WO2011102346A1

WO2011102346A1 - Agent and method for selectively anchoring halogenated aromatic compound contained in medium

Info

Publication number: WO2011102346A1
Application number: PCT/JP2011/053163
Authority: WO
Inventors: 栄一加藤; 祐樹野口; 和博宮脇; 信二久保; 英幸友田; 満明石; 敏之木田
Original assignee: 株式会社ネオス; 国立大学法人大阪大学
Priority date: 2010-02-16
Filing date: 2011-02-15
Publication date: 2011-08-25
Also published as: CN102762294A; KR20120112832A; CN102762294B; JP5532359B2; KR101437252B1; JPWO2011102346A1

Abstract

An agent for selectively anchoring a halogenated aromatic compound contained in an organic medium, which comprises a porous cyclodextrin polymer, wherein the porous cyclodextrin polymer is produced by reacting the terminal of a polymer produced by the condensation of cyclodextrin with an organic dibasic acid or a halogenated organic dibasic acid with an alcohol, an aryl alcohol or a phenol and can interact with a halogenated aromatic compound in an attractive manner; and a selective anchoring agent which can selectively anchor a halogenated aromatic compound contained in an organic medium to remove or concentrate the halogenated aromatic compound from the organic medium, whereby the decomposition of the halogenated aromatic compound can be achieved in a simple manner.

Description

Selective fixing agent and selective fixing method of halogenated aromatic compound contained in medium

The present invention can collect a halogenated aromatic compound contained in an organic medium typified by insulating oil, machine oil, heat medium, lubricating oil, plasticizer, paint and ink, and mixtures thereof. The present invention relates to a selective fixing agent and a method for obtaining an organic medium containing almost no halogenated aromatic compound using the selective fixing agent. More specifically, a novel structure that can be obtained by condensing cyclodextrin with an organic dibasic acid and esterifying alcohols, aryl alcohols, or phenols at the terminal of the resulting condensation polymer has a novel structure. The present invention relates to a method for selectively fixing a halogenated aromatic compound contained in an organic medium using a porous cyclodextrin polymer having the same. Furthermore, this invention relates to the cyclodextrin polymer which has said novel structure, and its manufacturing method. The polymer according to the present invention has a characteristic spherical porous shape, whereby various compounds contained in an organic medium can be selectively and efficiently fixed.

Halogenated aromatic compounds are compounds that are highly toxic to humans, animals and plants, and many of them are designated by the Law on Waste Disposal and Cleaning as hazardous substances, especially because of the potential for teratogenicity. . When these compounds are present in soil, groundwater, incineration ash, washing water, machine oil, etc., it is strictly determined that some treatment must be applied to reduce their concentration below the reference value.

Conventionally, an organic medium such as insulating oil containing a halogenated aromatic compound has been chemically treated as it is (Patent No. 2611900, Patent No. 3247505). However, in recent years, in Japan, as well as reclaimed oil without polychlorinated biphenyls (hereinafter referred to as “PCB”) or reclaimed oil without a PCB, it does not contain a PCB or a certificate that does not contain a PCB. Insulating oils (new oils and reclaimed oils) that have a large number of organic media containing halogenated aromatic compounds in trace amounts (about 0.5 to 100 ppm, especially about 0.5 to 10 ppm) have been confirmed one after another. The chemical treatment of such a large amount of organic medium by a conventional method requires a great deal of time and useful energy, so that there remains a problem efficiently and economically.

On the other hand, an organic medium containing a halogenated aromatic compound can be incinerated, but there are many difficult issues such as dioxin countermeasures, and there are still doubts about environmental safety.

Currently, as for halogenated aromatic compound processing technology, not only a medium containing a trace amount of a halogenated aromatic compound but also a technology for processing a halogenated aromatic compound itself has been established. A process (hereinafter referred to as “high concentration treatment”) for directly treating a high concentration medium containing an aromatic compound at a high concentration (1% or more) has started to operate (Japanese Patent Laid-Open No. 2003-112034) .

Therefore, if the halogenated aromatic compound is concentrated by selectively fixing the halogenated aromatic compound contained in a trace amount, only the halogenated aromatic compound is efficiently treated by the above-described high concentration treatment. As a result, the medium from which the halogenated aromatic compound has been removed can be used as a non-contained medium, and the storage place of the medium before processing can be saved.

JP-A-5-31212 discloses a method for collecting an organic halogen compound that forms an organic halogen compound inclusion complex using a modified cyclodextrin. However, the method described in JP-A-5-31212 relates to a method for collecting an organic halogen compound contained in an aqueous solution using the hydrophilic modified cyclodextrin, and the method using the modified cyclodextrin that is not lipophilic. It is difficult to apply as it is to an organic medium system.

From this point of view, the present inventors have earnestly devised a compound that can selectively fix a halogenated aromatic compound by interacting with a halogenated aromatic compound contained in an organic medium in an attractive manner. In search, a selective fixing agent containing a polymer obtained by condensing cyclodextrin and organic dibasic acid was proposed (Japanese Patent Laid-Open No. 2009-95792). A polymer containing a polymer obtained by condensing a cyclodextrin and an organic dibasic acid can selectively fix a halogenated aromatic compound contained in an organic medium. It has been clarified in the Examples that an organic medium containing almost no halogenated aromatic compound can be obtained by bringing the organic medium into contact therewith. However, in this prior art, since the recovery rate of the organic medium containing almost no halogenated aromatic compound is not so high (21 to 34% in the examples), the selective fixing agent that can further increase the recovery rate of the organic medium. Development is desired.

On the other hand, Japanese Patent No. 3010602 discloses various methods for synthesizing cyclodextrin polymers. However, it is disclosed that these compounds are brought into contact with an organic medium to selectively fix a halogenated aromatic compound contained therein. Not done.

As disclosed in JP-A-5-31212, JP-A-2009-95792 and Japanese Patent No. 3010602, cyclodextrin is well known as a compound that can include various compounds. Cyclodextrins are cyclic oligosaccharides in which 6, 7, or 8 glucoses are linked in a cyclic manner and are called α-, β-, or γ-cyclodextrin, respectively. Cyclodextrins have the property of enclosing various compounds in their cyclic vacancies. Due to this property, a hydrophobic substance can be included in cyclodextrin and dissolved in water, or used for various adsorption / separation operations. However, since cyclodextrin is highly water-soluble, its use in organic solvents is limited. Various attempts have been made to make cyclodextrin water insoluble.

As an attempt to make cyclodextrin water insoluble, there is a method of polymerizing it. So far, the reaction of chloromethylpolystyrene with a cyclodextrin derivative and the immobilization of cyclodextrin on a water-insoluble polymer compound have been known for a long time. In addition, a polymer compound obtained by crosslinking cyclodextrin with epichlorohydrin is well known.

JP-A-2009-95792 discloses the production of a polymer that interacts with a halogenated aromatic compound by suction by condensing a cyclodextrin and an organic dibasic acid. As described above, the polymer produced in JP-A-2009-95792 is terminated with a carboxyl group derived from phthalic dichloride.

Patent No. 3010602 discloses that cyclodextrin and terephthalic acid are reacted to form a polymer. In Patent No. 3010602, a method for producing a cyclodextrin polymer having a terminal carboxyl group derived from terephthaloyl dichloride by condensing cyclodextrin and terephthaloyl dichloride, condensing cyclodextrin and dimethyl terephthalate, Discloses a method for producing a cyclodextrin polymer, which is a methyl ester derived from dimethyl terephthalate, and a method for producing a crosslinked cyclodextrin polymer by condensing cyclodextrin and various organic dibasic acids. The example of Japanese Patent No. 3010602 describes that the cyclodextrin polymer thus produced can be formed into a film and decomposed by a specific enzyme.

The present invention makes it easy to decompose only a halogenated aromatic compound by selectively fixing a halogenated aromatic compound contained in an organic medium and removing or concentrating the halogenated aromatic compound from the organic medium. It is an object of the present invention to provide a selective fixing agent that can be used. Further, the present invention selectively collects a halogenated aromatic compound contained in an organic medium using such a selective fixing agent, and thus recovers an organic medium that does not contain a halogenated aromatic compound at a high recovery rate. Provide a way to get at rates.

The inventors have selected a halogenated aromatic compound contained in an organic medium using a novel water-insoluble porous cyclodextrin polymer produced from a water-soluble cyclodextrin as a selective fixing agent. It was found that an organic medium containing no halogenated aromatic compound can be obtained at a high recovery rate.

Aspects of the present invention are as follows:
1. Porous that interacts with halogenated aromatic compounds in an attractive manner by reacting alcohols, aryl alcohols or phenols at the end of the polymer condensed with cyclodextrin and organic dibasic acid or organic dibasic acid halide Selective fixing agent for halogenated aromatic compounds contained in an organic medium, comprising a high-quality cyclodextrin polymer.
2. The organic dibasic acid or organic dibasic acid halide is selected from terephthalic acid, isophthalic acid, maleic acid, malic acid, malonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, phthalic acid or their halides 2. The selective fixing agent according to 1 above.
3. The alcohol is selected from an alkyl group having 1 to 10 carbon atoms, the aryl alcohol is selected from benzyl alcohol, or benzyl alcohol substituted with an alkyl, aryl, or acyl group, and the phenol is phenol, alkyl, aryl, or aryl Or a selective sticking agent according to claim 1 or 2, selected from phenols substituted with acyl groups.
4). 4. The selective fixing agent according to any one of 1 to 3 above, wherein a porous cyclodextrin polymer that interacts with a halogenated aromatic compound in an aspiration manner is immobilized on a solid support.
5. 5. The selective fixing agent according to any one of 1 to 4 above, wherein the halogenated aromatic compound is dioxins, polychlorobiphenyls, or polychlorobenzenes.
6). 6. The selective fixing agent according to any one of the above 1 to 5, wherein the organic medium is selected from the group consisting of an organic liquid, an insulating oil, a heat medium, a lubricating oil, a plasticizer, a paint and an ink, and a mixture thereof.
7). Porous that interacts with halogenated aromatic compounds in an attractive manner by reacting alcohols, aryl alcohols or phenols at the end of a polymer obtained by condensing cyclodextrin with organic dibasic acid or organic dibasic acid halide A selective fixing agent for a halogenated aromatic compound containing a cyclodextrin polymer of the above and an organic medium containing a halogenated aromatic compound are brought into contact with each other, and the halogenated aromatic compound contained in the organic medium is subjected to the halogenation. A method characterized in that an organic medium containing no halogenated aromatic compound is obtained by fixing to a porous cyclodextrin polymer that interacts with an aromatic compound in an aspiration manner.
8). The organic dibasic acid or organic dibasic acid halide is selected from terephthalic acid, isophthalic acid, maleic acid, malic acid, malonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, phthalic acid or their halides 8. The method according to 7 above.
9. The alcohol is selected from alkyl groups having 1 to 10 carbon atoms, the aryl alcohol is selected from benzyl alcohol, or benzyl alcohol substituted with an alkyl, aryl, or acyl group, and the phenol is phenol, alkyl, aryl, or aryl Or the method according to 7 or 8 above, which is selected from phenol substituted with an acyl group.
10. 10. The selective fixing agent according to any one of the above 7 to 9, wherein a selective fixing agent is used, wherein the porous cyclodextrin polymer that interacts with the halogenated aromatic compound in a suction manner is immobilized on a solid support. Method.
11. 11. The method according to any one of 7 to 10 above, wherein the halogenated aromatic compound is dioxins, polychlorobiphenyls, or polychlorobenzenes.
12 12. The method according to any one of 7 to 11 above, wherein the organic medium is selected from the group consisting of organic liquid, insulating oil, machine oil, heat medium, lubricating oil, plasticizer, paint and ink, and mixtures thereof.
13. Add organic dibasic acid or organic dibasic acid halide-containing organic solvent dropwise to cyclodextrin dissolved in organic solvent, and then add alcohols, aryl alcohols, or phenols for esterification reaction A process for producing a porous cyclodextrin polymer.
14 The organic dibasic acid or organic dibasic acid halide is selected from terephthalic acid, isophthalic acid, maleic acid, malic acid, malonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, phthalic acid or their halides 14. The method according to 13 above.
15. 13 or 14 above, wherein the alcohol is selected from aliphatic alcohols having 1 to 10 carbon atoms, the aryl alcohol is selected from benzyl alcohol or substituted benzyl alcohol, and the phenol is selected from phenol or substituted phenols. The method described in 1.
16. The organic solvent for dissolving cyclodextrin is selected from pyridine, dimethyl sulfoxide, dimethylformamide, and 1-methylimidazole, and the organic solvent for dissolving organic dibasic acid or organic dibasic acid halide is tetrahydrofuran, dichloromethane, 1, 16. The method according to any one of the above 13 to 15, which is selected from 4-dioxane, xylene, dimethylformamide and toluene.

Hereinafter, the present invention will be described in detail.

In the present invention, the “halogenated aromatic compound” refers to all compounds in which an aromatic compound is substituted with one or more of fluorine, chlorine, bromine and iodine. In the present invention, for example, polychlorobiphenyls (PCB), dioxins, chlorofluorocarbons, polychloronaphthalenes, polychlorobenzenes and the like are indicated. PCB is a general term for compounds in which several chlorine atoms are substituted on the biphenyl skeleton, and there are many isomers depending on the substitution position and the number of substitutions of chlorine atoms. Dioxins refer to specific compounds specified by the Special Measures for Countermeasures against Dioxins in a narrow sense, but in the present invention, all halogenated compounds suspected as so-called endocrine disrupting substances (environmental hormones) are included.

In the present invention, an “organic medium” containing a halogenated aromatic compound is generally an organic solvent, and particularly an organic solvent that dissolves a halogenated aromatic compound well. From the aspect, it means an insulating oil, a machine oil, a heat medium, a lubricating oil, a plasticizer, a paint and an ink, a mixture thereof, and the like that are highly likely to contain a halogenated aromatic compound. In the present invention, the “organic medium” may be the majority of the organic medium (for example, 60% or more), and may contain water depending on the case. However, the organic medium containing the halogenated aromatic compound may be used. The property of the medium as a whole is not that of an aqueous solution but that of an organic solution.

In addition, in order to decompose halogenated aromatic compounds contained in solid substances (eg paper, wood, incinerated ash, rocks, soil, etc.), the halogenated aromatic compounds contained in these solid substances are extracted. Those transferred to an organic medium can also be an “organic medium containing a halogenated aromatic compound” to be treated with the selective fixing agent of the present invention.

In the present specification, “interacting with a halogenated aromatic compound in an attractive manner” means interacting with the above-described halogenated aromatic compound in an attractive manner (that is, not repulsive). The compounds having such properties are collectively referred to as “compounds that interact with a halogenated aromatic compound in an attractive manner”. Such compounds have cyclic moieties, substituents, sequences, etc. that interact with the halogenated aromatic compounds in an attractive manner. In the present specification, the “compound that interacts with a halogenated aromatic compound in an attractive manner” is sometimes simply abbreviated as “attractive interactive compound”, “interactive compound” or “interacting compound”. May be described.

In the present invention, “selectively fixing” a halogenated aromatic compound means that only a halogenated aromatic compound contained in the organic medium by dissolution, dispersion, or the like, or an organic medium containing the halogenated aromatic compound therein. Interacts with the association of molecules to take in or fix them. In this specification, “adhesion” includes all chemical bonding and adhesion, and physical adsorption, suction, or just being caught, and does not necessarily mean that it is always adhered. . For example, if it interacts with a halogenated aromatic compound and is located at a very short distance for a predetermined time, or if it is in contact for a predetermined time by an attractive interaction, this It shall correspond to the “fixed” state referred to in the specification. That is, the “selective sticking agent” of the present invention means that the active ingredient contained in the selective sticking agent interacts with the halogenated aromatic compound contained in the organic medium strongly and attractively, In addition to drugs that are firmly incorporated or anchored into the molecular structure of the active ingredient, such active ingredients must be in at least temporary contact with the halogenated aromatic compound or maintained in close proximity. Means a drug that can

Therefore, the selective fixing agent of the present invention includes a composition capable of fixing these by attracting interaction with the halogenated aromatic compound. As an active ingredient of such a composition, there can be mentioned a porous cyclodextrin polymer obtained by reacting alcohols, aryl alcohols or phenols at the terminal of a polymer obtained by condensing cyclodextrin and an organic dibasic acid. The compound that interacts with the halogenated aromatic compound exemplified here is a compound having in its molecule a cyclic part of cyclodextrin capable of interacting with the halogenated aromatic compound in the molecular structure. And the interactive compound can be at least dispersed in an organic medium. An interactively interacting moiety present in the molecule of the interacting compound, i.e., the cyclic part of cyclodextrin interacts with the halogenated aromatic compound, thereby allowing the halogenated aromatic compound to interact with or near the interacting part. Secure to.

The selective fixing agent of the present invention contains, as an active ingredient, a compound that interacts with the halogenated aromatic compound in an aspirate manner, and may contain auxiliary agents such as a carrier, a substrate, and a diluent as necessary. . In addition, the compound that interacts with the halogenated aromatic compound, which is the active ingredient, in an attractive manner may be immobilized on a carrier or a substrate as the case may be. For example, compounds that interact with halogenated aromatic compounds in aspiration on solid supports such as silica gel, polymer beads, ion exchange resins, glass, filters, membranes, various network or lattice structures, foams, porous materials, etc. Can be immobilized. Immobilization of a compound that interacts with a halogenated aromatic compound to a carrier or a substrate can be carried out by using a relatively strong chemical bond represented by, for example, covalent bond or ionic bond, as well as hydrophobic interaction, van der It can also be performed by physical interaction with a relatively weak force such as a Waals force.

Examples of the compound that interacts with the halogenated aromatic compound in an attractive manner include a polymer obtained by reacting an alcohol, an aryl alcohol, or a phenol with a terminal of a polymer obtained by condensing a cyclodextrin and an organic dibasic acid. Cyclodextrins are cyclic oligosaccharides in which 6, 7 or 8 glucoses are cyclically linked, and are called α-, β- or γ-cyclodextrin, respectively. Organic dibasic acids include, for example, aliphatic dicarboxylic acids, aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and fatty acids, and in the present invention, they react with the —CH ₂ OH group in the cyclodextrin molecule to sequentially condense. It is a compound that can form a polymer. Examples of such organic dibasic acids include terephthalic acid, isophthalic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, and phthalic acid. The organic dibasic acid halide refers to an acid halide of the above organic dibasic acid. In the present invention, it is particularly preferable to use terephthalic acid which is an organic dibasic acid or terephthalic acid dichloride (terephthaloyl dichloride) which is an organic dibasic acid halide.

Reacting alcohols, aryl alcohols or phenols at the polymer end means end-capping the carboxyl group derived from the organic dibasic acid remaining at the end of the condensation polymer with a specific substituent. To endcap the carboxyl group, alcohols, aryl alcohols or phenols can be reacted and esterified. In the present invention, the terminal is reacted with alcohols, aryl alcohols or phenols, for example, alcohols selected from alcohols having 1 to 10 carbon atoms, aryl alcohols selected from benzyl alcohol or substituted benzyl alcohols, Or it means reacting phenols selected from phenol or substituted phenols with carboxyl end groups to alkyl esters, aryl esters or phenyl esters. For example, when a condensation polymer is reacted with methanol, the end group is methyl ester (—COOMe), when reacted with ethanol, is ethyl ester (—COOEt), and when reacted with benzyl alcohol is benzyl ester (—COOBz). .

Here, if a plurality of cyclodextrins and organic dibasic acids are sequentially condensed and this end is treated with alcohols, aryl alcohols or phenols, for example, cyclodextrin and organic dibasic acids in total. Even so-called compounds generally called “oligomers” condensed by several to 10 are collectively referred to as “polymers” in the present specification. The porous cyclodextrin polymer of the present invention may be a composition in which polymers having different molecular weights are mixed.
The chemical structural formula of the cyclodextrin polymer used in the present invention can be represented, for example, by the following formula:

In this formula, the cyclodextrin part is represented by a truncated cone, and terephthalic acid is used as the organic dibasic acid. Hydroxyl groups and organic dibasic acids in cyclodextrin are alternately bonded by ester bonds to form a network structure. The polymer ends are capped with methyl groups as a result of reaction with methanol.

For example, when γ-cyclodextrin is condensed with terephthaloyl dichloride as an organic dibasic acid halide and then reacted with methanol at the terminal, the reaction proceeds according to the following scheme, and a polymer can be obtained. :

One acid chloride group (—COCl) of terephthaloyl dichloride reacts with the —CH ₂ OH group of γ-cyclodextrin to form an ester bond. The other acid chloride group then reacts with the —CH ₂ OH group of another γ-cyclodextrin. This is repeated to obtain a condensation polymer. Although many hydroxyl groups exist in cyclodextrins, the substituent involved in the condensation is a moiety of —CH ₂ OH, and such groups are 6 for α-cyclodextrin and 7 for β-cyclodextrin. In the case of γ-cyclodextrin, there are 8 molecules in the molecule. The obtained condensate may have a crosslinked structure or a three-dimensional network structure in addition to the one in which cyclodextrin and organic dibasic acid are alternately condensed. When methanol is reacted at the end of the condensation reaction, the terminal acid chloride group becomes —COOCH ₃ .

Here, when vigorously stirred during the condensation reaction between cyclodextrin and organic dibasic acid (or organic dibasic acid halide), a polymer having a spherical porous shape that is finally obtained as a selective fixing agent of the present invention is obtained. Found that you can get. Stirring is performed using a magnetic stirrer or a stirrer bar. Especially, a stirrer equipped with a stirring blade can be used to stir evenly so that there is no difference in the stirring speed between the upper part and the lower part of the reaction solution. It is convenient to use a stirrer. For example, as shown in FIG. 4, when using Max Blend with four blades attached at the top, the top and bottom in the reactor can be stirred uniformly. In addition, as long as the stirring blade can increase the stirring efficiency, various shapes of the stirring blade can be used. In order to use as a selective fixing agent for halogenated aromatic compounds, it has been found that it is important to obtain a polymer having a porous shape, particularly a spherical porous shape. Here, the porous shape generally means a shape in which small pores are opened in the polymer. The spherical porous shape means that sphere-shaped minute lumps are aggregated to form a shape having small pores as a whole. As an example, an electron micrograph of the spherical porous cyclodextrin polymer produced in Synthesis Example 1 (end-capped with a methyl group on a condensation polymer of γ-cyclodextrin and terephthaloyl dichloride) used in the present invention is shown in FIG. To According to FIG. 1, it can be seen that the polymer used in the present invention has a porous shape in which fine spherical crystals are aggregated. In general, as a method for obtaining a porous organic polymer, a chemical method such as acid / alkali treatment or a foaming method during production is well known. The polymer used as the selective fixing agent of the present invention can have a special shape by stirring during condensation.

For comparison, FIG. 2 shows an electron micrograph of the condensation polymer of γ-cyclodextrin and terephthaloyl dichloride produced in Comparative Synthesis Example 1 (a polymer whose terminal is not end-capped with alcohol or the like). It can be seen that the polymer of FIG. 2 also has a porous shape, but the spherical crystal spheres are incomplete. The polymer in FIG. 2 is shaped like a fusion of spheres, and can be said to have a smaller surface area than the polymer in FIG. Further, an electron micrograph of the polymer synthesized in Comparative Synthesis Example 2 is shown in FIG. It is surprising that a slight difference in the microstructure of the polymer shows a difference in the performance of the halogenated aromatic compound contained in the organic medium as a selective fixing agent.

FIG. 1 is an electron micrograph of a porous cyclodextrin polymer (terephthalic acid γ-CD-methyl polymer) of the present invention. FIG. 2 is an electron micrograph of a condensation polymer (Comparative Synthesis Example 1) produced by a method according to JP-A-2009-95792. FIG. 3 is an electron micrograph of a polymer produced by the method according to Japanese Patent No. 3010602 (Comparative Synthesis Example 2). FIG. 4 is a schematic view of an example of a stirring blade used in the method of the present invention. FIG. 4a is a side view of a stirring blade that can be used in the method of the present invention. FIG. 4b is a top view of a stirring blade that can be used in the method of the present invention.

As an active ingredient of the selective fixing agent of the present invention, a cyclodextrin polymer obtained by condensing a cyclodextrin and an organic dibasic acid and reacting an alcohol, an aryl alcohol or a phenol with a terminal is exemplified by the following method: Can be manufactured with:
γ-cyclodextrin is dissolved in an organic solvent (for example, pyridine, dimethyl sulfoxide, dimethylformamide, etc., preferably dry pyridine). On the other hand, terephthaloyl dichloride is dissolved in an organic solvent (for example, tetrahydrofuran, dichloromethane, 1,4-dioxane, etc., preferably dry tetrahydrofuran) and added dropwise to the previously prepared γ-cyclodextrin solution. At this time, since heat is generated by the condensation reaction, it is desirable to drop the γ-cyclodextrin solution while cooling with an ice bath or the like. The reactor is then placed in a 50-70 ° C. water bath and the reaction mixture is stirred vigorously. After completion of the reaction, the temperature in the reaction vessel is slightly lowered (approximately 5 to 10 ° C.), alcohols (alcohols having 1 to 10 carbon atoms such as methanol, ethanol, propanol, butanol, octanol), aryl alcohols (benzyl alcohol or Benzyl alcohol substituted with alkyl, aryl or acyl groups) or phenols (phenols substituted with phenol, alkyl, aryl or acyl groups) are added and stirring is continued. The obtained crystals are washed with a washing liquid such as alcohols, water, and acetone, and dried. Then, γ-cyclodextrin and terephthalic acid are condensed to form cyclohexane in which alcohols, aryl alcohols, or phenols are reacted at the terminal. A dextrin polymer can be obtained. In addition to γ-cyclodextrin, α- and β-cyclodextrin can form similar condensation polymers. In the present specification, the polymers thus obtained are referred to as “terephthalic acid-γ-CD-methyl polymer” (when the terminal is treated with methanol), “terephthalic acid-γ-CD-ethyl polymer” (terminal is ethanol). ), “Terephthalic acid-γ-CD-benzyl polymer” (when terminal is treated with benzyl alcohol), “terephthalic acid-γ-CD-phenyl polymer” (when terminal is treated with phenol) Although these may be abbreviated as “etc.”, they are porous cyclodextrin polymers that are used in the present invention and are compounds that interact with a halogenated aromatic compound in an attractive manner.

Next, a polymer obtained by condensing a commercially available γ-cyclodextrin (hereinafter referred to as “γ-CD”) and terephthaloyl dichloride with a methyl group (hereinafter referred to as “terephthalic acid-γ-CD”). A specific synthesis method of “methyl polymer” or “TPGCDM polymer”) is shown:
First, γ-CD is dissolved in an organic solvent (for example, pyridine, dimethyl sulfoxide, dimethylformamide, 1-methylimidazole, etc.). The concentration of γ-CD in the organic solvent is preferably 5 to 20% by weight. On the other hand, 4 to 12 times (mol) terephthaloyl dichloride prepared γ-CD in an organic solvent (eg, tetrahydrofuran, dichloromethane, 1,4-dioxane, xylene, dimethylformamide, toluene, etc.) at a concentration of 10 to 40 wt. It is dissolved in% and added dropwise to the previously prepared γ-CD solution and stirred vigorously. Stirring is performed using a magnetic stirrer or a stirrer bar. Especially, a stirrer equipped with a stirring blade can be used to stir evenly so that there is no difference in the stirring speed between the upper part and the lower part of the reaction solution. It is convenient to use a stirrer. For example, as shown in FIG. 4, when using Max Blend with four blades attached at the top, the top and bottom in the reactor can be stirred uniformly. In addition, as long as the stirring blade can increase the stirring efficiency, various shapes of the stirring blade can be used. As the condensation reaction between γ-CD and terephthaloyl dichloride proceeds, heat is generated. Therefore, the γ-CD solution is preferably dropped while being cooled in an ice bath or the like. Preferably, the temperature in the reaction vessel is maintained in the range of about 0-20 ° C. After the dropwise addition, the temperature in the reaction vessel is raised to a range of about 40 to 70 ° C. and stirred. Next, the temperature in the reaction vessel is slightly lowered to about 60 to 65 ° C., and then an alcohol (preferably an aliphatic having 1 to 10 carbon atoms) in an amount of 30 to 80% by weight with respect to γ-CD. Alcohols), aryl alcohols (preferably benzyl alcohol or substituted benzyl alcohol), or phenols (preferably phenol or substituted phenols) are added. For example, when methanol is added as an alcohol, stirring can be continued for about 1 to 24 hours. In this way, crystals of cyclodextrin polymer endcapped with methyl groups are precipitated. The precipitated crystals are collected by filtration, washed with water and acetone, and the cyclodextrin polymer of the present invention (terephthalic acid-γ-CD-methyl). Polymer) can be obtained. The obtained polymer can be identified by infrared absorption, and the morphology can be observed with an electron microscope.

Comparing the cyclodextrin polymer of the present invention with the cyclodextrin polymer prepared by the conventional method and the conventional condensation polymer without end caps, the cyclodextrin polymer of the present invention has a form in which fine spherical crystals are assembled. You can see that The cyclodextrin polymer of the present invention has a more complete spherical shape, and no collapse or distortion is observed. The cyclodextrin polymer of the present invention has a larger surface area than conventional polymers and can be brought into contact with more organic liquid. Therefore, the compound that interacts with the halogenated aromatic compound obtained by such a method in an attractive manner can be used as it is as a selective fixing agent, and it is selectively fixed with various additives or auxiliaries added as necessary. It can be set as an agent composition. When the cyclodextrin polymer of the present invention is used for the separation of a compound contained in an organic liquid, the cyclodextrin polymer is packed in, for example, a column and the desired liquid can be simply passed through the organic liquid. Compounds can be separated.

Next, a method for selectively removing a halogenated aromatic compound from an organic medium using the selective fixing agent of the present invention will be specifically described.

The organic medium containing the halogenated aromatic compound used in the present invention contains at least one halogenated aromatic compound described above. The halogenated aromatic compound may be dissolved at any concentration in the organic medium. However, particularly when the content of the halogenated aromatic compound is about 0.5 to 1%, “trace amount”, “trace amount” or “low concentration” It is said to contain. In particular, an organic medium containing a low concentration of a halogenated aromatic compound has a very small volume of the halogenated aromatic compound to be treated, but the volume of the organic medium itself becomes very large, thus making storage difficult. Chemical treatment takes a lot of time. Therefore, if a halogenated aromatic compound dissolved in an extremely small amount can be concentrated and separated from an organic medium and separated into a halogenated aromatic compound to be treated and a reusable organic medium, the halogenated aromatic compound While the processing efficiency of the compound increases, the problem of storage of such organic media can also be solved.

Organic media that are particularly likely to contain a halogenated aromatic compound include various organic liquids, insulating oils, machine oils, heat media, lubricating oils, plasticizers, paints, inks, and mixtures thereof. An organic medium containing a halogenated aromatic compound is placed in a reaction vessel. You may use the storage container which stores these organic media as a reaction container as it is. Here, the present invention includes a compound that interacts with a halogenated aromatic compound in an attractive manner 10 times to 50 times, preferably 50 to 200 times (molar basis) with respect to the contained halogenated aromatic compound. Add the selective fixing agent and stir well. A compound that interacts with the halogenated aromatic compound, which is an active component in the selective fixing agent of the present invention, or a composition containing such a compound is dispersed in an organic medium and halogenated in the organic medium. Contact with aromatic compounds. The halogenated aromatic compound is fixed to or near the attractive interaction portion by the interaction with the attractive interaction portion in the compound that interacts with the halogenated aromatic compound. Depending on the amount of the organic medium to be treated, the concentration of the halogenated aromatic compound, and the amount of the selective fixing agent of the present invention, the contact can be generally made by a method such as stirring for 5 hours to several days. The fixing reaction can be suitably performed at room temperature, and can be heated as necessary.

After the halogenated aromatic compound contained in the organic medium is fixed to the compound that interacts with the halogenated aromatic compound in this manner, the attractive interaction compound to which the halogenated aromatic compound is fixed Only (or the composition containing the compound) is isolated. Separation may be performed using an existing solid-liquid separation technique, for example, a method using a centrifugal separator or a pressure filter. The filter for separation can be performed using a commercially available filter, glass filter, membrane, absorbent cotton, metal, resin or the like. Any filter or membrane may be used as long as it has a pore size capable of separating the inclusion compounds contained in the selective fixing agent of the present invention, but in consideration of the particle size of a general interaction compound. It is preferable to use one having a pore diameter of about 0.1-100 μm.

The aspiration interaction compound to which the halogenated aromatic compound obtained by separation is fixed is separated from the halogenated aromatic compound, which is fixed, if necessary, and the halogenated aromatic compound to which the suction interaction compound is fixed or After the halogenated aromatic compound obtained by the desorption operation is diluted as necessary, it can be decomposed by a chemical processing method such as a chemical extraction decomposition method.

In the organic medium obtained after separating the attractive interaction compound to which the halogenated aromatic compound is fixed, the halogenated aromatic compound is substantially completely removed. Therefore, organic media that had previously been stored due to the inclusion of halogenated aromatic compounds should be reused if they can be reused, or disposed of by ordinary methods such as incineration. Can do.

As the selective fixing agent of the present invention, the active component, a compound that interacts with the halogenated aromatic compound in a suction manner, for example, silica gel, polymer beads, ion exchange resin, foam, film, membrane, various lattice-like structures and Those immobilized on a carrier such as a net-like structure or a porous material can be preferably used. For example, a solid carrier such as silica gel, polymer beads, or ion exchange resin, on which the attractive interaction compound of the present invention is supported, is laminated in a column, and an organic medium containing a halogenated aromatic compound is placed under normal pressure or By flowing under pressure and interacting with the attractive interaction compound, it becomes possible to effectively remove the halogenated aromatic compound contained in the organic medium. Alternatively, the organic medium containing a halogenated aromatic compound is filtered into the organic medium at normal pressure or reduced pressure using a solid carrier such as a filter or membrane that supports the suction interaction compound of the present invention. It becomes possible to remove the halogenated aromatic compound by fixing the contained halogenated aromatic compound to the membrane or filter. Alternatively, a solid carrier such as a foam, a net-like structure, a lattice-like structure, or a porous material that is loaded with the attractive interaction compound of the present invention is put into an organic medium containing a halogenated aromatic compound. The organic carrier is absorbed in the net-like portion, lattice-like portion or pore portion of the solid support, the contained halogenated aromatic compound is fixed, and then the solid support is pressurized (for example, squeezed, if necessary) Etc.) to obtain an organic medium from which the halogenated aromatic compound has been removed.

Thus, a composition in which a compound that interacts with the halogenated aromatic compound of the present invention in an attractive manner is immobilized on a solid support is obtained by batch treatment from an organic medium containing a halogenated aromatic compound. In addition to being used in a method for removing a compound, it is also very suitably used in a method for continuous treatment.

As a selective fixing agent of the present invention, a porous polymer itself, which is an active component, which interacts with a halogenated aromatic compound in a suction manner, is packed in a column or the like, and an organic medium containing the halogenated aromatic compound is subjected to normal pressure. It is also possible to remove the halogenated aromatic compound from the organic medium by flowing under pressure.

Thus, the selective fixing agent of the present invention can selectively fix the halogenated aromatic compound contained in the organic medium and remove it from the organic medium. By using the selective fixing agent of the present invention, only a halogenated aromatic compound that requires strict decomposition treatment is required from an organic medium that must be stored because a trace amount of the halogenated aromatic compound is dissolved. Can be removed and concentrated, so that the decomposition efficiency of halogenated aromatic compounds is dramatically increased, while the safe organic medium recovered efficiently can be processed or reused in the usual way It becomes. The method for removing the halogenated aromatic compound contained in the organic medium using the selective fixing agent of the present invention is the method of introducing and dispersing the selective fixing agent in the organic medium, and stirring the halogenated aromatic compound by stirring or the like. Since this is a relatively easy method of fixing and separating, and it can be carried out at room temperature, it is a safe method that does not cause the halogenated aromatic compound to diffuse into the atmosphere. As the selective fixing agent of the present invention, when a substance in which a compound that interacts with a halogenated aromatic compound is fixed to various solid carriers is used, the halogenated aromatic compound contained in the organic medium is continuously added. It can be removed.

[Synthesis Example 1] A polymer obtained by condensing a terminal of a polymer obtained by condensing γ-cyclodextrin (hereinafter referred to as “γ-CD”) and terephthaloyl dichloride with a methyl group (hereinafter referred to as “terephthalic acid-γ-CD”). -Synthesis of "methyl polymer" or "TPGCDM polymer")) Into a 1 liter four-necked separable flask equipped with a dropping funnel, a three-way cock with a balloon, a stopcock and a stirring rod (stirred by a stirrer), dry γ- CD (50 g, 0.039 mol, water content 1% or less, Junsei Chemical Industry) and special grade pyridine (660 ml, Wako Pure Chemical Industries, Ltd.) were added and stirred at room temperature for 1 hour. After placing the flask in an ice bath, terephthaloyl dichloride (78.3 g, 0.39 mol, Tokyo Chemical Industry) dissolved in special grade tetrahydrofuran (220 mL, Wako Pure Chemical Industries) was added dropwise over 1 hour. After dropping, the ice bath was removed, and the mixture was stirred for 3 hours at an internal temperature of 70 ° C. with a hot water bath (70 ° C.). After completion of the reaction, the internal temperature was lowered to 65 ° C., primary methanol (100 ml, Pure Chemical Industries) was added, and the mixture was stirred for 2 hours. After the crystals were suction filtered, the obtained crystals were washed with water (400 mL × 3) and primary acetone (400 ml × 1, Junsei Kagaku Kogyo) in this order, and the obtained solid was vacuum-dried at 120 ° C. overnight. 105 g of terephthalic acid-γ-CD-methyl polymer (hereinafter abbreviated as TPGCDM) was obtained.
IR (KBr) 3448,1719,1277,1105,1018,732 cm ^-1

[Example 1] 2,2 ', 3,3', 5,5'-hexachlorobiphenyl (hereinafter referred to as "2,2'3,3'5,5'-HECBP") using TPGCDM polymer. Selective fixing A stainless steel column (4mm ID x 10mm length) packed with TPGCDM polymer (240mg) is installed in an oven with temperature control, and 2,2 ', 3,3', 5,5'-HECBP in the column The contained insulating oil (concentration: 100 ppm, total weight: 400 mg, high-pressure insulating oil from Taniguchi Oil Refinery Co., Ltd.) was poured in with nitrogen gas and poured at 130 ° C. to obtain 349 mg of insulating oil. The internal standard by SIM (selective ion monitoring) method using M / Z 360 for the 2,2 ', 3,3', 5,5'-HECBP concentration of the insulating oil using QCMS-QP5050 (SHIMADZU) Measured by the method (internal standard substance: 2,2 ', 4,4', 5,5'-hexachlorobiphenyl), 2,2 ', 3,3', 5,5'-HECBP is included It wasn't. The results are listed in Table 1.

[Example 2] Selective fixation of polychlorinated biphenyl (hereinafter referred to as “PCB”) with TPGCDM polymer A stainless steel column (inner diameter 8 mm × length 300 mm) packed with TPGCDM polymer (1.5 g) was oven controlled with temperature. The insulating oil (hereinafter referred to as “actual liquid”; PCB concentration: 26.5 ppm, total weight: 2.6 g) where PCB is actually dissolved and left in the column is poured into the column with nitrogen gas, When poured out at 130 ° C., 1.6 g of insulating oil was obtained. When the PCB concentration of the insulating oil was measured by the gas chromatographic method according to the method prescribed in 1992, Ministry of Health and Welfare Notification No. 192 Attached Table 3, no PCB was contained. The results are listed in Table 2.

[Synthesis Example 2] Polymer obtained by condensing β-CD and terephthaloyl dichloride with a methyl group at the end (hereinafter referred to as “terephthalic acid-β-CD-methyl polymer” or “TPBCDM polymer”) )) Into a 1 L four-necked separable flask equipped with a dropping funnel, a three-way cock with a balloon, a stopcock and a stirring rod (stirred by a stirrer), dry β-cyclodextrin (hereinafter abbreviated as β-CD, 50 g, 0.044 mol, water content 1% or less, Pure Chemical) and special grade pyridine (660 mL, Wako Pure Chemical Industries) were added and stirred at room temperature for 1 hour. After placing the flask in an ice bath, terephthaloyl dichloride (89.4 g, 0.44 mol, Tokyo Kasei Kogyo) dissolved in special grade tetrahydrofuran (230 mL, Wako Pure Chemical Industries) was added dropwise over 1 hour. After the dropwise addition, the ice bath was removed, and the mixture was stirred for 4 hours at 70 ° C. with a hot water bath (70 ° C.). After completion of the reaction, the internal temperature was lowered to 65 ° C., primary methanol (35.6 mL, 0.88 mmol, Junsei Kagaku) was added, and the mixture was stirred for 4 hours. After the crystals were filtered off with suction, the crystals obtained were washed in the order of primary methanol (400 mL × 2, Junsei Chemical), water (400 mL × 3), primary acetone (400 ml × 2, Junsei Chemical), in that order. The resulting solid was vacuum dried at 120 ° C. overnight. 98.7 g of TPBCDM polymer was obtained.
IR (KBr): 3448, 1718, 1277, 1105, 1018, 731 cm ^-1

[Synthesis Examples 3 to 6]
In Synthesis Example 2, terephthalic acid-β-CD-ethyl polymer (hereinafter “TPBCDE”) was prepared in the same manner as in Synthesis Example 2, except that primary ethanol (Pure Chemical) was used instead of primary methanol. Was synthesized (Synthesis Example 3).
IR (KBr) 3448, 1717, 1277, 1105, 1018, 731 cm ^-1
Similarly, terephthalic acid-β-CD-propyl polymer (hereinafter referred to as “TPBCDP”) was synthesized using special grade 2-propanol (Tokyo Chemical Industry) (Synthesis Example 4).
IR (KBr) 3448, 1718, 1276, 1103, 1018, 732 cm ^-1
Similarly, terephthalic acid-β-CD-benzyl polymer (hereinafter referred to as “TPBCDB”) was synthesized using special grade 2-benzyl alcohol (Pure Chemical) (Synthesis Example 5).
IR (KBr) 3448, 1718, 1274, 1104, 1018, 731 cm ^-1
Similarly, terephthalic acid-β-CD-octyl polymer (hereinafter referred to as “TPBCDO”) was synthesized using special grade 1-octanol (Pure Chemical) (Synthesis Example 6).
IR (KBr) 3448, 1718, 1272, 1104, 1018, 731 cm ^-1

[Example 3] Selective fixation of 2,2'3,3'5,5'-HECBP with TPBCDM polymer Stainless steel column (inner diameter 4 mm) packed with TPBCDM polymer (350 mg) obtained in Synthesis Example 2 above × 10 mm in length) installed in an oven with temperature control, and 2,2 ', 3,3', 5,5'-HECBP-containing insulating oil (concentration: 100 ppm, total weight: 350 mg) in the column The insulating oil was Taniguchi Petroleum Refining Co., Ltd., high-pressure insulating oil) which was poured with nitrogen gas and poured out at 130 ° C. to obtain 269 mg of insulating oil. When 2,2 ', 3,3', 5,5'-HECBP concentration of the insulating oil was measured by gas chromatography, 2,2 ', 3,3', 5,5'-HECBP was not included. There wasn't. The results are listed in Table 1.

[Examples 4 to 7] Selective fixation of 2,2'3,3'5,5'-HECBP by the polymers synthesized in Synthesis Examples 3 to 6 TPBCDE, TPBCDP and TPBCDB synthesized in Synthesis Examples 3 to 6 above In addition, a selective fixation test of 2,2′3,3′5,5′-HECBP was conducted in the same manner as in Example 3 using TPBCDO. The results are listed in Table 1.

[Example 8] Selective fixing of PCB with TPBCDM polymer A stainless steel column (inner diameter 8 mm x length 300 mm) packed with the TPBCDM polymer (2.0 g) obtained in Synthesis Example 2 was mounted in an oven with temperature control. The actual liquid (PCB concentration: 26.5 ppm, total weight: 2.0 g) used in Example 2 was poured into the column with nitrogen gas and poured out at 130 ° C. to obtain 962 mg of insulating oil. When the PCB concentration of the insulating oil was measured by gas chromatography, it did not contain PCB. The results are listed in Table 2.

[Examples 9 to 12] Selective fixing of PCB by the polymers synthesized in Synthesis Examples 3 to 6 Using the TPBCDE, TPBCDP, TPBCDB, and TPBCDO synthesized in the above Synthesis Examples 3 to 6, the PCB was prepared in the same manner as in Example 8. A selective sticking test was performed. The results are listed in Table 2.

[Comparative Synthesis Example 1] Synthesis of condensation polymer of γ-CD and terephthalic acid (hereinafter referred to as “terephthalic acid-γ-CD polymer”) As a comparative example, the terminal is not treated with alcohols or the like. Terephthalic acid γ-CD was synthesized according to the method described in Synthesis Example 1 of JP-A-2009-95792.

In a 1L four-necked separable flask equipped with a dropping funnel, a three-way cock with a balloon, a stopcock and a stirring rod (stirred by a stirrer), dry γ-cyclodextrin (50 g, 0.039 mol, water content 1% or less, pure chemical Industrial) and special grade pyridine (660 ml, Wako Pure Chemical Industries) were added and stirred at room temperature for 1 hour. After placing the flask in an ice bath, terephthaloyl dichloride (78.3 g, 0.39 mol, Tokyo Chemical Industry) dissolved in special grade tetrahydrofuran (220 mL, Wako Pure Chemical Industries) was added dropwise over 1 hour. After the dropwise addition, the ice bath was removed, and the mixture was stirred for 3 hours at an internal temperature of 70 ° C. with a hot water bath (70 ° C.). After completion of the reaction, water (100 ml, Junsei Kagaku Kogyo) was added and stirred in a hot water bath (70 ° C.) for 2 hours. After the crystals were suction filtered, the obtained crystals were washed with water (400 mL × 3) and primary acetone (400 ml × 1, Junsei Kagaku Kogyo) in this order, and the obtained solid was vacuum-dried at 120 ° C. overnight. 105 g of terephthalic acid-γ-CD polymer (hereinafter referred to as “TPGCD”) was obtained.
IR (neat) 3418, 1716, 1409, 1266, 1097, 1041, 1017, 874, 730 cm ^-1

[Comparative Example 1] 2,2 ', 3,3', 5,5'-hexachlorobiphenyl (hereinafter referred to as "2,2 ', 3,3', 5,5'-HECBP") by TPGCD A stainless steel column (inner diameter 4 mm x length 10 mm) packed with TPGCD (450 mg) synthesized in Comparative Synthesis Example 1 above was mounted in an oven with temperature control, and 2,2 ', 3, When 3 ′, 5,5′-HECBP-containing insulating oil (100 ppm, 450 mg) was poured with nitrogen gas and poured out at 130 ° C., 374 mg of insulating oil was obtained. When 2,2 ', 3,3', 5,5'-HECBP concentration of the insulating oil was measured by gas chromatography, 2,2 ', 3,3', 5,5'-HECBP was not included. There wasn't. As is apparent from Table 1, in Example 1 of the present invention, even when the insulating oil: adsorbing material weight ratio is 400: 240 and the insulating oil is excessive, 2,2 ′, 3,3 ′, Although 5,5′-HECBP could be almost completely adsorbed, in Comparative Example 1, in order to obtain the same result as in Example 1, the same amount of adsorbing material (450 mg) as the insulating oil (450 mg) Was necessary. That is, the TPGCD polymer (the porous cyclodextrin polymer reacted with methanol at the end according to the present invention) has better adsorption performance than the TPGCD polymer (the polymer not reacted with methanol at the end). I found it.

[Comparative Example 2] Selective fixation of PCB by TPGCD A stainless steel column (inner diameter 2 cm x length 25 cm) filled with the TPGCD polymer (11 g) synthesized in the above Comparative Synthesis Example 1 was mounted in an oven with temperature control. The actual liquid (26.5 ppm, 9.0 g) was poured into the column with nitrogen gas and poured out at 130 ° C. to obtain 3.0 g of insulating oil. When the PCB concentration of the insulating oil was measured by gas chromatography, it did not contain PCB. In Example 2 of the present invention, PCB could be almost completely adsorbed even when the insulating oil: adsorbing material weight ratio of 2.6: 1.6 was excessive. In Comparative Example 2, in order to obtain the same result as in Example 2, more adsorbent material (11.0 g) than insulating oil (9.0 g) was required. That is, the TPGCD polymer (the porous cyclodextrin polymer reacted with methanol at the end according to the present invention) has better adsorption performance than the TPGCD polymer (the polymer not reacted with methanol at the end). I found it.

[Comparative Synthesis Example 2] Polymer synthesis according to Japanese Patent No. 3010602 A polymer was synthesized generally according to the method disclosed in paragraph No. 0025 of Japanese Patent No. 3010602.

In the polymerization reaction tube, dry β-CD (1.0 g, 0.88 mmol, water content 1% or less, Pure Chemical) and dimethyl terephthalate (1.7 g, 8.8 mmol, Kishida Chemical) (10 times equivalent of β-CD, synthesis) Same as Example 1, etc.) and calcium acetate dihydrate (3.5 mg, Kanto Chemical) and antimony trioxide (7.0 mg, Wako Pure Chemical Industries) in DMF (18 ml, Junsei) were added to form a homogeneous solution. . The mixture was heated and the capillary was passed through to the bottom of the reaction tube and flushed with nitrogen. After methanol in the mixture was distilled off at 110 ° C. for 6 hours, the mixture was heated at 150 ° C. for 6 hours. Then, the pressure was reduced, and the mixture was further heated for 12 hours. After completion of the reaction, the mixture was allowed to cool in a nitrogen stream. The DMF solution is placed in a large amount of water as it is for reprecipitation, and the resulting precipitate is filtered, washed thoroughly with water, and dried to obtain 196 mg of polymer (hereinafter referred to as “Comparative Synthesis Example 2 polymer”). Obtained.

[Comparative Example 3]
Comparative Synthesis Example 2 A stainless steel column (inner diameter 4 mm x length 10 mm) packed with polymer (350 mg) was installed in a temperature-controlled oven, and 2,2 ', 3,3', 5,5 Insulating oil (100 ppm, 350 mg) containing '-hexachlorobiphenyl (2,2', 3,3 ', 5,5'-HECBP) was poured with nitrogen gas and poured out at 130 ° C to give 298 mg of insulating oil was gotten. The 2,2 ', 3,3', 5,5'-HECBP concentration of the insulating oil was measured by gas chromatography, and the 2,2 ', 3,3', 5,5'-HECBP concentration was 96.1 ppm. Met. That is, it was found that the polymer synthesized in Comparative Synthesis Example 2 cannot effectively adsorb the halogenated aromatic compound.

[Comparative Example 4]
Comparative Synthesis Example 2 A stainless steel column (inner diameter 8 mm x length 300 mm) packed with polymer (2.0 g) was mounted in an oven with temperature control, and the actual liquid (26.5 ppm, 2.0 g) was placed in the column with nitrogen gas. After pouring and pouring at 130 ° C., 0.96 g of insulating oil was obtained. When the PCB concentration of the insulating oil was measured by gas chromatography, the PCB concentration was 26.2 ppm. That is, it was found that the polymer synthesized in Comparative Synthesis Example 2 cannot effectively adsorb PCB in the actual liquid.

The results of the above examples and comparative examples are summarized in Tables 1 and 2.

According to the present invention, it is represented by insulating oil, heat medium, lubricating oil, plasticizer, paint, ink, etc. that may contain halogenated aromatic compounds as toxic substances such as dioxins and polychlorobiphenyls that cannot be easily released to the environment. Safe and efficient use of these compounds in industries that must store organic media and in industries that must store solid materials such as paper, wood, incinerated ash, rocks, and soil that may contain these compounds. The simultaneous disassembling process and saving of the storage space for such a medium can be realized at the same time.

Claims

Porous that interacts with halogenated aromatic compounds in an attractive manner by reacting alcohols, aryl alcohols or phenols at the end of the polymer condensed with cyclodextrin and organic dibasic acid or organic dibasic acid halide Selective fixing agent for halogenated aromatic compounds contained in an organic medium, comprising a high-quality cyclodextrin polymer.
The organic dibasic acid or organic dibasic acid halide is selected from terephthalic acid, isophthalic acid, maleic acid, malic acid, malonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, phthalic acid or their halides The selective fixing agent according to claim 1.
The alcohol is selected from an alkyl group having 1 to 10 carbon atoms, the aryl alcohol is selected from benzyl alcohol, or benzyl alcohol substituted with an alkyl, aryl, or acyl group, and the phenol is phenol, alkyl, aryl, or aryl Or a selective sticking agent according to claim 1 or 2, selected from phenols substituted with acyl groups.
The selective fixing agent according to any one of claims 1 to 3, wherein a porous cyclodextrin polymer that interacts with the halogenated aromatic compound in a suction manner is immobilized on a solid support.
The selective fixing agent according to any one of claims 1 to 4, wherein the halogenated aromatic compound is dioxins, polychlorobiphenyls, or polychlorobenzenes.
The selective fixing agent according to any one of claims 1 to 5, wherein the organic medium is selected from the group consisting of an organic liquid, an insulating oil, a heat medium, a lubricating oil, a plasticizer, a paint and an ink, and a mixture thereof.
Porous that interacts with halogenated aromatic compounds in an attractive manner by reacting alcohols, aryl alcohols or phenols at the end of a polymer obtained by condensing cyclodextrin with organic dibasic acid or organic dibasic acid halide A selective fixing agent for a halogenated aromatic compound containing a cyclodextrin polymer of the above and an organic medium containing a halogenated aromatic compound are brought into contact with each other, and the halogenated aromatic compound contained in the organic medium is subjected to the halogenation. A method characterized in that an organic medium containing no halogenated aromatic compound is obtained by fixing to a porous cyclodextrin polymer that interacts with an aromatic compound in an aspiration manner.
The organic dibasic acid or organic dibasic acid halide is selected from terephthalic acid, isophthalic acid, maleic acid, malic acid, malonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, phthalic acid or their halides The method according to claim 7.
The alcohol is selected from an alkyl group having 1 to 10 carbon atoms, the aryl alcohol is selected from benzyl alcohol, or benzyl alcohol substituted with an alkyl, aryl, or acyl group, and the phenol is phenol, alkyl, aryl, or aryl Or a method according to claim 7 or 8, selected from phenols substituted with acyl groups.
10. The selective fixing agent characterized in that the porous cyclodextrin polymer that interacts with the halogenated aromatic compound in a suction manner is immobilized on a solid support. the method of.
The method according to any one of claims 7 to 10, wherein the halogenated aromatic compound is dioxins, polychlorobiphenyls, or polychlorobenzenes.
The method according to any one of claims 7 to 11, wherein the organic medium is selected from the group consisting of an organic liquid, an insulating oil, a machine oil, a heat medium, a lubricating oil, a plasticizer, a paint and an ink, and a mixture thereof.
Add organic dibasic acid or organic dibasic acid halide-containing organic solvent dropwise to cyclodextrin dissolved in organic solvent, and then add alcohols, aryl alcohols, or phenols for esterification reaction A process for producing a porous cyclodextrin polymer.
The organic dibasic acid or organic dibasic acid halide is selected from terephthalic acid, isophthalic acid, maleic acid, malic acid, malonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, phthalic acid or their halides The method of claim 13.
The alcohol is selected from aliphatic alcohols having 1 to 10 carbon atoms, the aryl alcohol is selected from benzyl alcohol or substituted benzyl alcohol, and the phenol is selected from phenol or substituted phenols, 14. The method according to 14.
The organic solvent for dissolving cyclodextrin is selected from pyridine, dimethyl sulfoxide, dimethylformamide, and 1-methylimidazole, and the organic solvent for dissolving the organic dibasic acid or organic dibasic acid halide is tetrahydrofuran, dichloromethane, 1, The process according to any of claims 13 to 15, selected from 4-dioxane, xylene, dimethylformamide and toluene.
A porous cyclodextrin polymer produced by the method according to any one of claims 13 to 16.