid halide with an azide group, a reaction product of carbon black and an alkyl oxirane halide, or a reaction product obtained by ring-opening this epoxy group The following are CD derivatives which can be used in the reaction. A CD derivative that can be used in (1). A CD derivative having at least one —NH ₂ group.

[0018]

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CD derivatives having arms extended with ethylene or ethyleneoxy chains and having at least one amino group at a terminal.

[0020]

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The carbon black used in the present invention is:
Any commonly used one can be used, but a black fine powder obtained by incomplete combustion or thermal decomposition of natural gas or liquid hydrocarbon, whose main component has an average particle diameter in the colloid range of 1 to 500 mμ Are preferred, and channel black is particularly preferred because it has a large number of hydroxyl groups and carboxyl groups on the surface.

As the diisocyanate used in the present invention, those represented by OCN- (CH ₂ ) _x -NCO are preferably used, wherein x is an integer in the range of 2 to 10. As the dicarboxylic acid halide, those represented by XOC— (CH ₂ ) _y —COX (X represents a halogen atom) are preferably used,
Here, y having a value of 0 to 10 is used. Further, the diisocyanates and the dicarboxylic acid halides also include aromatic compounds.

As the dicarboxylic acid halide and alkyl oxirane halide used in the present invention, each chloride, bromide and iodide is preferably used.

Hereinafter, specific reaction examples of the CD immobilization method of the present invention will be described.

[0025]

Embedded image The above reaction can be specifically performed as follows. The numbers correspond to the numbers shown in the respective reaction examples.

(A) The dried carbon black is refluxed in thionyl chloride under a nitrogen atmosphere for 12 hours. Thereafter, the reaction carbon black is allowed to cool, filtered, and washed with dehydrated acetone. Then, the surface carboxyl groups are chlorinated by drying under reduced pressure to obtain a reaction product (a).

Next, the obtained reaction product (a) is dehydrated with DMS.
Hexamethylenediamine (x) in O (or DMF)
= 6) and stirring at 40-50 ° C for about 24 hours under a nitrogen stream. After completion of the reaction, the mixture is filtered and washed with methanol, and the carbon black is refluxed in methanol for about 24 hours. Thereafter, the mixture is allowed to cool, filtered, and dried at 80 to 90 ° C. under reduced pressure to obtain a reaction product (b).
Get. Hexamethylenediamine supported amount: about 300 μmol / g of carbon black

Further, the reaction product (b) is stirred with monotosyl-β-CD (or monoiodo-β-CD, n = 7) at 90-100 ° C. for about 72 hours in dehydrated DMSO (or DMF). After the completion of the reaction, the reaction carbon black is allowed to cool and filtered, and the reaction carbon black is washed with hot water. Thereafter, the resultant is dried under reduced pressure at 80 to 90 ° C. to obtain carbon black (C) immobilized on CD. CD fixed amount: about 200 μmol / g of carbon black

[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

Embedded image The above reaction can be specifically performed as follows. The numbers correspond to the numbers shown in the respective reaction examples.

(B) (1) -1 Carbon black and hexamethylene diisocyanate (H) in dehydrated DMSO (or DMF)
MDI) (x = 6) and added at 90-100 ° C. under a nitrogen stream.
Stir for 72 hours. After the completion of the reaction, the mixture is filtered and the reaction carbon black is thoroughly washed with dehydrated acetone. Thereafter, the product is dried under reduced pressure to obtain a reaction product [1]. HMDI supported amount: about 250 μmol / g of carbon black

Next, β-CD (n = 7) dissolved in dehydrated DMSO (or DMF) is slowly dropped (under a nitrogen stream). Thereafter, the mixture is stirred at room temperature for about 48 hours. After the completion of the reaction, the mixture was filtered to remove CD-carbon black, refluxed in methanol for about 12 hours to crush the remaining isocyanate groups, filtered and dried under reduced pressure to obtain CD-immobilized carbon black.
[2] is obtained. CD fixed amount: about 80 μmol / g of carbon black

(1) -2 Carbon black is dehydrated DM
The mixture is stirred in SO (or DMF) with hexamethylene diisocyanate (x = 6) at 40-50 ° C. for about 36 hours under a nitrogen stream. After completion of the reaction, the mixture is filtered and washed with methanol, and the carbon black is refluxed in methanol for about 12 hours. Thereafter, it is allowed to cool, filtered, and dried at 80 to 90 ° C. under reduced pressure.
(Amount of hexamethylene diisocyanate supported: about 300 μmol / g of carbon black)
Β-CD in SO (or DMF) at 90-100 ° C
After stirring for 72 hours, the reaction is allowed to cool after completion of the reaction, and the reaction carbon black is washed with hot water. Thereafter, drying is performed under reduced pressure at 80 to 90 ° C. CD fixed amount: about 220 μmol / g of carbon black

(2) The reaction product was prepared in the same manner as in Synthesis Example (1) except that adipic dichloride (y = 4) was used instead of hexamethylene diisocyanate.
A reactant [3] corresponding to [1] was obtained, and further a reactant [3]
CD-immobilized carbon black [4]
Get. Amount of adipate dichloride supported in reaction product [3]; about 250
μmol / g of carbon black CD fixed amount; about 70 μmol / g of carbon black

(3) A carbon black-adipic acid dichloride reactant [3] is obtained in the same manner as in the above Synthesis Example (2), and the reactant is dissolved in dehydrated DMSO (or DMF).
[3] was dispersed in the same DMSO at 0-5 ° C under a nitrogen stream.
(Or DMF). Monoamino-β
-Slowly drop CD (n = 7). After completion of the dropwise addition, the mixture is stirred at room temperature for about 48 hours. After the completion of the reaction, filtration was performed, and CD-carbon black was separated by filtration. To obtain a CD-immobilized carbon black [5]. Monoamino CD fixed amount: about 100 μmol / g of carbon black

(4) A carbon black-adipic acid dichloride reactant [3] is obtained in the same manner as in Synthesis Example (2), and the reactant [3] is dispersed in water and stirred at 100 ° C. for 24 hours. After the completion of the reaction, the reaction carbon black was separated by filtration, washed repeatedly with acetone, dried at 80 to 90 ° C. under reduced pressure, and dried.
[6] is obtained.

The above reactant [6] is dispersed in dehydrated pyridine, and DCC (dicyclohexylcarbodiimide) is dispersed therein.
, And β-CD dissolved in the same pyridine at room temperature.
(N = 7) is added dropwise. After completion of the dropwise addition, the mixture is stirred under reflux for 48 hours. After the completion of the reaction, the reaction carbon black is filtered off, washed repeatedly with water, and dried at 80 to 90 ° C. under reduced pressure to obtain a CD-immobilized carbon black [7]. CD fixed amount: about 50 μmol / g of carbon black

(5) In the same manner as in Synthesis Example (4),
The reaction product [6] is obtained. The reaction product [6] is dispersed in a 5N-KOH aqueous solution and stirred at 70 to 80 ° C for 12 hours. After completion of the reaction, the reaction carbon black was filtered off, washed repeatedly with dehydrated methanol, and dried under reduced pressure at 80 to 90 ° C.
[8] is obtained.

The reactant [8] was dispersed in dehydrated DMSO (or DMF), and the same DMS was added at room temperature under a nitrogen stream.
Monotosyl-β-CD dissolved in O (or DMF)
(Or monoiod, n = 7) is dropped. After the completion of the dropwise addition, the reaction is carried out at 90 to 100 ° C for 48 hours.

After completion of the reaction, the reaction carbon black is left to cool, the reaction carbon black is separated by filtration, washed repeatedly with hot water, and dried under reduced pressure at 80 to 90 ° C. to obtain a CD-immobilized carbon black [9]. Fixed amount of CD: about 90 μmol / g of carbon black

(6) A reactant [3] is obtained in the same manner as in Synthesis Example (2). The reactant [3] is dispersed in THF, and an aqueous solution of sodium azide (NaN ₃ ) is added at 0 to 5 ° C.
Drip below. After completion of the dropwise addition, the mixture was stirred at the same temperature for 24 hours,
After completion of the reaction, the reaction carbon black is separated by filtration, washed repeatedly with ice-cold water, and dried under reduced pressure at 80 to 90 ° C. to obtain a reaction product [10].

The obtained reaction product [10] was dispersed in dehydrated DMSO, and monoamino β-CD dissolved in the same DMSO was dissolved.
(N = 7) was dropped at room temperature,
Incubate for 24 hours. After completion of the reaction, the reaction carbon black is separated by filtration and further refluxed in methanol (about 24 hours). Thereafter, the mixture is filtered and dried under reduced pressure at 80 to 90 ° C. to obtain CD-immobilized carbon black [11]. Monoamino CD fixed amount: about 100 μmol / g of carbon black

(7) CD-immobilized carbon black in the same manner as in Synthesis Example (6) except that β-CD was used instead of monoamino β-CD (n = 7).
[12] is obtained. CD fixed amount: about 100 μmol / g of carbon black

(8) Carbon black is dispersed in a 5N-NaOH aqueous solution, and chloromethyloxirane is added at room temperature. After the addition, the mixture was stirred at 140 to 150 ° C. for 24 hours.
Dry under reduced pressure at ℃ to obtain reaction product [13]. Chloromethyloxirane carrying amount; about 200 μmol / g of carbon black

The reactant [13] is dispersed in dehydrated pyridine,
At room temperature, β-CD (n = 7) dissolved in the pyridine is added dropwise, and after the completion of the addition, the mixture is stirred under reflux for 24 hours. After completion of the reaction, the reaction carbon black is separated by filtration, washed repeatedly with water and methanol, and dried at 80 to 90 ° C. under reduced pressure to obtain CD-immobilized carbon black [14]. β-CD fixed amount; about 50 μmol / g of carbon black

(9) In the above synthesis example (8), β-
A CD-immobilized carbon black [15] is obtained in the same manner except that monoamino β-CD is used instead of CD. Monoamino-β-CD fixed amount; about 70 μmol / g of carbon black

(10) -1 The reaction product [13]
Stir at 80 ° C for about 12 hours, allow to cool, filter, wash well with methanol, and dry under reduced pressure to obtain reaction product [16] (epoxy ring opening amount: about 100%). This is performed in the same manner as in the synthesis of [14] in Reaction Example (8) to obtain a reactant [17]. CD fixed amount: about 60 μmol / g of carbon black

(10) -2 After a reaction product [16] was obtained in the same manner as in (10) -1, the same procedure was repeated except that the β-CD of (10) -1 was changed to monoamino β-CD. Reactant [18]
Get. Amino-CD fixed amount: about 80 μmol / carbon black 1
g Each of the above-mentioned supported amount and fixed amount was determined from the elemental analysis value.

[0055]

As described in detail above, according to the present invention, it is possible to obtain a CD-immobilized carbon black in which a CD is chemically bonded to carbon black and which is satisfactory in the amount of CD immobilized. Can be provided with a method for immobilizing a CD.

Further, by immobilizing CD on carbon black, an insoluble separation / adsorbent can be obtained by utilizing its inclusion function.

Since the hydroxyl groups of carbon black are more stable than the silanol groups of activated silica gel, even if there are unreacted hydroxyl groups in carbon black, they have excellent long-term stability in an aqueous solution as compared with activated silica gel. I have.
In addition, it is stably present even in strong acids and strong alkalis.

Claims (7)

(57) [Claims] 1. A cyclodextrin-immobilized carbon black obtained by binding cyclodextrin to the surface of carbon black. 2. A method for immobilizing cyclodextrin, comprising chlorinating a carboxyl group of carbon black, reacting with a diamine, and then reacting with a cyclodextrin derivative. 3. A method for immobilizing cyclodextrin, which comprises reacting carbon black with a diisocyanate and then reacting it with cyclodextrin or a cyclodextrin derivative. 4. A method for immobilizing cyclodextrin, comprising reacting carbon black with a dicarboxylic acid halide or further converting the same to an azide group, and then reacting with cyclodextrin or a cyclodextrin derivative. 5. A method in which carbon black is reacted with a dicarboxylic acid halide and then converted into a carboxylic acid, and the obtained compound is reacted with cyclodextrin or a cyclodextrin derivative, or an alkali of the compound obtained as the carboxylic acid is reacted. A method for immobilizing cyclodextrin, comprising reacting a metal salt with a cyclodextrin derivative. 6. A method for immobilizing cyclodextrin, which comprises reacting carbon black with an alkyl oxirane halide and then reacting with a cyclodextrin or a cyclodextrin derivative. 7. A method for immobilizing cyclodextrin, comprising reacting carbon black with an alkyl oxirane halide, opening the epoxy group and reacting with cyclodextrin or a cyclodextrin derivative.