JP2016069652A - Cyclodextrin derivative and method for producing the same, and polymer of cyclodextrin derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cyclodextrin derivative from which can remove a phenol compound well.SOLUTION: To provide a cyclodextrin derivative obtained by amidating amino groups of a compound represented by the following formula with 2-methacryloyloxyethyl succinate, 2-methacryloyloxyethyl phthalate, and the like, which can adsorb pollutants such as phenols generated in a chemical plant, a petrochemical refinery, or the like. (In the formula, x is an integer of 1 to 3; and k is an integer of 6 to 8.)SELECTED DRAWING: None

Description

  The present invention relates to a cyclodextrin derivative and a method for producing the same, and a polymer of the cyclodextrin derivative.

  Many factories such as chemical factories, oil refineries, and steel mills generate wastewater containing environmental pollutants. The release of these polluted waters into the sea, rivers, and atmosphere is regulated and must be detoxified before discharge.

  For example, phenols are one of the environmental pollutants, but are strictly regulated by the Water Supply Law and Water Pollution Control Law. Phenols are basic substances in the organic synthetic chemical industry, and are important as raw materials for phenol resins, picric acid, dyes, agricultural chemicals and the like. It is also used in analytical reagents, preservatives, pharmaceuticals, etc., and the sources of pollution include wastewater from business sites, research facilities, hospitals, etc. that handle these. Therefore, separating and removing phenolic compounds from these wastewaters has become an extremely important issue.

  As a method for solving such problems, a method using cyclodextrin has been proposed. Cyclodextrin is a cyclic compound composed of α-D-glucose units. Cyclodextrin is a monodisperse cyclic oligomer having a small molecular size of several 直径 in diameter, and it is well known that a hydrophobic substance is incorporated into a molecule to form an inclusion compound.

  As a method for removing a phenol compound using cyclodextrin, for example, Patent Documents 1 and 2 disclose a method for removing a phenol compound using a polymer obtained by crosslinking cyclodextrin with diisocyanate. Patent Document 3 discloses removal of a phenol compound by a cyclodextrin having a photocrosslinking group.

JP 2005-125193 A JP 2006-83379 A JP 2007-46041 A

  However, the removal method of the phenol compound by cyclodextrin as described above has a low removal rate, and it cannot be said that the phenol compound can be sufficiently separated and removed.

  In view of the circumstances as described above, an object of the present invention is to provide a polymer capable of removing a phenol compound satisfactorily and its peripheral technology.

  As a result of intensive studies in view of the above problems, the present inventors have found that a monomer obtained by adding a polymerizable functional group to cyclodextrin is polymerized by radical polymerization, thereby efficiently including a phenol compound. As a result, the present invention has been completed.

  In order to achieve the above object, a cyclodextrin derivative according to one embodiment of the present invention has a structure represented by Formula (1).

…（１）
（式（１）中、ｘは１〜３の整数、ｋは６〜８の整数、Ｒ^１は水素原子もしくはメチル基、Ｒ^２は炭素原子数１〜４の炭化水素基、Ｒ^３は炭素原子数１〜６の炭化水素基を示す。）

... (1)
(In formula (1), x is an integer of 1 to 3, k is an integer of 6 to 8, R ¹ is a hydrogen atom or a methyl group, R ² is a hydrocarbon group having 1 to 4 carbon atoms, and R ³ is carbon. (A hydrocarbon group having 1 to 6 atoms is shown.)

  The cyclodextrin derivative may have a structure represented by the formula (2).

…（２）
（式（２）中、ｙは５〜７の整数、Ｒ^１は水素原子もしくはメチル基、Ｒ^２は炭素原子数１〜４の炭化水素基、Ｒ^３は炭素原子数１〜６の炭化水素基を示す。）

... (2)
(In the formula (2), y is an integer of 5 to 7, R ¹ is a hydrogen atom or a methyl group, R ² is a hydrocarbon group having 1 to 4 carbon atoms, and R ³ is a hydrocarbon having 1 to 6 carbon atoms. Group.)

  The method for producing a cyclodextrin derivative according to one aspect of the present invention includes the step of producing the cyclodextrin derivative by amidating the compound represented by the formula (3) and the compound represented by the formula (4). including.

…（３）
（式（３）中、ｘは１〜３の整数、ｋは６〜８の整数を示す。）

... (3)
(In formula (3), x represents an integer of 1 to 3, and k represents an integer of 6 to 8.)

…（４）
（式（４）中、Ｒ^１は水素原子もしくはメチル基、Ｒ^２は炭素原子数１〜４の炭化水素基、Ｒ^３は炭素原子数１〜６の炭化水素基を示す。）

... (4)
(In Formula (4), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrocarbon group having 1 to 4 carbon atoms, and R ³ represents a hydrocarbon group having 1 to 6 carbon atoms.)

  According to this configuration, the cyclodextrin derivative can be obtained efficiently.

Moreover, the manufacturing method of the cyclodextrin derivative which concerns on one form of this invention includes (A) process and (B) process.
In the step (A), a compound represented by the formula (6) is produced by benzylamination of the compound represented by the formula (5) using benzylamine.
In the step (B), the compound represented by the formula (3) is generated by reducing the compound represented by the formula (6) obtained in the step (A).

…（５）
（式（５）中、ｘは１〜３の整数、ｋは６〜８の整数を示す。）

... (5)
(In formula (5), x represents an integer of 1 to 3, and k represents an integer of 6 to 8.)

…（６）
（式（６）中、ｘは１〜３の整数、ｋは６〜８の整数を示す。）

... (6)
(In formula (6), x represents an integer of 1 to 3, and k represents an integer of 6 to 8.)

…（３）
（式（３）中、ｘは１〜３の整数、ｋは６〜８の整数を示す。）

... (3)
(In formula (3), x represents an integer of 1 to 3, and k represents an integer of 6 to 8.)

  According to this structure, the compound represented by Formula (3) which is an intermediate body of the said cyclodextrin derivative can be obtained efficiently.

  The polymer of the cyclodextrin derivative according to one embodiment of the present invention can be obtained by polymerizing the cyclodextrin derivative represented by the formula (1) or the formula (2).

  According to this configuration, the obtained polymer can efficiently remove phenol from a low concentration phenol compound-containing aqueous solution.

  The polymer which can remove a phenol compound favorably, and its peripheral technique can be provided.

[Cyclodextrin derivative]
The cyclodextrin derivative according to the present embodiment is a compound represented by formula (1) or formula (2).

…（１）

... (1)

…（２）

... (2)

  The value of x in the formula (1) represents the number of glucose units having a substituent in the cyclodextrin derivative according to this embodiment, that is, the number of the substituent.

  The value of x is an integer from 1 to 3. Further, the value of x is preferably 1 or 2, and more preferably 1. On the other hand, when the value of x is more than 3, the viscosity of the polymer aqueous solution obtained by polymerization becomes high, so that the handling becomes difficult, or the polymer may be insoluble in water.

  The value of k−x in the formula (1) represents the number of glucose units having no substituent in the cyclodextrin derivative according to this embodiment. The value of k in Formula (1) is an integer of 6-8.

  Here, when the value of x is 1, the cyclodextrin derivative according to this embodiment has a structure represented by Formula (2). The value of y in Formula (2) is an integer of 5-7.

R ¹ in the formulas (1) and (2) represents a hydrogen atom or a methyl group. Moreover, R < ² > in Formula (1), (2) represents a C1-C4 hydrocarbon group. Specific examples of the hydrocarbon group having 1 to 4 carbon atoms include a methylene group, an ethylene group, a propylene group, and a butylene group.

R ³ in the formulas (1) and (2) represents a hydrocarbon group having 1 to 6 carbon atoms. Examples of the hydrocarbon group having 1 to 6 carbon atoms include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, cyclohexylene group, and phenylene group.

R ³ in the formulas (1) and (2) may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Further, R ³ in the formulas (1) and (2) may be a cyclic hydrocarbon group when the number of carbon atoms is 3 to 6.

  Examples of the compound represented by the formula (1) include 6-deoxy-6- (2-methacryloyloxyethyl succinamide) cyclodextrin, 6-deoxy-6- (2-methacryloyloxyethyl hexahydrophthalic acid amide). ) Cyclodextrin, 6-deoxy-6- (2-methacryloyloxyethylphthalamide) cyclodextrin, 6-deoxy-6- (2-acryloyloxyethyl succinamide) cyclodextrin, 6-deoxy-6- (2 -Acryloyloxyethyl hexahydrophthalamide) cyclodextrin, 6-deoxy-6- (2-acryloyloxyethylphthalamide) cyclodextrin, and the like.

[Cyclodextrin]
Cyclodextrin, which is a raw material of the cyclodextrin derivative according to this embodiment, is a cyclic compound composed of α-D-glucose units, and is represented by, for example, formula (7).

…（７）

... (7)

  The value of k in formula (7) represents the number of α-D-glucose units. In the formula (7), when k = 6, α-cyclodextrin (hereinafter sometimes referred to as α-CD) is constituted, and when k = 7, β-cyclodextrin (hereinafter referred to as β-CD). In the case where k = 8, γ-cyclodextrin (hereinafter sometimes referred to as γ-CD) is configured.

  Each of the above cyclodextrins (α-CD, β-CD, γ-CD) may be used alone or as a mixture. From the viewpoint of availability, use of α-CD with k = 6 or β-CD with k = 7 is preferable, and use of β-CD with k = 7 is more preferable.

  Furthermore, the cyclodextrin according to the present embodiment is not limited to the structure represented by the formula (7). The cyclodextrin according to the present embodiment may be one in which a hydroxyl group in the cyclodextrin is modified by adding another functional group. Examples of such cyclodextrins include cyclodextrins substituted with alkyl groups, hydroxyalkyl groups, sulfo groups, aryl groups, amino groups, and the like.

[Outline of production method of cyclodextrin derivative]
The cyclodextrin derivative according to this embodiment can be obtained by reacting a compound represented by formula (3) (hereinafter referred to as aminated cyclodextrin) with a compound represented by formula (4).

…（３）

... (3)

  About the value of x and k in Formula (3), the value equivalent to x and k in Formula (1) can be taken.

…（４）

... (4)

For ^{R 1,} R 2, ^{R 3} in the formula (4), equation (1), (2) ^{R 1,} R 2, ^{R 3} and may be mentioned the same ones as in, aspects that can be taken also The same can be mentioned.

Specific examples of the compound represented by the formula (4) include 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl phthalic acid, 2-acryloyloxyethyl succinic acid, Examples include 2-acryloyloxyethyl hexahydrophthalic acid and 2-acryloyloxyethyl phthalic acid. When the number of carbon atoms of R ¹ , R ² and R ³ is larger than the above compounds, it is difficult to obtain them.

  Specifically, the cyclodextrin derivative according to the present embodiment comprises an aminated cyclodextrin represented by the formula (3) and a compound represented by the formula (4) by the reaction route 2 represented by the formula (8). Obtained by amidation.

…（８）

... (8)

CD-NH ₂ in formula (8) represents an aminated cyclodextrin represented by formula (3). Further, embodiments for ^{R 1,} R 2, ^{R 3} in the formula (8), equation (1), may be mentioned the same as the ^{R 1,} R 2, ^{R 3} in (2) may take The same can be mentioned.

  (D) in the formula (8) is obtained by amidating the aminated cyclodextrin represented by the formula (3) and the compound represented by the formula (4) to obtain the cyclodextrin derivative according to this embodiment. Step (step (C)) is represented.

  Furthermore, the cyclodextrin derivative according to this embodiment can be produced using an aminated cyclodextrin represented by the formula (3) obtained by the reaction route 1 shown in the formula (9).

…（９）

... (9)

CD in formula (9) represents a cyclodextrin represented by formula (7), CD-Ts represents a compound represented by formula (5) (hereinafter referred to as tosylated cyclodextrin), and CD. -NBn compounds represented by formula (6) (hereinafter, referred to as benzylamino cyclodextrin.) represent, CD-NH ₂ represents an amino cyclodextrin represented by the formula (3). Further, R ⁴ in the formula (9) represents a chlorine atom or an imidazole group.

  (A) in the formula (9) is a step of obtaining a tosylated cyclodextrin represented by the formula (5) by tosylating the cyclodextrin represented by the formula (7) with a sulfonic acid derivative ((a- 1) represents step).

  (B) in the formula (9) is a step of benzylamination of the tosylated cyclodextrin represented by the formula (5) using benzylamine to obtain a benzylaminated cyclodextrin represented by the formula (6) ( (A) Step).

  (C) in the formula (9) is a step of reducing the benzyl aminated cyclodextrin represented by the formula (6) to obtain an aminated cyclodextrin represented by the formula (3) as an intermediate (( B) represents step).

…（５）

... (5)

  About the value of x and k in Formula (5), it is possible to change variously by the (a-1) process.

…（６）

(6)

  As for the values of x and k in the equation (6), values equivalent to x and k in the equation (5) can be taken.

[Details of production method of cyclodextrin derivative]
As described above, the method for producing a cyclodextrin derivative according to this embodiment includes reaction path 1 [(a-1) step, (A) step, (B) step] and reaction route 2 [(C) step]. And have. Hereinafter, each reaction route and each step will be described in detail.

<Reaction route 1>
[Step (a-1) (Reaction (a) in Reaction Path 1)]
In the step (a-1), tosylation is obtained by reacting the cyclodextrin represented by the formula (7) with a sulfonic acid derivative to obtain a tosylated cyclodextrin represented by the formula (5). It is a reaction.

  Regarding the tosylated cyclodextrin represented by the formula (5) obtained by the above tosylation reaction, Non-Patent Document 1 (Org. Synth., 77, 220 (2000)) and Non-Patent Document 2 (Org. Synth., 77, 225 (2000)), and can be obtained by reacting a cyclodextrin represented by the formula (7) with a sulfonic acid derivative such as p-toluenesulfonyl chloride or p-toluenesulfonylimidazole. .

  The cyclodextrin derivative according to this embodiment varies the value of x in formula (1), that is, the introduction rate of substituents, by changing the charge ratio of cyclodextrin and sulfonic acid derivative represented by formula (7). It is possible to change to

  In the tosylation reaction, the sulfonic acid derivative can be used in a molar ratio of 1 to 30 times the cyclodextrin represented by formula (7), and 3 to 20 times the amount. preferable. By making the use amount of the sulfonic acid derivative 1 time or more, the reaction can sufficiently proceed. Moreover, the target substituent introduction | transduction rate can be obtained efficiently by the usage-amount of a sulfonic acid derivative being 30 times or less.

  The tosylation reaction can be performed in the presence of a solvent. As the solvent, a solvent that dissolves the cyclodextrin represented by the formula (7) and does not react with the sulfonic acid derivative or has low reactivity can be used. For example, sodium hydroxide aqueous solution, pyridine, picoline, etc. are mentioned. These solvents may be used alone or in combination.

  The reaction temperature of the tosylation reaction is usually −20 ° C. to 60 ° C., preferably −5 ° C. to 25 ° C. By setting the reaction temperature to −20 ° C. or higher, the reaction can sufficiently proceed. Moreover, by making reaction temperature 60 degrees C or less, a side reaction (decomposition reaction) can be prevented and the tosylated cyclodextrin represented by Formula (5) can be obtained efficiently.

  In the tosylation reaction, the concentration of cyclodextrin represented by formula (7) is usually 1% to 20%, preferably 2% to 10%. By setting the concentration to 1% or more, the amount of the solvent to be used can be reduced, thereby improving the production efficiency. Moreover, the introduction | transduction rate of a tosyl group can be suppressed by making the said density | concentration 20% or less, and, thereby, the value of x in Formula (5) can be controlled to 3 or less.

  The reaction time of the tosylation reaction is usually 30 minutes to 12 hours, preferably 1 hour to 6 hours.

  The product obtained by the tosylation reaction can be precipitated by adding an acid such as hydrochloric acid or by reprecipitation in a solvent such as acetone. For purification of the product, general purification methods such as silica gel chromatography and recrystallization can be used.

[Step (A) (Reaction (b) in Reaction Path 1)]
In the step (A), the tosylated cyclodextrin represented by the formula (5) obtained in the step (a-1) and benzylamine are reacted to obtain the benzyl aminated cyclodextrin represented by the formula (6). Benzyl amination reaction.

  The benzyl amination reaction can be performed in the presence of a solvent. As the solvent, a solvent capable of dissolving the tosylated cyclodextrin represented by the formula (5) can be used. Examples of such a solvent include N, N-dimethylformamide, N, N-dimethylsulfoxide, N, N-dimethylacetamide and the like. These solvents may be used alone or in combination.

  The amount of benzylamine used in the benzylamination reaction can be 1 to 30 times the molar amount of the tosylated cyclodextrin represented by the formula (5), and 2 to 20 times. It is preferable to use an amount. By making the amount of benzylamine used more than 1 time, the reaction can be sufficiently advanced. Moreover, it is economical that the usage-amount of benzylamine is 30 times or less.

  The reaction temperature of the benzyl amination reaction is usually 25 ° C to 120 ° C, preferably 40 ° C to 100 ° C. By setting the reaction temperature to 25 ° C. or higher, the reaction can sufficiently proceed. Moreover, decomposition | disassembly of a product can be prevented by making reaction temperature into 120 degrees C or less.

  In the benzylamination reaction, the concentration of the tosylated cyclodextrin represented by the formula (5) during the reaction is usually 5% to 60%, preferably 10% to 40%. By setting the concentration to 5% or more, the reaction can proceed sufficiently, or the amount of solvent used can be reduced. Thereby, production efficiency can be improved. In addition, by setting the concentration to 60% or less, an increase in the viscosity of the reaction solution can be suppressed, whereby the handling of the reaction solution can be facilitated.

  The reaction time for the benzylamination reaction is usually 30 minutes to 24 hours, preferably 1 to 12 hours.

  For purification of the product obtained by the benzylamination reaction, a general purification method such as reprecipitation or recrystallization can be used.

[Step (B) (Reaction (c) in Reaction Path 1)]
Step (B) is a reduction reaction in which the benzyl aminated cyclodextrin represented by formula (6) obtained in step (A) is reduced to obtain an aminated cyclodextrin represented by formula (3).

  The reduction reaction can be performed in the presence of a metal catalyst. As the metal catalyst, for example, a palladium catalyst can be used. When using a palladium catalyst, it is preferable to use palladium activated carbon in which palladium is supported on activated carbon.

  The amount of the palladium activated carbon used can be usually 0.1% by mass to 50% by mass with respect to the benzylaminated cyclodextrin represented by the formula (6), and preferably 1% by mass to 30% by mass. . By setting the amount of palladium activated carbon used to be 0.1% by mass or more, the reaction can sufficiently proceed. Moreover, it is economical that the usage-amount of palladium activated carbon is 50 mass% or less.

  The reduction reaction can be performed in the presence of a solvent. As the said solvent, what can dissolve the benzyl aminated cyclodextrin represented by Formula (6) and the aminated cyclodextrin represented by Formula (3) can be used. Examples of such a solvent include N, N-dimethylformamide, N, N-dimethylsulfoxide, N, N-dimethylacetamide, water and the like. These solvents may be used alone or in combination.

  The reaction temperature of the reduction reaction is usually 25 ° C to 120 ° C, preferably 40 ° C to 100 ° C. By setting the reaction temperature to 25 ° C. or higher, the reaction can sufficiently proceed. Moreover, decomposition | disassembly of a product can be prevented by making reaction temperature into 120 degrees C or less.

  In the above reduction reaction, the concentration of the benzylaminated cyclodextrin represented by formula (6) during the reaction is usually 1% to 30%, preferably 2% to 20%. By setting the concentration to 1% or more, the reaction can sufficiently proceed, or the amount of solvent used can be reduced. Thereby, production efficiency can be improved. In addition, by setting the concentration to 30% or less, an increase in the viscosity of the reaction solution can be suppressed, whereby the handling of the reaction solution can be facilitated.

  The reaction time of the reduction reaction is usually 1 hour to 48 hours, and preferably 2 hours to 24 hours.

  For purification of the product obtained by the reduction reaction, a general purification method such as reprecipitation or recrystallization can be used.

<Reaction route 2>
[Step (C) (Reaction (d) in Reaction Path 2)]
In the step (C), the compound represented by the formula (4) is condensed with the aminated cyclodextrin represented by the formula (3) which is the intermediate obtained in the step (B), and then the formula (1) or the formula This is an amidation reaction to obtain a cyclodextrin derivative represented by (2).

  The amidation reaction can be performed in the presence of a solvent. As the solvent, a solvent in which the aminated cyclodextrin represented by the formula (3) and the compound represented by the formula (4) are dissolved and does not react can be used. Examples of such a solvent include N, N-dimethylformamide, N, N-dimethylsulfoxide, N, N-dimethylacetamide and the like.

  The amidation reaction is preferably performed in the presence of a condensing agent in order to avoid side reactions. Examples of the condensing agent include carbodiimide condensing agents such as N, N′-dicyclohexylcarbodiimide, phosphonium condensing agents such as benzotriazol-1-yloxy-trisdimethylaminophosphonium salt, and triazole such as 1-hydroxybenzotriazole. Condensing agents, triazine condensing agents such as 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride, and the like. 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride to be formed is preferred.

  The amount of the condensing agent used can be 1 to 5 times the molar ratio of the aminated cyclodextrin represented by formula (3). By making the use amount of the condensing agent 1 time or more by the molar ratio, the reaction can be sufficiently advanced. Moreover, it is economical when the amount of the condensing agent used is 5 times or less in terms of the molar ratio.

  The reaction temperature of the amidation reaction is usually −20 ° C. to 100 ° C., preferably 0 ° C. to 80 ° C. By setting the reaction temperature to −20 ° C. or higher, the reaction can sufficiently proceed. Moreover, side reactions, such as superposition | polymerization, can be prevented by making reaction temperature into 100 degrees C or less.

  In the amidation reaction, the concentration of the aminated cyclodextrin represented by the formula (3) during the reaction is usually 1% to 30%, preferably 2% to 20%. By setting the concentration to 1% or more, the reaction can sufficiently proceed, or the amount of solvent used can be reduced. Thereby, production efficiency can be improved. In addition, by setting the concentration to 30% or less, an increase in the viscosity of the reaction solution can be suppressed, whereby the handling of the reaction solution can be facilitated.

  The reaction time of the amidation reaction is usually 30 minutes to 24 hours, preferably 1 hour to 12 hours.

  For purification of the product obtained by the amidation reaction, a general purification method such as reprecipitation or recrystallization can be used.

  The cyclodextrin derivative represented by the formula (1) or the formula (2) can be obtained by the above production method. Moreover, in order to obtain the cyclodextrin derivative represented by the formula (2), purification is performed before the amidation reaction in the step (C), and the value of x is represented by the formula (3) of 2 or more. It is preferable to remove the aminated cyclodextrin. In particular, it is more preferable to purify the tosylated cyclodextrin represented by the formula (5) obtained in the step (a-1) and remove those having a value of x of 2 or more.

  A commercially available product may be used as the aminated cyclodextrin represented by the formula (3), but since it affects the purity of the cyclodextrin derivative represented by the formula (1) or the formula (2), a high-purity product should be used. Is preferred.

  The production method for obtaining the cyclodextrin derivative of the present invention is not limited to the production method described above. The intermediate aminated cyclodextrin represented by the formula (3) obtained in the reaction route 1 is generally also synthesized by a production method described in, for example, Langmuir 1999, 15, 5589-5495. In the production method, the aminated cyclodextrin is obtained by the reaction route 3 shown in the formula (10).

…（１０）

(10)

CD in Equation (10), CD-Ts and CD-NH ₂ is, CD in Equation (9) represents the same compound CD-Ts and _{CD-NH 2, CD-N} 3 is azide cyclodextrin Represents.

  As shown in the equation (10), the reaction path 3 includes a path for the reaction (e) and the reaction (f) and a path for only the reaction (g). The production method for carrying out the azination reaction (e) is unsuitable for production since the raw material sodium azide has explosive properties. On the other hand, in the reaction (g) in which ammonia is reacted, hydrolysis tends to occur as a side reaction, resulting in a low yield. Therefore, the reaction route 1 of the present invention is preferable as a method for producing an aminated cyclodextrin.

[Polymer of cyclodextrin derivative]
The polymer of the cyclodextrin derivative according to this embodiment is a polymer obtained by polymerizing the cyclodextrin derivative represented by the above formula (1) or formula (2).

  The molecular weight of the polymer is usually a number average molecular weight of about 5,000 to 500,000, but is not particularly limited, and can be appropriately determined by adjusting the polymerization conditions and the like so that the performance required for each application can be exhibited. .

  The polymerization reaction for producing the polymer is performed in the presence of a radical polymerization initiator in an inert atmosphere such as nitrogen, carbon dioxide, argon, helium, etc., for example, bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization. It can carry out by well-known methods, such as. From the viewpoint of purification and the like, solution polymerization is preferable. The polymer is obtained by this polymerization reaction.

  The polymerization reaction may be performed with the cyclodextrin derivative represented by formula (1) or formula (2) alone, or may be a copolymer with other general monomers. Other common monomers include, for example, 2-hydroxyethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, (meth) Various (meth) acrylic esters such as acryloyloxyethyl phosphorylcholine, methyl (meth) acrylate, dimethylaminoethyl (meth) acrylate; various vinyl ethers such as methyl vinyl ether; acrylamide, N, N′-dimethylacrylamide, (meth) acrylic acid , Allyl alcohol, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, styrene, vinyl chloride, itaconic acid, itaconic acid ester, fumaric acid, fumaric acid ester, malein Various radically polymerizable monomers such as acid and maleic acid ester are listed. Hereinafter, the monomer constituting the polymer or a mixture thereof is referred to as a monomer composition.

  Examples of the radical polymerization initiator that can be used in the polymerization reaction include 2,2-azobis (2-amidinopropyl) dihydrochloride, 2,2-azobis (2- (5-methyl-2-imidazoline-2). -Yl) propane) dihydrochloride, 4,4-azobis (4-cyanovaleric acid), 2,2-azobisisobutyramide dihydrate, 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobisisobutyronitrile (AIBN), dimethyl-2,2′-azobisisobutyrate, 1-((1-cyano-1-methylethyl) azo) formamide, 2,2′-azobis (2-methyl-N-phenylpropionamidin) dihydrochloride, 2,2′-azobis (2-methyl-N- (2-hydroxyethyl) -propionamide), 2,2′-azobis ( Azo radical polymerization initiators such as 2-methylpropionamido) dihydrate, 4,4′-azobis (4-cyanopentanoic acid), 2,2′-azobis (2- (hydroxymethyl) propionitrile) . Further, for example, benzoyl peroxide, diisopropyl peroxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, t-butylperoxydiisobutyrate, lauroyl peroxide, t-butylperoxyneodeca Noate, succinic peroxide (= succinyl peroxide), glutar peroxide, succinyl peroxyglutarate, t-butyl peroxymalate, t-butyl peroxypivalate, di-2-ethoxyethyl peroxycarbonate, 3-hydroxy-1,1 -Organic peroxides such as dimethylbutyl peroxypivalate. Furthermore, persulfate oxides, such as ammonium persulfate, potassium persulfate, and sodium persulfate, are mentioned. These radical polymerization initiators may be used alone or in combination.

  The usage-amount of a radical polymerization initiator is 0.001 mass part-10 mass parts normally with respect to 100 mass parts of monomer compositions, and 0.01 mass part-5.0 mass parts are preferable.

  The polymerization reaction can be performed in the presence of a solvent. As the solvent, a solvent that dissolves the monomer composition and does not react can be used. Examples of such solvents include alcohol solvents such as water, methanol, ethanol, n-propanol, and isopropanol, N, N-dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, pyridine, and the like. Can be given. In particular, N, N-dimethylsulfoxide, N, N-dimethylformamide or a mixed solvent of these solvents and water is preferable.

  In the above polymerization reaction, the solution concentration during the reaction can be 1% by mass to 50% by mass. The concentration of the solution includes both the concentration of the monomer composition that is a reactant and the concentration of the polymer that is a product. Manufacturing efficiency can be improved by making the said solution concentration into 1 mass% or more. In addition, by setting the solution concentration to 50% by mass or less, it is possible to prevent the reaction solution from becoming highly viscous and allow the reaction to proceed sufficiently.

  For purification of the polymer obtained by the polymerization reaction, a general purification method such as a reprecipitation method, a dialysis method, or an ultrafiltration method can be used.

  As a solvent that can be used in each of the above purification methods, a solvent that does not react with a cyclodextrin derivative can be used, and examples thereof include water, methanol, ethanol, n-propanol, and isopropanol. In particular, water, methanol, ethanol or a mixed solvent thereof is preferable.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to the range of these Examples. Various measurements in the examples were performed as follows.

^[1 H-NMR analysis]
Measurement was carried out under the conditions of solvent: D ₂ O, sample concentration: 10 mg / g, integration number: 128 times, using a product name “JNM-AL400” manufactured by JEOL Ltd.

[Mass Spectrometry (ESI-MS)]
Product name “Q-micro2695” manufactured by Waters Inc., sample concentration: 100 ppm, solvent: 10 mM aqueous solution containing 10 mM ammonium acetate, detection mode: ESI +, capillary voltage: 3.54 V, cone voltage: 30 V, ion source heater : Measurement was performed under the conditions of 120 ° C. and solvent removal gas: 350 ° C.

[Measurement of number average molecular weight (GPC)]
Preparation of mobile phase: 2.61 g of lithium bromide and 2.94 g of phosphoric acid were dissolved in 1 L of DMF. Preparation of measurement sample: 2 mg of sample was dissolved in 1 g of mobile phase. Other measurement conditions are as follows. Column: KD-806M (manufactured by Showa Denko KK), standard material: PEO (manufactured by Tosoh Corporation), detection: parallax refractometer RI-8020 (manufactured by Tosoh Corporation), calculation of number average molecular weight (Mn): molecular weight calculation program ( Measurement was performed under the conditions of GPC program for SC-8020), flow rate: 1.0 mL / min, column temperature: 40 ° C., sample solution injection amount: 100 μL, measurement time: 30 minutes.

[Measurement of phenolic compounds (HPLC)]
Preparation of mobile phase: Prepared by mixing 700 mL of ion-exchanged water and 300 mL of acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.). Preparation of measurement sample: 0.1 g of sample was dissolved in 0.9 g of mobile phase. Other measurement conditions are as follows. Column: Inertsil ODS-3V (manufactured by GL Science), detection: UV-visible detector UV-8020 (manufactured by Tosoh Corporation), flow rate: 1.0 mL / min, column temperature: 40 ° C., sample solution injection amount: 20 μL, measurement Time: Measurement was performed under the condition of 30 minutes.

[Example 1-1]
<Synthesis of 6-O-tosyl-β-cyclodextrin>
250.0 g of β-cyclodextrin (β-CD, manufactured by Tokyo Chemical Industry Co., Ltd.) and 125.0 g of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 7500 g of ion-exchanged water and cooled to 0 ° C. or lower. Thereafter, 150.0 g of p-toluenesulfonic acid chloride (p-TsCl, manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and a tosylation reaction was performed for 3 hours. After the reaction, 100.0 g of p-TsCl was added, and a tosylation reaction was further performed for 2 hours. After completion of the tosylation reaction, unreacted p-TsCl was filtered off, and the filtrate was recovered. The filtrate was cooled to 4 ° C., and 3165.2 g of 10% aqueous solution of concentrated hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added to precipitate the target product. The precipitate was collected by filtration, and the precipitate on the filter paper was washed with 1000.0 g of ion-exchanged water and 500.0 g of acetone (manufactured by China Seiyaku Co., Ltd.), and then dried at 50 ° C. under reduced pressure. To the white powder obtained by drying under reduced pressure, 894.6 g of ion-exchanged water was added and stirred at 85 ° C. for 2 hours. After stirring, the mixture was cooled to room temperature and allowed to stand for 2 hours. After standing, the precipitate is recovered by filtration, and the precipitate on the filter paper is washed with 894.6 g of ion-exchanged water and 894.6 g of acetone, and then dried under reduced pressure at 50 ° C. to obtain k = 7 in formula (5). A white powder of 6-O-tosyl-β-cyclodextrin corresponding to

<Synthesis of 6-deoxy-6-benzylamino-β-cyclodextrin>
100.0 g of 6-O-tosyl-β-cyclodextrin obtained as described above and 200.0 g of N, N-dimethylformamide (DMF, manufactured by Wako Pure Chemical Industries, Ltd.) are mixed and heated to 40 ° C. Dissolved. Thereafter, 99.8 g of benzylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, the temperature was raised to 75 ° C., and benzylamination reaction was performed for 7 hours. After completion of the benzylamination reaction, the mixture was cooled to 40 ° C. or lower, and 2000.0 g of a 15 wt% aqueous acetonitrile solution was added to obtain a white precipitate. The precipitate was collected by filtration, and the filtrate was washed with 1000.0 g of acetone and then dried under reduced pressure at 50 ° C. To the white powder obtained by drying under reduced pressure, 1000.0 g of ion-exchanged water was added and stirred vigorously to obtain a slurry-like white liquid. Water is removed by filtering the white liquid, and the crystals on the filter paper are washed with 500.0 g of ion-exchanged water and 1000.0 g of acetone, and then dried under reduced pressure at 50 ° C. to obtain k = 7 in formula (6). The corresponding 6-deoxy-6-benzylamino-β-cyclodextrin white powder was obtained.

<Synthesis of 6-deoxy-6-amino-β-cyclodextrin>
78.0 g of 6-deoxy-6-benzylamino-β-cyclodextrin obtained as described above was dissolved in 780.0 g of N, N-dimethylacetamide (DMAc, manufactured by Wako Pure Chemical Industries, Ltd.), and the temperature was raised to 65 ° C. did. After heating, 7.8 g of palladium activated carbon (10%) (manufactured by Wako Pure Chemical Industries, Ltd.) dispersed in 780.0 g of ion-exchanged water was added, the inside of the reaction vessel was placed in a hydrogen atmosphere, and hydrogen was maintained at 70 ° C for 7 hours. Addition decomposition reaction was performed. After completion of the hydrogenolysis reaction, 780.0 g of ion-exchanged water was added and the mixture was cooled to 40 ° C. or lower, and filtered through a filter paper covered with celite to collect the filtrate. Furthermore, the activated carbon on the filter paper was washed with 1950.0 g of ion exchange water, and the filtrate was recovered. The collected filtrate was distilled under reduced pressure and concentrated to about 300 g, and then the concentrated solution was added to 1950.0 g of acetone to precipitate a precipitate. The precipitate was collected by filtration, and the filtrate was washed twice with 780.0 g of ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) and then dried under reduced pressure at 50 ° C. To the powder obtained by drying under reduced pressure, 361.3 g of ion-exchanged water was added and stirred at 50 ° C. for 1 hour. After stirring, the filtrate was collected by filtration without cooling. Further, the filtrate was washed with 180.6 g of ion exchange water, and the filtrate was recovered. The collected filtrate was added to 2709.6 g of acetone to precipitate a precipitate. The precipitate was collected by filtration, and the filtrate was washed with 780.0 g of ethyl acetate, and then the filtrate was dried under reduced pressure at 50 ° C., thereby corresponding to 6-deoxy-6-amino corresponding to k = 7 in formula (3). A powder of -β-cyclodextrin was obtained.

<Synthesis of 6-deoxy-6- (2-methacryloyloxyethyl succinamide) -β-cyclodextrin>
To 60.0 g of 6-deoxy-6-amino-β-cyclodextrin obtained above, ² -methacrylic acid corresponding to R ¹ = methyl group, R ² = ethylene group, R ³ = ethylene group in formula (4) 300.0 g of DMF in which 16.04 g of leuoxyethyl succinic acid (HO-MS, manufactured by Kyoeisha Chemical Co., Ltd.) was dissolved was added and dispersed uniformly. Thereafter, 20.5 g of 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride (DMT-MM, manufactured by Wako Pure Chemical Industries, Ltd.) was added at room temperature. The amidation reaction was carried out for 8 hours. After completion of the amidation reaction, the reaction solution was added to 1500.0 g of acetone to precipitate a precipitate. The precipitate was collected by filtration, and the filtrate was washed with 900.0 g of acetonitrile. To the obtained filtrate, 1600.0 g of a 75 wt% aqueous acetonitrile solution was added, and the mixture was sufficiently stirred and dispersed. The dispersion was filtered, and the filtrate was washed twice with 300.0 g of acetone and dried under reduced pressure at 40 ° C., whereby k = 7, x = 1, R ¹ = methyl group, R ² = ethylene of formula (1). Group, R ³ = 99% mono-6-deoxy-6- (2-methacryloyloxyethyl succinamide) -β-cyclodextrin corresponding to ethylene group, k = 7 in formula (1), x = 2, 6 containing 1% of di-6-deoxy-6- (2-methacryloyloxyethylsuccinamide) -β-cyclodextrin corresponding to R ¹ = methyl group, R ² = ethylene group, R ³ = ethylene group A white powder of deoxy-6- (2-methacryloyloxyethyl succinamide) -β-cyclodextrin was obtained.

The results of ¹ H NMR measurement and ESI-MS measurement of the obtained product are as follows.
¹ H NMR (solvent: D ₂ O, standard peak: HOD): 2.0 ppm (3H, CH ₃ ), 2.4-2.8 ppm (4H, CO— (CH ₂ ) ₂ —CO), 3.5 _{-4.1ppm (42H, - CH (OH} ) -, - CH 2 OH), 4.3-4.5ppm (4H, -O- (CH 2) 2 -O -), 4.6-5.0ppm (20H, OH), 5.1ppm ( 7H, - CH (OH) -), 5.7-6.3ppm (2H, CH 2)
ESI-MS (M + H ⁺ ): 1347 (mono-6-deoxy (2-methacryloyloxyethyl succinamide) -β-cyclodextrin), 1558 (di-6-deoxy (2-methacryloyloxyethyl succinamide)- β-cyclodextrin)

[Example 2-1]
<Synthesis of Mono-6-O-tosyl-β-cyclodextrin>
To 102.0 g of the white powder of 6-O-tosyl-β-cyclodextrin obtained in the same procedure as in Example 1-1, 644.1 g of ion-exchanged water and 787.2 g of acetonitrile were added and stirred. Refluxed for 2 hours. After refluxing, it was cooled to room temperature and allowed to stand for 2 hours. After standing, the precipitate was collected by filtration, washed with 894.6 g of 55 wt% acetonitrile aqueous solution, and then dried under reduced pressure at 50 ° C., so that mono-6 corresponding to k = 7 and x = 1 in formula (5) A white powder of -O-tosyl-β-cyclodextrin was obtained.

<Synthesis of mono-6-deoxy-6-benzylamino-β-cyclodextrin>
Mono-6-O-tosyl-β-cyclodextrin 80.0 g obtained above and DMF 160.0 g were mixed and heated to 40 ° C. to dissolve. Thereafter, 79.8 g of benzylamine was added, the temperature was raised to 75 ° C., and a benzylamination reaction was performed for 7 hours. After completion of the benzylamination reaction, the mixture was cooled to 40 ° C. or lower, and 1600.0 g of a 15 wt% aqueous acetonitrile solution was added to obtain a white precipitate. The precipitate was collected by filtration, and the filtrate was washed with 800.0 g of acetone and dried under reduced pressure at 50 ° C. To the white powder obtained by drying under reduced pressure, 800 g of ion-exchanged water was added and stirred vigorously to obtain a slurry-like white liquid. Water is removed by filtering the white liquid, and the crystals on the filter paper are washed with 400 g of ion-exchanged water and 800 g of acetone, and then dried under reduced pressure at 50 ° C., so that k = 7 and x = 1 in formula (6). The corresponding mono-6-deoxy-6-benzylamino-β-cyclodextrin white powder was obtained.

<Synthesis of mono-6-deoxy-6-amino-β-cyclodextrin>
Mono-6-deoxy-6-benzylamino-β-cyclodextrin 64.0 g obtained above was dissolved in 640.0 g of DMAc, and the temperature was raised to 65 ° C. After the temperature elevation, 6.4 g of palladium activated carbon (10%) dispersed in 640.0 g of ion-exchanged water was added, the inside of the reaction vessel was placed in a hydrogen atmosphere, and a hydrogenolysis reaction was performed at 70 ° C. for 7 hours. After completion of the hydrogenolysis reaction, 640.0 g of ion-exchanged water was added, the mixture was cooled to 40 ° C. or lower, and filtered through a filter paper covered with celite to collect the filtrate. Furthermore, the activated carbon on the filter paper was washed with 1280.0 g of ion exchange water, and the filtrate was recovered. The collected filtrate was distilled under reduced pressure and concentrated to about 250 g, and then the concentrated solution was added to 1600.0 g of acetone to precipitate a precipitate. The precipitate was recovered by filtration, and the filtrate was washed twice with 780.0 g of ethyl acetate and then dried under reduced pressure at 50 ° C. To the powder obtained by drying under reduced pressure, 296.4 g of ion-exchanged water was added and stirred at 50 ° C. for 1 hour. After stirring for 1 hour, the filtrate was recovered by filtration without cooling. Further, the filtrate was washed with 148.2 g of ion exchange water, and the filtrate was recovered. The collected filtrate was added to 2223.3 g of acetone to precipitate a precipitate. The precipitate was collected by filtration, and the filtrate was washed with 640.0 g of ethyl acetate, and then the filtrate was dried at 50 ° C. under reduced pressure to obtain mono-6 corresponding to k = 7 and x = 1 in formula (3). A powder of -deoxy-6-amino-β-cyclodextrin was obtained.

<Synthesis of mono-6-deoxy-6- (2-methacryloyloxyethyl succinamide) -β-cyclodextrin>
250.0 g of DMF in which 12.54 g of HO-MS was dissolved was added to 50.0 g of mono-6-deoxy-6-amino-β-cyclodextrin obtained as described above and dispersed uniformly. Thereafter, 17.08 g of DMT-MM was added, and an amidation reaction was performed at room temperature for 8 hours. After completion of the amidation reaction, the reaction solution was added to 1250.0 g of acetone to precipitate a precipitate. The precipitate was collected by filtration, and the filtrate was washed with 750.0 g of acetonitrile. To the obtained filtrate was added 1333.3 g of a 75 wt% acetonitrile aqueous solution, and the mixture was sufficiently stirred and dispersed. The dispersion was filtered, and the filtrate was washed twice with 250.0 g of acetone and dried under reduced pressure at 40 ° C., whereby y = 6, R ¹ = methyl group, R ² = ethylene group, R ³ in formula (2). = White powder of mono-6-deoxy-6- (2-methacryloyloxyethyl succinamide) -β-cyclodextrin corresponding to ethylene group was obtained.

The results of ¹ H NMR measurement and ESI-MS measurement of the obtained product are as follows.
¹ H NMR (solvent: D ₂ O, standard peak: HOD): 2.0 ppm (3H, CH ₃ ), 2.4-2.8 ppm (4H, CO— (CH ₂ ) ₂ —CO), 3.5 _{-4.1ppm (42H, - CH (OH} ) -, - CH 2 OH), 4.3-4.5ppm (4H, -O- (CH 2) 2 -O -), 4.6-5.0ppm (20H, OH), 5.1ppm ( 7H, - CH (OH) -), 5.7-6.3ppm (2H, CH 2)
ESI-MS (M + H ^< + ^> ): 1347

[Example 3-1]
<Synthesis of mono-6-deoxy-6- (2-methacryloyloxyethylhexahydrophthalamide) -β-cyclodextrin>
To a mono-6-deoxy-6-amino-β-cyclodextrin (2.0 g) obtained by the same procedure as in Example 2-1, R ¹ = methyl group, R ² = ethylene group, R of formula (4) ³ = 2-methacryloyloxyethyl hexahydrophthalic acid (HO-HH, manufactured by Kyoeisha Chemical Co., Ltd.) HO-HH corresponding to cyclohexylene group was added to 10.0 g of DMF and dissolved uniformly. Thereafter, 0.68 g of DMT-MM was added, and an amidation reaction was performed at room temperature for 8 hours. After completion of the amidation reaction, the reaction solution was added to 50.0 g of acetone to precipitate a precipitate. The precipitate was collected by filtration, and the filtrate was washed with 30.0 g of acetonitrile. To the obtained filtrate was added 53.3 g of a 75 wt% acetonitrile aqueous solution, and the mixture was sufficiently stirred and dispersed. The dispersion was filtered, and the filtrate was washed twice with 10.0 g of acetone and dried under reduced pressure at 40 ° C., whereby y = 6, R ¹ = methyl group, R ² = ethylene group, R ³ in formula (2). = White powder of mono-6-deoxy-6- (2-methacryloyloxyethylhexahydrophthalamide) -β-cyclodextrin corresponding to cyclohexylene group was obtained.

The results of ¹ H NMR measurement and ESI-MS measurement of the obtained product are as follows.
¹ H NMR (solvent: D ₂ O, standard peak: HOD): 1.0-2.0 ppm (8H, —CH ₂ — ) 2.0 ppm (3H, CH ₃ ), 2.6-3.1 ppm (2H , CO- CH-CH -CO), 3.3-4.2ppm (42H, - CH (OH) -, - CH 2 OH), 4.2-4.5ppm (4H, -O- (CH 2) _{2 -O -), 4.6-5.0ppm (20H} , OH), 5.1ppm (7H, - CH (OH) -), 5.8-6.2ppm (2H, CH 2)
ESI-MS (M + Na ^< + ^> ): 1423

[Example 4-1]
<Synthesis of 6-O-tosyl-α-cyclodextrin>
After 10.0 g of α-cyclodextrin (α-CD, manufactured by Cyclochem) was dissolved in 80.0 g of picoline (manufactured by Wako Pure Chemical Industries, Ltd.), nitrogen substitution was performed and the mixture was cooled to 0 ° C. In a separate container, 10.0 g of p-TsCl was dissolved in 15.0 g of pyridine (Wako Pure Chemical Industries, Ltd.). While maintaining the picoline solution in which α-CD was dissolved at 5 ° C. or lower, a pyridine solution in which p-TsCl was dissolved was dropped to perform a tosylation reaction. After completion of the dropwise addition, stirring was continued at room temperature for 2 hours. After completion of the tosylation reaction, the mixture was added to 115.0 g of acetone to precipitate a precipitate. The precipitate was collected by filtration, and the filtrate was washed with 600 g of acetone and then dried under reduced pressure to obtain a white to yellow powder. The obtained powder was dispersed and dissolved in 100.0 g of water, passed through a column filled with Diaion HP-20 (manufactured by Mitsubishi Chemical Corporation), and washed with sufficient water. Next, a sufficient amount of 25% aqueous ethanol solution was passed through to elute the target product. The collected 25% ethanol aqueous solution was distilled off under reduced pressure to obtain a white powder of 6-O-tosyl-α-cyclodextrin corresponding to k = 6 in formula (5).

<Synthesis of 6-deoxy-6-benzylamino-α-cyclodextrin>
7.0 g of 6-O-tosyl-α-cyclodextrin obtained above, 14.0 g of DMF, and 12.0 g of benzylamine were added, the temperature was raised to 75 ° C., and a benzylamination reaction was performed for 7 hours. After completion of the benzylamination reaction, the reaction mixture was cooled to 40 ° C. or lower and poured into 165.0 g of acetone to precipitate a precipitate. The precipitate was collected by filtration, and the filtrate was washed with 165.0 g of acetone, and then dried under reduced pressure at 50 ° C., whereby 6-deoxy-6-benzylamino-α-corresponding to k = 6 in formula (6). A white powder of cyclodextrin was obtained.

<Synthesis of 6-deoxy-6-amino-α-cyclodextrin>
5.0 g of 6-deoxy-6-benzylamino-α-cyclodextrin obtained as described above was dissolved in 50.0 g of DMAc. 0.5 g of palladium activated carbon (10%) dispersed in 50.0 g of ion-exchanged water was added, the inside of the reaction vessel was placed in a hydrogen atmosphere, and a hydrogenolysis reaction was performed at 70 ° C. for 7 hours. After completion of the hydrogenolysis reaction, 25.0 g of ion-exchanged water was added, the mixture was cooled to 40 ° C. or lower, and filtered through a filter paper covered with celite, and the filtrate was recovered. Furthermore, the activated carbon on the filter paper was washed with 100.0 g of ion exchange water, and the filtrate was recovered. The collected filtrate was distilled under reduced pressure and concentrated to about 20 g, and then the concentrated solution was poured into 125.0 g of acetone to precipitate a precipitate. The precipitate was recovered by filtration, and the filtrate was washed with 100.0 g of acetone and then dried under reduced pressure at 50 ° C. to thereby obtain 6-deoxy-6-amino-α-cyclo which corresponds to k = 6 in formula (3). A dextrin powder was obtained.

<Synthesis of 6-deoxy-6- (2-methacryloyloxyethyl succinamide) -α-cyclodextrin>
To 3.5 g of 6-deoxy-6-amino-α-cyclodextrin obtained as described above, 3.32 g of HO-MS of formula (4) and 17.5 g of DMF were added and dissolved uniformly. Thereafter, 2.99 g of DMT-MM was added, and an amidation reaction was performed at room temperature for 8 hours. After completion of the amidation reaction, the reaction solution was added to 87.5 g of acetone to precipitate a precipitate. The precipitate is recovered by filtration, and the filtrate is washed with 35.0 g of acetonitrile and 35.0 g of acetone and dried under reduced pressure at 40 ° C., so that k = 6, x = 1, R ¹ = methyl group in formula (1). , R ² = ethylene group, R ³ = 75% mono-6-deoxy-6- (2-methacryloyloxyethylsuccinamide) -α-cyclodextrin corresponding to ethylene group, k = 6 in formula (1) X = 2, R ¹ = methyl group, R ² = ethylene group, R ³ = 24 corresponding to di-6-deoxy-6- (2-methacryloyloxyethyl succinamide) -α-cyclodextrin %, Mono-6-deoxy-6- (2-methacryloyloxyethyl succinate corresponding to k = 6, x = 3, R ¹ = methyl group, R ² = ethylene group, R ³ = ethylene group in formula (1) Acid amide) -α To give a white powder of a cyclodextrin containing 1% 6-deoxy-6- (2-methacryloyloxyethyl succinic acid amide)-.alpha.-cyclodextrin.

The results of ¹ H NMR measurement and ESI-MS measurement of the obtained product are as follows.
¹ H NMR (solvent: D ₂ O, standard peak: HOD): 2.0 ppm (4H, CH ₃ ), 2.4-2.8 ppm (5H, CO— (CH ₂ ) ₂ —CO), 3.4 _{-4.2ppm (36H, - CH (OH} ) -, - CH 2 OH), 4.2-4.6ppm (5H, -O- (CH 2) 2 -O -), 4.7-4.9ppm (20H, OH), 5.1ppm ( 6H, - CH (OH) -), 5.7-6.3ppm (3H, CH 2)
ESI-MS (M + H ⁺ ): 1185 (mono-6-deoxy (2-methacryloyloxyethyl succinamide) -α-cyclodextrin), 1397 (di-6-deoxy (2-methacryloyloxyethyl succinamide)- α-cyclodextrin), 1609 (tri-6-deoxy (2-methacryloyloxyethyl succinamide) -α-cyclodextrin)

[Example 5-1]
<Synthesis of mono-6-O-tosyl-α-cyclodextrin>
After 10.0 g of α-CD was dissolved in 80.0 g of picoline, nitrogen substitution was performed and the mixture was cooled to 0 ° C. In a separate container, 10.0 g of p-TsCl was dissolved in 15.0 g of pyridine. While maintaining the picoline solution in which α-CD was dissolved at 5 ° C. or lower, a pyridine solution in which p-TsCl was dissolved was dropped to perform a tosylation reaction. After completion of the dropwise addition, stirring was continued at room temperature for 2 hours. After completion of the tosylation reaction, the mixture was added to 115.0 g of acetone to precipitate a precipitate. The precipitate was collected by filtration, and the filtrate was washed with 600 g of acetone and then dried under reduced pressure to obtain a white to yellow powder. The obtained powder was dispersed and dissolved in 100.0 g of water, passed through a column filled with Diaion HP-20, and washed with sufficient water. Next, a 20% aqueous ethanol solution was passed through to elute the target product. The collected 20% aqueous ethanol solution was distilled off under reduced pressure to obtain a white powder of mono-6-O-tosyl-α-cyclodextrin corresponding to k = 6 and x = 1 in formula (5).

<Synthesis of mono-6-deoxy-6-benzylamino-α-cyclodextrin>
Mono-6-O-tosyl-α-cyclodextrin (3.2 g) obtained above, 6.4 g of DMF and 3.65 g of benzylamine were added, the temperature was raised to 75 ° C., and a benzylamination reaction was performed for 7 hours. After completion of the benzylamination reaction, the reaction mixture was cooled to 40 ° C. or lower and charged into 66.3 g of acetone to precipitate a precipitate. The precipitate was collected by filtration, and the filtrate was washed with 66.3 g of acetone, and then dried under reduced pressure at 50 ° C., whereby mono-6-deoxy-6 corresponding to k = 6 and x = 1 in formula (6). -A white powder of benzylamino-α-cyclodextrin was obtained.

<Synthesis of mono-6-deoxy-6-amino-α-cyclodextrin>
2.8 g of mono-6-deoxy-6-benzylamino-α-cyclodextrin obtained as described above was dissolved in 28.0 g of DMAc. 0.28 g of palladium activated carbon (10%) dispersed in 28.0 g of ion-exchanged water was added, the inside of the reaction vessel was placed in a hydrogen atmosphere, and a hydrogenolysis reaction was performed at 70 ° C. for 7 hours. After completion of the hydrogenolysis reaction, 14.0 g of ion-exchanged water was added, the mixture was cooled to 40 ° C. or lower, and filtered through a filter paper covered with celite to collect the filtrate. Further, the activated carbon on the filter paper was washed with 56.0 g of ion exchange water, and the filtrate was recovered. The collected filtrate was distilled under reduced pressure and concentrated to about 10 g, and then the concentrated solution was put into 70.0 g of acetone to precipitate a precipitate. The precipitate was collected by filtration, and the filtrate was washed with 70.0 g of acetone, and then dried under reduced pressure at 50 ° C. to thereby obtain mono-6-deoxy-6-amino-α corresponding to k = 7 in formula (3). -A powder of cyclodextrin was obtained.

<Synthesis of mono-6-deoxy-6- (2-methacryloyloxyethyl succinamide) -α-cyclodextrin>
To 2.4 g of mono-6-deoxy-6-amino-β-cyclodextrin obtained as described above, 1.14 g of HO-MS of formula (4) and 12.0 g of DMF were added and dissolved uniformly. Thereafter, 1.03 g of DMT-MM was added, and an amidation reaction was performed at room temperature for 8 hours. After completion of the amidation reaction, the reaction solution was added to 60.0 g of acetone to precipitate a precipitate. The precipitate is recovered by filtration, the filtrate is washed with 60.0 g of acetone, and dried under reduced pressure at 40 ° C., whereby y = 5, R ¹ = methyl group, R ² = ethylene group, R ³ in formula (2). = White powder of mono-6-deoxy-6- (2-methacryloyloxyethyl succinamide) -α-cyclodextrin corresponding to ethylene group was obtained.

The results of ¹ H NMR measurement and ESI-MS measurement of the obtained product are as follows.
¹ H NMR (solvent: D ₂ O, standard peak: HOD): 2.0 ppm (3H, CH ₃ ), 2.4-2.8 ppm (4H, CO— (CH ₂ ) ₂ —CO), 3.4 _{-4.2ppm (36H, - CH (OH} ) -, - CH 2 OH), 4.2-4.6ppm (4H, -O- (CH 2) 2 -O -), 4.7-4.9ppm (20H, OH), 5.1ppm ( 6H, - CH (OH) -), 5.7-6.3ppm (2H, CH 2)
ESI-MS (M + H ^< + ^> ): 1185

[Example 6]
<Synthesis of cyclodextrin derivative polymer>
The white powder as the cyclodextrin derivative obtained in Examples 1-1, 2-1, 3-1, 4-1, 5-1 was dissolved in DMF or a mixed solvent of DMF and water, Nitrogen was bubbled through the flask for 30 minutes. Then, the radical polymerization reaction was started by heating to 50 ° C. and adding t-butyl peroxyneodecanoate (PB-ND, manufactured by NOF Corporation) dissolved in DMF. PB-ND was washed with DMF. After the radical polymerization reaction at 50 ° C. for 4 hours, the temperature was raised to 70 ° C. and the radical polymerization reaction was further performed for 3 hours. After completion of the radical polymerization reaction, the reaction solution was cooled to room temperature and reprecipitated in 135.0 g of a mixed solvent of ion-exchanged water: ethanol (Wako Pure Chemical Industries, Ltd.) = 25:75 (v / v). The obtained precipitate was collected by filtration and dried under reduced pressure to obtain a white powder of a polymer of cyclodextrin derivative. GPC measurement of the obtained polymer was performed, and molecular weight was measured.

[Example 6-1]
The cyclodextrin derivatives were mono-6-deoxy-6- (2-methacryloyloxyethyl succinamide) -β-cyclodextrin) obtained in Example 1-1 and di-6-deoxy-6- (2- 3.0 g of a mixture with methacryloyloxyethyl succinamide) -β-cyclodextrin). The solvent for dissolving the cyclodextrin derivative is 11.29 g of DMF. The amount of PB-ND is 0.018 g. The DMF for dissolving PB-ND is 0.35 g. The DMF for washing with PB-ND is 0.37 g.

[Example 6-2]
The cyclodextrin derivatives were mono-6-deoxy-6- (2-methacryloyloxyethyl succinamide) -β-cyclodextrin) obtained in Example 1-1 and di-6-deoxy-6- (2- 3.0 g of a mixture with methacryloyloxyethyl succinamide) -β-cyclodextrin). The solvent for dissolving the cyclodextrin derivative is 25.57 g of DMF. The amount of PB-ND is 0.037 g. The DMF for dissolving PB-ND is 0.70 g. The DMF for co-washing with PB-ND is 0.73 g.

[Example 6-3]
The cyclodextrin derivatives were mono-6-deoxy-6- (2-methacryloyloxyethyl succinamide) -β-cyclodextrin) obtained in Example 1-1 and di-6-deoxy-6- (2- 3.0 g of a mixture with methacryloyloxyethyl succinamide) -β-cyclodextrin). The solvent for dissolving the cyclodextrin derivative is a mixed solvent of 8.29 g of DMF and 3.0 g of water. The amount of PB-ND is 0.018 g. The DMF for dissolving PB-ND is 0.35 g. The DMF for washing with PB-ND is 0.37 g.

[Example 6-4]
The cyclodextrin derivatives were mono-6-deoxy-6- (2-methacryloyloxyethyl succinamide) -β-cyclodextrin) obtained in Example 1-1 and di-6-deoxy-6- (2- 3.0 g of a mixture with methacryloyloxyethyl succinamide) -β-cyclodextrin). The solvent for dissolving the cyclodextrin derivative is a mixed solvent of 18.82 g of DMF and 6.75 g of water. The amount of PB-ND is 0.037 g. The DMF for dissolving PB-ND is 0.70 g. The DMF for co-washing with PB-ND is 0.73 g.

[Example 6-5]
The cyclodextrin derivative is 3.0 g of mono-6-deoxy-6- (2-methacryloyloxyethyl succinamide) -β-cyclodextrin) obtained in Example 2-1. The solvent for dissolving the cyclodextrin derivative is 11.29 g of DMF. The amount of PB-ND is 0.018 g. The DMF for dissolving PB-ND is 0.35 g. The DMF for washing with PB-ND is 0.37 g.

[Example 6-6]
The cyclodextrin derivative is 3.0 g of mono-6-deoxy-6- (2-methacryloyloxyethyl succinamide) -β-cyclodextrin) obtained in Example 2-1. The solvent for dissolving the cyclodextrin derivative is 25.57 g of DMF. The amount of PB-ND is 0.037 g. The DMF for dissolving PB-ND is 0.70 g. The DMF for co-washing with PB-ND is 0.73 g.

[Example 6-7]
The cyclodextrin derivative is 3.0 g of mono-6-deoxy-6- (2-methacryloyloxyethyl succinamide) -β-cyclodextrin) obtained in Example 2-1. The solvent for dissolving the cyclodextrin derivative is a mixed solvent of 8.29 g of DMF and 3.0 g of water. The amount of PB-ND is 0.018 g. The DMF for dissolving PB-ND is 0.35 g. The DMF for washing with PB-ND is 0.37 g.

[Example 6-8]
The cyclodextrin derivative is 3.0 g of mono-6-deoxy-6- (2-methacryloyloxyethyl succinamide) -β-cyclodextrin) obtained in Example 2-1. The solvent for dissolving the cyclodextrin derivative is a mixed solvent of 18.82 g of DMF and 6.75 g of water. The amount of PB-ND is 0.037 g. The DMF for dissolving PB-ND is 0.70 g. The DMF for co-washing with PB-ND is 0.73 g.

[Example 6-9]
The cyclodextrin derivative is 1.6 g of mono-6-deoxy (2-methacryloyloxyethylhexahydrophthalamide) -β-cyclodextrin obtained in Example 3-1. The solvent for dissolving the cyclodextrin derivative is 6.02 g DMF. The amount of PB-ND is 0.010 g. The DMF for dissolving PB-ND is 0.19 g. The DMF for washing with PB-ND is 0.20 g.

[Example 6-10]
The cyclodextrin derivatives were mono-6-deoxy-6- (2-methacryloyloxyethyl succinamide) -α-cyclodextrin obtained in Example 4-1, di-6-deoxy-6- (2 -Methacryloyloxyethyl succinamide) -α-cyclodextrin and tri-6-deoxy-6- (2-methacryloyloxyethyl succinamide) -α-cyclodextrin 2.0 g. The solvent for dissolving the cyclodextrin derivative is 7.52 g of DMF. The amount of PB-ND is 0.012 g. The DMF for dissolving PB-ND is 0.23 g. The DMF for washing with PB-ND is 0.24 g.

[Example 6-11]
The cyclodextrin derivative is 1.5 g of mono-6-deoxy-6- (2-methacryloyloxyethyl succinamide) -α-cyclodextrin obtained in Example 5-1. The solvent for dissolving the cyclodextrin derivative is 5.64 g of DMF. The amount of PB-ND is 0.009 g. The DMF for dissolving PB-ND is 0.17 g. The DMF for co-washing with PB-ND is 0.18 g.

[Comparative Example 6-1]
<Synthesis of cyclodextrin cross-linked polymer>
2.0 g of β-CD was dissolved in 13.5 g of DMF, and 1 drop of di-n-butyltin dilaurate was added. After nitrogen substitution, 1.2 g of 2,4tolylene diisocyanate (TDI) dissolved in 4.5 g of DMF was slowly added dropwise and reacted at 70 ° C. for 24 hours. After completion of the reaction, the reaction solution was put into 100 mL of chloroform and stirred overnight. The precipitate was collected by filtration, and the cyclodextrin crosslinked polymer was obtained by reducing the pressure at 60 ° C.

[Composition result]
Table 1 shows the cyclodextrin derivative polymer according to Examples 6-1 to 6-11 and the cyclodextrin crosslinked polymer of Comparative Example 6-1. And the number average molecular weight Mn of the cyclodextrin crosslinked polymer.

[Example 7]
<Phenol removal experiment using polymer of cyclodextrin derivative>
A white powder of a polymer of cyclodextrin derivative, 5.9 mg of phenol (manufactured by Wako Pure Chemical Industries, Ltd.), and ion-exchanged water are weighed in a sample tube, uniformly mixed and dissolved, and then stirred overnight with a waveblower. did. By stirring overnight, a white precipitate of a polymer of a cyclodextrin derivative encapsulating phenol was obtained. The obtained white precipitate was removed with a 0.2 μm cellulose acetate filter (manufactured by ADVANTEC), and the obtained filtrate was subjected to HPLC measurement to calculate phenol in the filtrate.

[Example 7-1]
The polymer of the cyclodextrin derivative is 0.17 g of the polymer obtained in Example 6-1. The amount of ion-exchanged water charged is 1.83 g.

[Example 7-2]
The polymer of the cyclodextrin derivative is 0.17 g of the polymer obtained in Example 6-2. The amount of ion-exchanged water charged is 1.83 g.

[Example 7-3]
The polymer of the cyclodextrin derivative is 0.17 g of the polymer obtained in Example 6-3. The amount of ion-exchanged water charged is 1.83 g.

[Example 7-4]
The polymer of the cyclodextrin derivative is 0.17 g of the polymer obtained in Example 6-4. The amount of ion-exchanged water charged is 1.83 g.

[Example 7-5]
The polymer of the cyclodextrin derivative is 0.17 g of the polymer obtained in Example 6-5. The amount of ion-exchanged water charged is 1.83 g.

[Example 7-6]
The polymer of the cyclodextrin derivative is 0.17 g of the polymer obtained in Example 6-6. The amount of ion-exchanged water charged is 1.83 g.

[Example 7-7]
The polymer of the cyclodextrin derivative is 0.17 g of the polymer obtained in Example 6-7. The amount of ion-exchanged water charged is 1.83 g.

[Example 7-8]
The polymer of the cyclodextrin derivative is 0.17 g of the polymer obtained in Example 6-8. The amount of ion-exchanged water charged is 1.83 g.

[Example 7-9]
The polymer of the cyclodextrin derivative is 0.18 g of the polymer obtained in Example 6-9. The amount of ion-exchanged water charged is 1.82 g.

[Example 7-10]
The polymer of the cyclodextrin derivative is 0.15 g of the polymer obtained in Example 6-10. The amount of ion-exchanged water charged is 1.85 g.

[Example 7-11]
The polymer of the cyclodextrin derivative is 0.15 g of the polymer obtained in Example 6-11. The amount of ion-exchanged water charged is 1.85 g.

[Comparative Example 7-1]
Instead of the polymer of the cyclodextrin derivative, 0.23 g of the cyclodextrin crosslinked polymer obtained in Comparative Example 6-1 was used. The amount of ion-exchanged water charged is 1.77 g.

[Comparative Example 7-2]
Instead of the cyclodextrin derivative polymer, β-CD 0.14 g represented by the formula (7) was used. The amount of ion-exchanged water charged is 1.86 g.

[Experimental result]
Table 2 shows the polymer of the cyclodextrin derivative used for the phenol removal experiments according to Examples 7-1 to 7-11 and Comparative Examples 7-1 and 7-2, the amounts of phenol and water charged, and after stirring. This shows the state of the solution and the phenol removal rate.

[Example 8]
<Removal experiment of cresol by polymer of cyclodextrin derivative>
A white powder of a polymer of a cyclodextrin derivative, 6.8 mg of cresol (manufactured by Wako Pure Chemical Industries, Ltd.) and ion-exchanged water are weighed into a sample tube, uniformly mixed and dissolved, and then stirred overnight with a waveblower. did. By stirring overnight, a white precipitate of a polymer of cyclodextrin derivatives enclosing cresol was obtained. The obtained white precipitate was removed with a 0.2 μm cellulose acetate filter, and the obtained filtrate was subjected to HPLC measurement to calculate cresol in the filtrate.

[Example 8-1]
The polymer of the cyclodextrin derivative is 0.17 g of the polymer obtained in Example 6-1. The amount of ion-exchanged water charged is 1.83 g.

[Example 8-2]
The polymer of the cyclodextrin derivative is 0.17 g of the polymer obtained in Example 6-2. The amount of ion-exchanged water charged is 1.83 g.

[Example 8-3]
The polymer of the cyclodextrin derivative is 0.17 g of the polymer obtained in Example 6-3. The amount of ion-exchanged water charged is 1.83 g.

[Example 8-4]
The polymer of the cyclodextrin derivative is 0.17 g of the polymer obtained in Example 6-4. The amount of ion-exchanged water charged is 1.83 g.

[Example 8-5]
The polymer of the cyclodextrin derivative is 0.17 g of the polymer obtained in Example 6-5. The amount of ion-exchanged water charged is 1.83 g.

[Example 8-6]
The polymer of the cyclodextrin derivative is 0.17 g of the polymer obtained in Example 6-6. The amount of ion-exchanged water charged is 1.83 g.

[Example 8-7]
The polymer of the cyclodextrin derivative is 0.17 g of the polymer obtained in Example 6-7. The amount of ion-exchanged water charged is 1.83 g.

[Example 8-8]
The polymer of the cyclodextrin derivative is 0.17 g of the polymer obtained in Example 6-8. The amount of ion-exchanged water charged is 1.83 g.

[Example 8-9]
The polymer of the cyclodextrin derivative is 0.18 g of the polymer obtained in Example 6-9. The amount of ion-exchanged water charged is 1.82 g.

[Example 8-10]
The polymer of the cyclodextrin derivative is 0.15 g of the polymer obtained in Example 6-10. The amount of ion-exchanged water charged is 1.85 g.

[Example 8-11]
The polymer of the cyclodextrin derivative is 0.15 g of the polymer obtained in Example 6-11. The amount of ion-exchanged water charged is 1.85 g.

[Comparative Example 8-1]
Instead of the polymer of the cyclodextrin derivative, 0.23 g of the cyclodextrin crosslinked polymer obtained in Comparative Example 6-1 was used. The amount of ion-exchanged water charged is 1.77 g.

[Comparative Example 8-2]
Instead of the cyclodextrin derivative polymer, β-CD 0.14 g represented by the formula (7) was used. The amount of ion-exchanged water charged is 1.86 g.

[Experimental result]
Table 3 shows the polymer of the cyclodextrin derivative used for the experiments for removing cresol according to Examples 8-1 to 8-11 and Comparative Examples 8-1 and 8-2, the charged amounts of cresol and water, and after stirring. The state of the solution and the removal rate of cresol are shown.

  From Tables 2 and 3, in Examples 7-1 to 7-11 and 8-1 to 8-11, by using the polymer of cyclodextrin derivatives according to Examples 6-1 to 6-11, An inclusion compound was formed by incorporating phenol or cresol (hereinafter referred to as a phenol compound) in the molecule or between the molecules, and white turbidity due to precipitates was observed after stirring. From the HPLC measurement, the phenol removal rate was 67% to 98%, and the cresol removal rate was 61% to 97%, indicating that the phenolic compound in the aqueous solution was efficiently removed. Furthermore, it was found that the higher the number average molecular weight Mn of the polymer of cyclodextrin derivatives, the higher the inclusion ability of the phenol compound and the higher the removal rate. On the other hand, Comparative Examples 7-1 and 8-1 are polymers cross-linked with high density by TDI, are difficult to include phenol compounds, and the removal rate is 54% to 56%. Comparative Example 7-2, In 8-2, since β-CD, which is not a polymer, was used, no precipitate was formed even when the inclusion compound was formed, and the phenol compound removal rate was 0%.

  The embodiment of the present invention has been described above, but the present invention is not limited to the above-described embodiment, and it is needless to say that various modifications can be made without departing from the gist of the present invention.

Claims (5)

A cyclodextrin derivative represented by the formula (1).

... (1)
(In formula (1), x is an integer of 1 to 3, k is an integer of 6 to 8, R ¹ is a hydrogen atom or a methyl group, R ² is a hydrocarbon group having 1 to 4 carbon atoms, and R ³ is carbon. (A hydrocarbon group having 1 to 6 atoms is shown.) The cyclodextrin derivative according to claim 1,
A cyclodextrin derivative represented by the formula (2).

... (2)
(In the formula (2), y is an integer of 5 to 7, R ¹ is a hydrogen atom or a methyl group, R ² is a hydrocarbon group having 1 to 4 carbon atoms, and R ³ is a hydrocarbon having 1 to 6 carbon atoms. Group.) The manufacturing method of a cyclodextrin derivative which produces | generates the cyclodextrin derivative of Claim 1 or 2 by amidating the compound represented by Formula (3) and the compound represented by Formula (4).

... (3)
(In formula (3), x represents an integer of 1 to 3, and k represents an integer of 6 to 8.)

... (4)
(In Formula (4), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrocarbon group having 1 to 4 carbon atoms, and R ³ represents a hydrocarbon group having 1 to 6 carbon atoms.) A method for producing a cyclodextrin derivative according to claim 3,
(A) a step of producing a compound represented by the formula (6) by benzylamination of the compound represented by the formula (5) using benzylamine;
And (B) step of producing a compound represented by the formula (3) by reducing the compound represented by the formula (6) obtained in the step (A). .

... (5)
(In formula (5), x represents an integer of 1 to 3, and k represents an integer of 6 to 8.)

... (6)
(In formula (6), x represents an integer of 1 to 3, and k represents an integer of 6 to 8.) A polymer of a cyclodextrin derivative obtained by polymerizing the cyclodextrin derivative according to claim 1 or 2.