JP2006083379A - Globular cyclodextrin polymer, method for producing the same, and adsorbent containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a globular cyclodextrin polymer easily handled, endurable to be continuously operated in a column, and industrially usable, and to provide the globular cyclodextrin polymer obtained by the method, and to provide an adsorbent containing the same. <P>SOLUTION: This method for producing the globular cyclodextrin polymer includes a process for mixing (1) a cyclodextrin polymer obtained by reacting cyclodextrin with a diisocyanate compound with (2) an aqueous solution of a polysaccharide carboxylic acid salt and a process for dropping (3) a mixed liquid obtained by the mixing process into an aqueous solution of an alkaline earth metal halide salt. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a spherical cyclodextrin polymer, a spherical cyclodextrin polymer obtained by the production method, and an adsorbent containing the same, and more particularly, a phenol compound that adversely affects the environment from a phenol compound-containing solution efficiently. The present invention relates to a spherical cyclodextrin polymer which can be removed, a process for producing the polymer, and an adsorbent containing the polymer.

The release of environmental pollutants discharged from manufacturing processes into rivers, seas, and the atmosphere is strictly regulated by the government, and it is obliged to perform detoxification treatment before discharge. For example, a phenol resin obtained by reacting phenols with formaldehydes is produced by an addition condensation reaction to produce condensed water. When this condensed water or the like is removed under high-temperature vacuum, unreacted phenols azeotrope and waste liquid containing phenols is generated. These waste liquids contain several to several tens of percent of phenols, and discarding them as they are is extremely problematic from the influence on the environment and also increases the production cost of phenol resins.
For this reason, recovery of a phenol compound from these waste liquids is an extremely important issue in the production of phenol resins.
As a method for solving such problems, a method using a cyclodextrin polymer has been proposed (see, for example, Non-Patent Document 1).
Specifically, a cyclodextrin polymer cross-linked with β-cyclodextrin and epicurhydrin is disclosed (for example, see Non-Patent Document 2). And using this cyclodextrin polymer, the adsorption effect of phenol is measured from a phenol aqueous solution. However, a cyclodextrin polymer obtained by crosslinking β-cyclodextrin with epicurhydrin has a small adsorption amount and insufficient removal efficiency.
Further, a cyclodextrin polymer composed of cyclodextrin and polyisocyanate is disclosed (for example, see Patent Document 1). And the adsorption effect of nitrophenol is examined using this polymer.
However, when a phenol compound is adsorbed by a stationary phase column system using the cyclodextrin polymer obtained in these documents as an adsorption carrier, the cyclodextrin polymer seems to be indefinite shape, but the carrier expands in an irregular shape, Has been pointed out as a problem.
As a solution to this, a method of grinding the cyclodextrin polymer to obtain a uniform particle size and shape is assumed. However, by making the cyclodextrin polymer spherical during the manufacturing process, the packing property of the column can be improved and efficient. It is expected that continuous stationary phase column operation will be possible.
However, there is no known method for producing a spherical cyclodextrin polymer in the production process.

PETROTEC, 26, 21 (2003) Angew. Makromol. Chem. , 119, 207 (1992) JP-T-2001-504879

  An object of the present invention is to provide an industrially usable method for producing a spherical cyclodextrin polymer that is easy to handle and can withstand continuous column operation, a spherical cyclodextrin polymer obtained by the production method, and an adsorbent containing the polymer. That is.

The subject of the present invention is
(1) A cyclodextrin polymer obtained by reacting a cyclodextrin with a diisocyanate compound,
(2) mixing with a polysaccharide carboxylate aqueous solution;
(3) dropping the mixed solution obtained in the step into an alkaline earth metal halide salt solution;
It solves by the manufacturing method of the spherical cyclodextrin polymer characterized by including this.
Or
The problem can also be solved by a method for producing a spherical cyclodextrin polymer, which comprises reacting at least a diisocyanate compound with the spherical cyclodextrin polymer (A) obtained by the above production method.

  If the production method of the present invention is carried out, a spherical cyclodextrin polymer can be obtained directly, which is easy to handle and enables speedy column separation.

The cyclodextrin (hereinafter sometimes abbreviated as CD) used in the present invention shows a huge cavity structure and usually contains 6 or more glucoses obtained from starch by the action of cyclodextrin gluconotransferase (abbreviated as CDTase). A cyclic oligosaccharide consisting of Specifically, α-cyclodextrin having 6 glucose units as shown in FIG. 1 (hereinafter sometimes abbreviated as α-CD), 7 β-cyclodextrin (hereinafter abbreviated as β-CD). 8) γ-cyclodextrin (hereinafter sometimes abbreviated as γ-CD), and preferably β-cyclodextrin.
These cyclodextrins may be used alone or in combination.

  Furthermore, the cyclodextrin may be modified by addition of other functional groups. Examples include cyclodextrins substituted by lower alkyl such as C1-C4 groups, long-chain aliphatics containing C8-C20 carbon, hydroxyalkyl groups, sulfone groups or alkylsulfone groups.

  The diisocyanate used in the present invention is generally well-known aromatic, aliphatic and cycloaliphatic diisocyanates and high-functional or high-molecular diisocyanates, preferably aromatic diisocyanates and aliphatic diisocyanates, more preferably Is an aliphatic diisocyanate. Specifically, 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene Diisocyanate, 1,4-phenylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2, 4,4-trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane , 4'-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate and derivatives thereof. Preferably, 2,4-tolylene diisocyanate (hereinafter sometimes abbreviated as TDI), 4,4-diphenylmethane diisocyanate (hereinafter sometimes abbreviated as MDI), hexamethylene diisocyanate (hereinafter abbreviated as HDI). Sometimes). More preferred is hexamethylene diisocyanate.

  The range of use of the cyclodextrin and diisocyanate compound of the present invention is not particularly limited, but is preferably 1 to 24 mol of diisocyanate with respect to 1 mol of CD. More preferably, the diisocyanate is 2 to 16 moles, more preferably 6 to 12 moles, and most preferably 8 to 10 moles relative to 1 mole of CD. If the amount of diisocyanate used is too small, the yield of cyclodextrin polymer will be low.

There are no particular limitations on the reaction conditions between the cyclodextrin and the diisocyanate compound, and the reaction is carried out within the usual range. Specifically, it is about 0.5 to 24 hours in a temperature range of 30 to 150 ° C., preferably 50 to 100 ° C. The reaction can also be performed in a solvent.
There is no problem as long as the solvent used is an organic solvent that does not affect the reaction. Preferred solvents include dialkylformamides such as dimethylformamide and diethylformamide, dialkyl sulfoxides such as dimethyl sulfoxide and diethyl sulfoxide, aliphatic nitriles and aromatic nitriles such as acetonitrile and benzonitrile, pyridine and n-butylamine, and the like. Aromatic and aliphatic amines, aliphatic ethers such as dimethyl ether and diethyl ether, cyclic ethers such as dioxane, and aromatic hydrocarbons such as benzene, toluene and xylene. Preferably, dialkyl formaldehydes and dialkyl sulfoxides are mentioned in consideration of stability and solubility.
Further, if necessary, transition metal compound catalysts such as titanium tetrabutoxide, dibutyltin oxide, dibutyltin dilaurate, tin 2-ethylcaproate, zinc naphthenate, cobalt naphthenate, zinc 2-ethylcaproate, molybdenum glycolate, Iron chloride, zinc chloride and the like, and amine catalysts such as triethylamine, tributylamine, triethylenediamine and benzyldibutylamine may be added. Usually, the reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon, but there is no problem as long as moisture is not mixed in such as a dry air atmosphere or a sealed condition.

The obtained cyclodextrin polymer is obtained as a liquid or a solid, but when it is obtained as a solid, it is preferably used after being finely pulverized. The particle size obtained by pulverization is preferably 0.1 mm or less, and more preferably 0.08 mm or less.
In the liquid cyclodextrin polymer, it is usually used as it is.

Although there is no restriction | limiting in particular about the method for making the obtained cyclodextrin polymer spherical, The method of using the polysaccharide carboxylate aqueous solution is preferable.
Polysaccharide carboxylic acid refers to a group of compounds having at least one carboxyl group in a part of the polysaccharide, and the compound group has a carboxyl group even if it is obtained by extraction or purification from a natural product. There is no problem even if it is a compound group in which a non-polysaccharide has a carboxyl group synthetically.
Examples of substances extracted from natural products include alginic acid and pectinic acid. Examples of the artificially synthesized polysaccharide carboxylic acid include cellulose glycolic acid obtained by reacting chloroacetate with alkali cellulose.
Examples of the polysaccharide used as a raw material when synthesized include the above cellulose, starch, glycogen, dextrin, inulin, mannan, chitin and the like.
Examples of the salt that can be used here include an alkali metal salt, an alkaline earth metal salt (excluding calcium), and a transition metal salt, and an alkali metal salt is preferable. Specifically, sodium and potassium.
Alternatively, the cyclodextrin polymer-containing solution can be dripped into an insoluble solvent in a cocoon state to form a sphere. Specifically, the method of dripping in solvents, such as a chloroform solution, paraffin, and oil, is also mentioned.
Furthermore, a method in which a cyclodextrin polymer-containing solution mixed with agar is dropped into soybean oil or the like and spheroidized is also included.

Hereinafter, the manufacturing method of the spherical cyclodextrin polymer using polysaccharide carboxylate aqueous solution is demonstrated. The polysaccharide carboxylic acid is a group of compounds having at least a carboxyl group in the above-mentioned polysaccharide, but it is preferable to use alginic acid, pectinic acid and cellulose glycolic acid in view of availability.
These polysaccharide carboxylic acids may be used alone or in combination of two or more.
There is no particular limitation on the mixing method (mixing step) of the polysaccharide carboxylate aqueous solution and the cyclodextrin polymer. The cyclodextrin polymer may be added to the polysaccharide carboxylate aqueous solution, or the polysaccharide carboxylate aqueous solution may be poured into the cyclodextrin polymer or mixed at the same time without any problem.
The concentration of the polysaccharide carboxylate aqueous solution to be used is not particularly limited, but preferably 0.1 to 10 wt% aqueous solution, more preferably 0.5 to 5 wt% aqueous solution, considering the viscosity in the mixed state. A 0.8 to 3 wt% aqueous solution is preferred.
There is no particular problem with the mixing ratio of the cyclodextrin polymer and the polysaccharide carboxylate aqueous solution, but the ratio is 30% by weight to 30:30 from the viscosity of the mixed liquid and the shape of the obtained cyclodextrin polymer. (Wt / wt%) is preferred. More preferably, it is 40: 60-60: 40 (wt / wt%), More preferably, it is 45: 55-55: 45 (wt / wt%).
The mixing conditions are not particularly limited, and are usually performed at normal temperature and normal pressure.

A spherical cyclodextrin polymer can be obtained through a step of dropping the obtained mixed solution into an alkaline earth metal halide salt solution. Preferred alkaline earth metal halide salts include calcium chloride and magnesium chloride. Although there is no restriction | limiting in particular about the density | concentration of halogenated alkaline-earth metal salt aqueous solution, The 1-10 wt% density | concentration is preferable when the time etc. when the dripped liquid mixture is shape | molded spherically are considered. More preferably, it is 2-5 wt%.
There is no restriction | limiting in particular also about the dripping method, For example, a liquid mixture should just be dripped drop by drop through a tube. In addition, it is clear that the spherical diameter of the obtained spherical cyclodextrin polymer varies depending on the inner diameter of the tube. Various devices or tools are conceivable for the jig for making a sphere, but in short, there is no problem as long as it has at least one hole through which the mixed liquid can be dropped drop by drop.
There is no problem with the dropping conditions, and it may be carried out at ordinary temperature and pressure.

Furthermore, a spherical cyclodextrin polymer can also be obtained by reacting the spherical cyclodextrin polymer obtained by the above method with at least a diisocyanate compound.
Here, the spherical cyclodextrin polymer obtained by the above method is referred to as (A) and referred to as a primary crosslinked spherical cyclodextrin polymer. A spherical cyclodextrin polymer obtained by reacting (A) with at least a diisocyanate compound is referred to as (B) and is referred to as a secondary crosslinked spherical cyclodextrin polymer.

In the method for producing a secondary crosslinked spherical cyclodextrin polymer, the diisocyanate compound described above can be used as it is. A preferred diisocyanate compound is hexamethylene diisocyanate.
Reaction conditions can also be implemented according to the manufacturing method of the above-mentioned cyclodextrin polymer.
In addition, about the usage-amount of a primary crosslinked spherical cyclodextrin polymer and diisocyanate, 1-10 weight part of diisocyanate is preferable with respect to 1 weight part of primary crosslinked spherical cyclodextrin polymer. Exceeding this range may adversely affect the physical properties of the spherical cyclodextrin polymer, such as compressive strength that can be reused for column separation, porosity showing high material permeability, and specific surface area that leads to excellent inclusion ability. .

Next, in the production method of the secondary crosslinked spherical cyclodextrin polymer (B) to be reacted with at least the diisocyanate compound, a polyether polyol compound may be added.
The polyether polyol compound is a group of aliphatic polyhydric alcohol compounds having at least two hydroxyl groups in the molecule, and specifically includes ethylene glycol, propylene glycol, 1,4-butanediol, 1,6- Preferable examples include aliphatic diols having 2 to 12 straight-chain or branched hydroxyl groups such as hexanediol and 1,12-dodecanediol.
Furthermore, polyether polyols obtained by condensation reaction from these polyhydric alcohols are also preferred. Specific examples include polycondensation products such as polyethylene glycol, polypropylene glycol, 1,4-butanediol, 1,6-hexanediol, and 1,12-dodecanediol.
A more preferred polyether polyol compound is polypropylene glycol.

The addition amount of the polyether polyol compound is not particularly limited, but is preferably 0.01 to 1 part by weight with respect to 1 part by weight of the primary crosslinked spherical cyclodextrin polymer. More preferably, it is 0.1-0.8 weight part, More preferably, it is 0.2-0.6 weight part.
Although there is no restriction | limiting in particular also about the usage-amount of the diisocyanate compound to add and the polyether polyol compound to add, 0.001 to 100% (wt / wt%) is preferable. More preferably, it is 0.05-80% (wt / wt%), More preferably, it is 2-60% (wt / wt%), Most preferably, it is 3-50% (wt / wt%).

  The method for adding the polyether polyol compound is not particularly limited. However, there is a method in which the polyether polyol compound is allowed to coexist in a system containing a mono-crosslinked spherical cyclodextrin (A) and then reacted with the diisocyanate compound. preferable. There is no problem with the above-mentioned three methods, that is, a method in which a mono-crosslinked spherical cyclodextrin (A), a polyether polyol compound and a diisocyanate compound are simultaneously mixed and brought into contact with each other.

  The reaction conditions are the same as those for the cyclodextrin and diisocyanate compound described above.

The compound to be adsorbed and separated using the spherical cyclodextrin polymer obtained in the present invention is an organic pollutant or a contaminant thereof.
Specific organic pollutants or contaminants include aromatic compounds such as polycyclic aromatic compounds and phenolic compounds including condensed ring structure compounds containing about 2 to 10 rings such as benzene, toluene and xylene. It is done. A phenol compound is preferred.

  The phenol compound that is preferably the target of adsorption / separation removal is a compound represented by the general formula (1).

Preferably R1 is hydrogen or methyl.
Specific examples include phenol, cresol, ethylphenol, isopropylphenol, tert-butylphenol, sec-butylphenol, allylphenol, and xylenol. These phenol compounds can be used alone or in combination.
Preferable are phenol, cresol, and xylenol, and more preferable is phenol.

The solution containing these phenol compounds is usually in the form of an aqueous solution, and the concentration of the solution containing the phenol compound (generally an aqueous solution) is not particularly limited, but the content of the phenol compound is 0.01. % By weight to 50% by weight is preferred. More preferably, it is 0.1-30 weight%, More preferably, it is 1-20 weight%.
If the phenol concentration is too low, the removal efficiency may decrease.
If the concentration is too high, the removal operability may be hindered.
Specific examples of the phenol compound-containing solution include phenol-containing waste liquid discharged from the phenol resin production process.

  The method of bringing the phenol compound-containing solution into contact with the spherical cyclodextrin polymer is not particularly limited, but a column chromatography type is usually simple and preferable. Specifically, a method in which a column is filled with a spherical cyclodextrin polymer and a phenol compound-containing solution is continuously passed is exemplified. Alternatively, a method in which a certain amount of a spherical cyclodextrin polymer is charged in a reaction vessel, a phenol compound-containing solution is further added, and the mixture is stirred for a certain time to take in and remove the phenol compound.

  The conditions for contacting are not particularly limited, and are usually carried out at normal temperature and normal pressure.

  Since the spherical cyclodextrin polymer used for the removal of the phenolic compound removes the phenolic compound due to the inclusion effect, the inclusion of the phenolic compound with an appropriate extractant or solvent can be released and separated. Suitable extractants or solvents can include alcohols such as methanol and ethanol.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples.
The present invention is not limited to these examples.
(Measurement method of physical properties)
Regarding the physical properties of the obtained cyclodextrin polymer, the following measuring apparatus was used.
・ Compressive strength: Desktop material testing machine RTC-1150A manufactured by Orientec
-Porosity: Yuasa Ionics' fully automatic pore distribution measuring device NOVA-1200
Specific surface area: Quanta Chrome Co. Made
High-speed specific surface area / pore diameter distribution measuring device PoreMaster60-GT
・ Diameter: Digimatic micrometer manufactured by Mitutomo ・ Liquid prepolymer molecular weight measurement: manufactured by PerSeptive Biosystems
Flight mass spectrometer Yoyager ^TM DEPRO Y
-Surface observation: Digital HF microscope VH-8000 manufactured by Keyence Corporation
-Cross-sectional observation: Hitachi, Ltd. scanning electron microscope (SEM) S-4300
-CHN elemental analysis: JC Science Lab Microcoder JM10 type

Reference example 1
(Synthesis of fine solid cyclodextrin polymer)
10 drops of di-n-butyltin dilaurate (sometimes abbreviated as BLT) for 20.0 g of β-cyclodextrin (abbreviated as β-CD) in a 500 ml flask equipped with a reflux condenser and dropping funnel Then, 150 ml of purified dimethylformamide (abbreviated as DMF) and a football type stirrer were added and dissolved uniformly with stirring. After sufficient nitrogen substitution in the flask, 50 ml of a DMF solution containing 23.7 g of a cross-linking agent hexamethylene diisocyanate (abbreviated as HDI) was slowly added dropwise and stirred at 70 ° C. for 24 hours. The molar ratio of β-cyclodextrin and hexamethylene diisocyanate used at this time was 1: 8. As the reaction proceeded, a white polymer precipitated. The reaction solution was poured into chloroform and stirred overnight to remove DMF, catalyst and unreacted crosslinking agent.
The residue was filtered with suction, and then poured into water and stirred for several hours to remove unreacted CD. The residue after solvent extraction was subjected to suction filtration and then vacuum dried at 60 ° C. to obtain a purified cyclodextrin polymer. The purified cyclodextrin polymer was pulverized by a ball mill and used with a particle size of 0.075 mm or less.
From the result of CHN elemental analysis of the purified cyclodextrin polymer, the ratio of β-cyclodextrin and diisocyanate was 1: 9.2 molar ratio.

Reference example 2
(Synthesis of liquid cyclodextrin polymer)
A 300 ml flask equipped with a reflux condenser and a dropping funnel is charged with 1.76 mmol of β-cyclodextrin (β-CD), 1 drop of di-n-butyltin dilaurate (sometimes abbreviated as BLT), and purified dimethyl 15 ml of formamide (abbreviated as DMF) and a football-type stirrer were added and dissolved while stirring. After sufficiently replacing the nitrogen in the flask, 5 ml of a DMF solution containing 3.52 mmol of the cross-linking agent hexamethylene diisocyanate was slowly added dropwise and stirred at 70 ° C. for 24 hours. The molar ratio of β-cyclodextrin and hexamethylene diisocyanate used at this time was 1: 2. As the reaction proceeded, a prepolymer suspension was obtained. The reaction solution was poured into chloroform and stirred overnight to remove DMF, catalyst and unreacted crosslinking agent. The obtained prepolymer is obtained as a highly viscous liquid, the number average molecular weight (Mn) is about 11200, the weight average molecular weight (Mw) is about 15200, and the molecular weight distribution (Mn / Mw) is 1.36. As a result of mass spectrometry, it was found that the degree of polymerization was about 9.6.

Example 1
(Synthesis of primary cross-linked spherical cyclodextrin polymer)
Liquid cyclodextrin polymer obtained in Reference Example 2: 1 wt% sodium alginate 50:50 (wt / wt%) mixed liquid was prepared, and it was put into a syringe and dropped onto a 3 wt% calcium chloride solution, followed by filtration. Separated and freeze-dried or vacuum dried at 60 ° C. to synthesize a primary crosslinked spherical cyclodextrin polymer.

Example 2
(Synthesis of primary cross-linked spherical cyclodextrin polymer)
A liquid cyclodextrin polymer obtained in Reference Example 2: 1 wt% sodium alginate 60:40 (wt / wt%) mixed liquid was prepared, filled in a syringe, dropped onto a 3 wt% calcium chloride solution, and filtered. Separated and freeze-dried or vacuum dried at 60 ° C. to synthesize a primary crosslinked spherical cyclodextrin polymer.

Example 3
(Synthesis of primary cross-linked spherical cyclodextrin polymer)
4 g of a mixed liquid of fine particulate solid cyclodextrin polymer obtained in Reference Example 1: 1 wt% sodium alginate 50:50 (wt / wt%) is prepared, and 1.6 ml of water is added to prepare a paste sample. The mixture was filled in a syringe, dropped onto a 3 wt% calcium chloride solution, filtered and separated, and freeze-dried or vacuum dried at 60 ° C. to synthesize a primary crosslinked spherical cyclodextrin polymer. The compression strength of the obtained primary crosslinked spherical cyclodextrin polymer was measured and found to be 0.16 Mpa.

Example 4
(Synthesis of secondary cross-linked spherical cyclodextrin polymer)
1 g of the primary crosslinked spherical cyclodextrin polymer obtained in Example 2 and 1.48 g of hexamethylene diisocyanate were added to dehydrated benzene, 1 drop of di-n-butyltin dilaurate was added, and the mixture was reacted at 80 ° C. for 24 hours. It was. After the reaction, the mixture was filtered, washed with chloroform and methanol, and vacuum dried at 60 ° C. to obtain a secondary crosslinked spherical cyclodextrin polymer.
FIG. 2 shows an optical micrograph of the secondary crosslinked spherical cyclodextrin polymer obtained.
The compression strength of the obtained secondary crosslinked spherical cyclodextrin polymer was measured and found to be 0.98 Mpa.

Example 5
(Synthesis of secondary cross-linked spherical cyclodextrin polymer)
1 g of the primary crosslinked spherical cyclodextrin polymer obtained in Example 3 and 1.48 g of hexamethylene diisocyanate were added to dehydrated benzene, and 1 drop of di-n-butyltin dilaurate was added and reacted at 80 ° C. for 24 hours. It was. After the reaction, the mixture was filtered, washed with chloroform and methanol, and vacuum dried at 60 ° C. to obtain a secondary crosslinked spherical cyclodextrin polymer. The spherical dextrin polymer had physical properties of a compression strength of 1.80 MPa, a porosity of 47%, a specific surface area of 3.48 m ² / g, and a diameter of 2.7 to 4.0 mm.
FIG. 3 shows an optical micrograph of this polymer, and FIG. 4 shows an SEM photograph of the fracture surface.
Furthermore, when this secondary crosslinked spherical cyclodextrin polymer was subjected to CHN elemental analysis, the ratio of β-cyclodextrin to diisocyanate was 1: 10.4 molar ratio.

Example 6
(Synthesis of secondary cross-linked spherical cyclodextrin polymer containing PPG)
In a 300 ml Erlenmeyer flask, 1 g of the primary crosslinked spherical cyclodextrin polymer obtained in Example 3 was added with 0.7 g of benzene and 0.1 g of polypropylene glycol (abbreviated as PPG) and triethylenediamine (abbreviated as TEDA). 2) impregnated with 2 mg of solution. To this mixture was added 1.48 g of hexamethylene diisocyanate (abbreviated as HDI) and about 100 ml of dehydrated benzene solution containing 1 enemy of tin 2-ethylhexanoate (abbreviated as OLT), followed by refluxing for 24 hours for secondary crosslinking. It used for reaction. After the reaction, the mixture was filtered, washed with chloroform and methanol, and vacuum dried at 60 ° C. to obtain a secondary crosslinked spherical cyclodextrin polymer containing PPG.

Example 7
(Synthesis of secondary cross-linked spherical cyclodextrin polymer containing PPG)
A secondary cross-linked spherical cyclodextrin polymer containing PPG was obtained according to Example 5 except that 0.3 g of PPG was added.

Example 8
(Synthesis of secondary cross-linked spherical cyclodextrin polymer containing PPG)
A secondary cross-linked spherical cyclodextrin polymer containing PPG was obtained according to Example 5 except that 0.5 g of PPG was added.

Example 9
(Synthesis of primary cross-linked spherical cyclodextrin polymer)
A mixture of 0.5 g of the finely divided solid cyclodextrin polymer obtained in Reference Example 1 and 0.5 g of a mixed aqueous solution of 1 wt% sodium alginate and sodium aspartate (1: 1 weight ratio) was prepared, and the mixture was placed in a syringe. Then, the solution was dropped onto a 3 wt% calcium chloride solution, filtered and separated, and freeze-dried or vacuum dried at 60 ° C. to synthesize a primary crosslinked spherical cyclodextrin polymer. The shape was not a perfect sphere, but a product according to Example 3 was obtained.

Example 10
(Synthesis of primary cross-linked spherical cyclodextrin polymer)
4 g of a mixture of fine-particle solid cyclodextrin polymer obtained in Reference Example 1: 2 wt% sodium cellulose glycolate 50:50 (wt / wt%) is prepared, and 1.6 ml of water is added to prepare a paste sample. The mixture was filled in a syringe and dropped onto a 3 wt% calcium chloride solution, followed by filtration and separation, and freeze-drying or vacuum drying at 60 ° C. to synthesize a primary crosslinked spherical cyclodextrin polymer. The same primary crosslinked spherical cyclodextrin polymer as in Example 3 was obtained.

Reference example 3
(Synthesis of primary cross-linked spherical cyclodextrin polymer by iota carrageenan method)
A 1 wt% iota carrageenan aqueous solution was prepared, 0.25 g of the aqueous solution and 1.0 g of the fine solid cyclodextrin polymer obtained in Reference Example 1 were mixed, and dropped into a 3 wt% calcium chloride aqueous solution from a syringe. Filtration, separation, and lyophilization were performed to synthesize a primary crosslinked spherical cyclodextrin polymer.
The shape did not go completely spherical, but a bowl shape was obtained.

Reference example 4
(Synthesis of primary cross-linked spherical cyclodextrin polymer by agar method)
A 1.5 wt% agar aqueous solution was prepared, 1.0 g of the aqueous solution and 0.4 g of the fine solid cyclodextrin polymer obtained in Reference Example 1 were mixed, dropped from a syringe into liquid paraffin, and refrigerated. After isolation, washing with hexane and lyophilization, a spherical cyclodextrin polymer was synthesized.
The shape did not go completely spherical, but a bowl shape was obtained.

Example 11
(Phenol compound removal test)
1.0 g of the primary crosslinked spherical cyclodextrin polymer obtained in Example 3 was added to a 50 ml Erlenmeyer flask and heated to 60 ° C. to obtain a homogeneous aqueous solution (phenol 8.9% by weight, cresol 0.33). (5% by weight and 0.044% by weight of xylenol) were added, and the mixture was stirred at room temperature for 2 hours. Thereafter, the cyclodextrin polymer was subjected to suction filtration, the filtrate was measured by gas chromatography, and the phenolic compound in the filtrate was measured. As a result, 83.1% of the charged phenol was removed.

Example 12
(Phenol compound removal test)
1.0 g of the secondary crosslinked spherical cyclodextrin polymer obtained in Example 5 was added to a 50 ml Erlenmeyer flask and heated to 60 ° C. to obtain a homogeneous solution (phenol 8.9% by weight, cresol 0.8%). 5 ml) (containing 33 wt% and xylenol 0.044 wt%) was added and stirred at room temperature for 2 hours. Thereafter, the cyclodextrin polymer was subjected to suction filtration, the filtrate was measured by gas chromatography, and the phenolic compound in the filtrate was measured. As a result, 89.0% of the charged phenol was removed.

Example 13
(Phenol compound removal test)
1.0 g of the secondary crosslinked spherical cyclodextrin polymer obtained in Example 4 was added to a 50 ml Erlenmeyer flask and heated to 60 ° C. to obtain a homogeneous aqueous solution (phenol 8.9% by weight, cresol 0.8%). 5 ml) (containing 33 wt% and xylenol 0.044 wt%) was added and stirred at room temperature for 2 hours. Thereafter, the cyclodextrin polymer was subjected to suction filtration, the filtrate was measured by gas chromatography, and the phenolic compound in the filtrate was measured. As a result, 68.5% of the charged phenol was removed.

Example 14
(Phenol compound removal test)
25 g of the secondary crosslinked spherical cyclodextrin polymer obtained in Example 5 was packed in a cylindrical column (inner diameter φ 70 mm, height 135 mm, actual volume 129 ml) and heated to 70 ° C. to obtain a homogeneous aqueous solution of phenol ( 125 ml (containing 8.9% by weight of phenol, 0.33% by weight of cresol, and 0.044% by weight of xylenol) was placed in an Erlenmeyer flask and circulated through the column from the bottom of the column at a predetermined flow rate. 2 ml of an aqueous phenol solution was collected at a predetermined time from the start. The collected liquid was measured by gas chromatography, and the phenol compound in the filtrate was measured. As a result of passing for 3 hours at a flow rate of 310 ml, 61.0% of the charged phenol was removed.

Example 15
(Phenol compound removal test)
1.0 g of the secondary crosslinked spherical cyclodextrin polymer obtained in Example 5 was added to a 50 ml Erlenmeyer flask and heated to 60 ° C. to obtain a homogeneous solution (phenol 11.9% by weight, cresol 0. 5 ml) (containing 38 wt% and xylenol 0.042 wt%) was added and stirred at room temperature for 2 hours. Thereafter, the cyclodextrin polymer was subjected to suction filtration, the filtrate was measured by gas chromatography, and the phenolic compound in the filtrate was measured. As a result, 64.0% of the charged phenol was removed.

Example 16
(Phenol compound removal test)
1.0 g of the secondary crosslinked spherical cyclodextrin polymer obtained in Example 6 was added to a 50 ml Erlenmeyer flask and heated to 60 ° C. to obtain a homogeneous aqueous solution (phenol 11.9% by weight, cresol 0.8%). 5 ml) (containing 38 wt% and xylenol 0.042 wt%) was added and stirred at room temperature for 2 hours. Thereafter, the cyclodextrin polymer was subjected to suction filtration, the filtrate was measured by gas chromatography, and the phenolic compound in the filtrate was measured. As a result, 59.4% of the charged phenol was removed.

Example 17
(Phenol compound removal test)
1.0 g of the secondary crosslinked spherical cyclodextrin polymer obtained in Example 7 was added to a 50 ml Erlenmeyer flask and heated to 60 ° C. to obtain a homogeneous solution (phenol 11.9% by weight, cresol 0. 5 ml) (containing 38 wt% and xylenol 0.042 wt%) was added and stirred at room temperature for 2 hours. Thereafter, the cyclodextrin polymer was subjected to suction filtration, the filtrate was measured by gas chromatography, and the phenolic compound in the filtrate was measured. As a result, 63.3% of the charged phenol was removed.

Example 18
(Phenol compound removal test)
1.0 g of the secondary crosslinked spherical cyclodextrin polymer obtained in Example 8 was added to a 50 ml Erlenmeyer flask and heated to 60 ° C. to obtain a homogeneous aqueous solution (phenol 11.9% by weight, cresol 0. 5 ml) (containing 38 wt% and xylenol 0.042 wt%) was added and stirred at room temperature for 2 hours. Thereafter, the cyclodextrin polymer was subjected to suction filtration, the filtrate was measured by gas chromatography, and the phenolic compound in the filtrate was measured. As a result, 64.9% of the charged phenol was removed.

Example 19
(Phenol compound removal test)
25 g of the secondary crosslinked spherical cyclodextrin polymer obtained in Example 5 was packed in a cylindrical column (inner diameter φ70 mm, height 135 mm, actual volume 129 ml), and heated to 60 ° C. to obtain a homogeneous aqueous solution of phenol ( 125 ml (containing 8.9% by weight of phenol, 0.33% by weight of cresol, and 0.044% by weight of xylenol) was placed in an Erlenmeyer flask and circulated through the column from the bottom of the column at a predetermined flow rate. 2 ml of an aqueous phenol solution was collected at a predetermined time from the start. The collected liquid was measured by gas chromatography, and the phenol compound in the filtrate was measured. As a result of passing for 2 hours at a flow rate of 310 ml, 59.3% was removed from the charged phenol.

It is a schematic diagram of cyclodextrin (α-CD, β-CD and γ-CD) of the present invention. 4 is an optical micrograph of the secondary crosslinked spherical cyclodextrin polymer obtained in Example 4. FIG. 4 is an optical micrograph of the secondary crosslinked spherical cyclodextrin polymer obtained in Example 5. FIG. 4 is an SEM photograph of a fracture surface of a secondary crosslinked spherical cyclodextrin polymer obtained in Example 5. FIG.

Claims (12)

(1) A cyclodextrin polymer obtained by reacting a cyclodextrin with a diisocyanate compound,
(2) mixing with a polysaccharide carboxylate aqueous solution;
(3) dropping the mixed solution obtained in the step into an alkaline earth metal halide salt solution;
A process for producing a spherical cyclodextrin polymer, comprising: (2) The method for producing a spherical cyclodextrin polymer according to claim 1, wherein the polysaccharide carboxylate aqueous solution contains at least one aqueous solution selected from the group consisting of an alginate aqueous solution, a pectate aqueous solution and a cellulose glycolate aqueous solution. . (1) For 1 mol of cyclodextrin,
The manufacturing method of the spherical cyclodextrin polymer of Claim 1 or 2 using the cyclodextrin polymer obtained by reacting 1-24 mol of diisocyanate compounds. (1) The method for producing a spherical cyclodextrin polymer according to any one of claims 1 to 3, wherein the cyclodextrin is β-cyclodextrin and the diisocyanate compound is hexamethylene diisocyanate. (1) a cyclodextrin polymer obtained by reacting cyclodextrin with a diisocyanate compound;
(2) The mixing ratio with the aqueous solution of polysaccharide carboxylate is 40:60 to 60:40 (wt / wt%). The method for producing a spherical cyclodextrin polymer according to any one of claims 1 to 4. .   A method for producing a spherical cyclodextrin polymer, comprising reacting at least a diisocyanate compound with the spherical cyclodextrin polymer (A) obtained by the production method according to any one of claims 1 to 5. For 1 part by weight of spherical cyclodextrin polymer (A),
The method for producing a spherical cyclodextrin polymer according to claim 6, wherein 1 to 10 parts by weight of a diisocyanate compound is reacted.   A method for producing a spherical cyclodextrin polymer, comprising reacting at least a diisocyanate compound and a polyether polyol with the spherical cyclodextrin polymer (A) obtained by the production method according to any one of claims 1 to 5. For 1 part by weight of spherical cyclodextrin polymer (A),
1 to 10 parts by weight of a diisocyanate compound
The method for producing a spherical cyclodextrin polymer according to claim 8, wherein 0.01 to 1 part by weight of a polyether polyol is reacted.   The spherical cyclodextrin polymer obtained with the manufacturing method of any one of Claims 1-9.   An organic pollutant adsorbent comprising the spherical cyclodextrin polymer according to claim 10. 11. A phenol compound adsorbent comprising the spherical cyclodextrin polymer according to claim 10.