KR20120112832A - Agent and method for selectively anchoring halogenated aromatic compound contained in medium - Google Patents

Abstract

A porous cyclodextrin polymer which interacts with a halogenated aromatic compound by reacting alcohols, aryl alcohols or phenols at a terminal of a polymer obtained by condensing cyclodextrin with an organic dibasic acid or an organic dibasic acid halide. It provides a selective fixing agent of halogenated aromatic compounds contained in an organic medium. Furthermore, the selective fixing agent which makes it possible to facilitate the decomposition | decomposition process of a halogenated aromatic compound by selectively fixing to the halogenated aromatic compound contained in an organic medium, and removing or concentrating a halogenated aromatic compound from an organic medium is provided.

Description

Selective Fixing Agent and Selective Fixing Method of Halogenated Aromatic Compounds in the Medium {AGENT AND METHOD FOR SELECTIVELY ANCHORING HALOGENATED AROMATIC COMPOUND CONTAINED IN MEDIUM}

The present invention provides a selective fixing agent capable of trapping a halogenated aromatic compound contained in an organic medium represented by insulating oil, mechanical oil, heat medium, lubricating oil, plasticizer, paint, ink, mixtures thereof, and the like. It relates to a method of obtaining an organic medium that does not contain. More specifically, by using a porous cyclodextrin polymer having a novel structure obtained by condensing cyclodextrin and organic dibasic acid and esterifying alcohols, aryl alcohols, or phenols at the ends of the resulting condensation polymer, And a method for selectively fixing a halogenated aromatic compound contained in an organic medium. Moreover, 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 the organic medium can be selectively and efficiently fixed.

Halogenated aromatic compounds are compounds that exhibit strong toxicity to humans and animals and plants. In particular, halogenated aromatic compounds are designated by the Act on the Treatment and Cleaning of Wastes as Hazardous Substances, in particular due to fear of teratogenicity. If such compounds are present in soil, groundwater, incineration ash, washing water, machine oil and the like, it is strictly determined that these treatments should be carried out to reduce these concentrations below the reference values.

Conventionally, organic media, such as insulating oil containing a halogenated aromatic compound, were chemically processed as it was (Japanese Patent No. 261900 and Japanese Patent No. 3247505). By the way, in recent years in Japan, insulating oil with a PCB-free viewpoint or a PCB-free certificate, as well as a reclaimed oil without a polychlorobiphenyl (hereinafter referred to as "PCB") or a non-PCB certificate. Organic oils containing a very small amount (about 0.5-100 ppm, particularly about 0.5-10 ppm) of halogenated aromatic compounds have also been identified from fresh oil and regenerated oil. The chemical treatment of such large quantities of organic media in a conventional manner requires a great deal of time and useful energy, and thus remains an efficient and economical problem.

On the other hand, although the method of incineration of the organic medium containing a halogenated aromatic compound can also be taken, there are many difficult problems, such as a dioxin countermeasure, and there exists a question about safety to an environment.

Currently, the halogenated aromatic compound treatment technology has established not only a medium containing a trace amount of a halogenated aromatic compound, but also a technology for treating the halogenated aromatic compound itself, and contains a halogenated aromatic compound and a halogenated aromatic compound at a high concentration (1% or more). A process for directly treating a high concentration-containing medium (hereinafter referred to as "high concentration treatment") is beginning 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 very small amount, only the halogenated aromatic compound can be efficiently treated by the above-described high concentration treatment, and the medium from which the halogenated aromatic compound is removed is not available. As the inclusion, the length of the application can be opened and the storage place of the medium before treatment can be saved.

Japanese Unexamined Patent Application Publication No. 5-31212 discloses a method for capturing an organic halogen compound that forms an organic halogen compound inclusion complex using a modified cyclodextrin. However, the method described in Japanese Unexamined Patent Publication No. 5-31212 uses the modified cyclodextrin which is not lipophilic with respect to a method of capturing an organic halogen compound contained in an aqueous solution using the hydrophilic modified cyclodextrin. It is difficult to apply this method as it is to an organic medium system.

In view of this, the present inventors have made a thorough search for a compound capable of selectively fixing a halogenated aromatic compound by aspirating interaction with a halogenated aromatic compound contained in an organic medium, and condensed cyclodextrin and organic dibasic acid. A selective fixing agent containing a polymer has been proposed (Japanese Patent Laid-Open No. 2009-95792). The polymer containing the polymer obtained by condensing cyclodextrin and organic dibasic acid can selectively fix the halogenated aromatic compound contained in the organic medium, and the halogenated aromatic compound is brought into contact with the organic medium containing the halogenated aromatic compound. It is clear from the examples that an organic medium containing almost no content can be obtained. However, in this prior art, since the recovery rate of the organic medium which hardly contains a halogenated aromatic compound is not so high (21-34% in the Example), development of the selective fixing agent which can raise the recovery rate of an organic medium further is desired.

On the other hand, Japanese Patent No. 3010602 discloses a method for synthesizing various cyclodextrin polymers, but it does not disclose contacting them with an organic medium to selectively fix the contained halogenated aromatic compound.

As disclosed in Japanese Unexamined Patent Publication Nos. Hei 5-31212, Japanese Unexamined Patent Publication No. 2009-95792, and Japanese Patent No. 3010602, cyclodextrins are well known as compounds capable of encapsulating various compounds. Cyclodextrins are cyclic oligosaccharides in which six, seven or eight glucoses are cyclically bonded, and are called α-, β- or γ-cyclodextrins, respectively. Cyclodextrin has the property of enclosing various compounds in the cyclic vacancy. By this property, a hydrophobic substance is contained in cyclodextrin, it can be dissolved in water, or can be used for various adsorption and separation operations, and the like. However, since cyclodextrin has high water solubility, its use in organic solvents is limited. Thus, various attempts have been made to make the cyclodextrin water insoluble.

A method of polymerizing is mentioned as an attempt to make cyclodextrin water-insoluble. It has been known for a long time that the cyclodextrin derivative is reacted with chloromethyl polystyrene and the cyclodextrin is immobilized to a water-insoluble high molecular compound. It is also well known to form a high molecular compound by crosslinking cyclodextrin with epichlorohydrin.

Japanese Laid-Open Patent Publication No. 2009-95792 discloses a preparation of a polymer that condensates cyclodextrin and organic dibasic acid to suction-interact with a halogenated aromatic compound. As mentioned above, the polymer manufactured by Unexamined-Japanese-Patent No. 2009-95792 is a carboxyl group derived from phthalic-acid dichloride in the terminal.

Japanese Patent No. 3010602 discloses polymerizing a cyclodextrin by reacting terephthalic acid. In Japanese Patent No. 3010602, a method of condensing cyclodextrin and terephthaloyl dichloride and producing a cyclodextrin polymer whose terminal is a carboxyl group derived from terephthaloyl dichloride, a condensation of cyclodextrin and dimethyl terephthalate, and the terminal terephthalic acid A method for producing a cyclodextrin polymer, which is a methyl ester derived from dimethyl, and a method for producing a crosslinked cyclodextrin polymer by condensing cyclodextrin and various organic dibasic acids are disclosed. In the examples of Japanese Patent No. 3010602, it is described that the cyclodextrin polymer thus prepared can be molded into a film and decomposed by a specific enzyme.

The present invention provides a selective fixing agent which makes it possible to facilitate the decomposition treatment of only halogenated aromatic compounds by selectively fixing the halogenated aromatic compounds contained in the organic medium and removing or concentrating the halogenated aromatic compounds from the organic medium. It aims to do it. Moreover, this invention provides the method of selectively collecting the halogenated aromatic compound contained in an organic medium using such a selective fixing agent, and thereby obtaining the organic medium which does not contain a halogenated aromatic compound with high recovery rate.

The present inventors use a water-insoluble novel porous cyclodextrin polymer, produced as a water-soluble cyclodextrin, as a selective fixing agent to selectively collect a halogenated aromatic compound contained in an organic medium and to contain no halogenated aromatic compound. It was found that the medium can be obtained with high recovery rate.

Aspects of the present invention are as follows:

1.Contains a porous cyclodextrin polymer which interacts with the halogenated aromatic compound 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. The selective fixing agent of the halogenated aromatic compound contained in the organic medium.

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 a halide thereof. Selective fixing agent described in.

3. Alcohol is 1? Selected from alkyl groups of 10, aryl alcohols are selected from benzyl alcohols or benzyl alcohols substituted with alkyl, aryl, or acyl groups, and phenols are selected from phenols or phenols substituted with alkyl, aryl, or acyl groups, The selective fixing agent of Claim 1 or 2.

4. The porous cyclodextrin polymer which interacts with the halogenated aromatic compound by suction is immobilized on the solid carrier. The selective fixing agent in any one of 3.

5. Said 1-I whose halogenated aromatic compound is dioxins, polychloro biphenyls, or polychlorobenzenes. The selective fixing agent in any one of 4.

6. 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. The selective fixing agent in any one of 5.

7. Contains a porous cyclodextrin polymer which interacts with the halogenated aromatic compound by reacting alcohols, aryl alcohols or phenols at the ends of the polymer condensed with cyclodextrin and organic dibasic acid or organic dibasic acid halide. The contact fixing agent of the halogenated aromatic compound and the organic medium containing the halogenated aromatic compound are brought into contact with each other, and the halogenated aromatic compound contained in the organic medium is fixed to the porous cyclodextrin polymer which attracts and interacts with the halogenated aromatic compound. An organic medium containing no halogenated aromatic compound is obtained.

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 halides thereof. The method described in.

9. Alcohols have 1 or more carbon atoms? Selected from alkyl groups of 10, aryl alcohols are selected from benzyl alcohols or benzyl alcohols substituted with alkyl, aryl, or acyl groups, and phenols are selected from phenols or phenols substituted with alkyl, aryl, or acyl groups, The method as described in said 7 or 8.

10. The porous cyclodextrin polymer which interacts with the halogenated aromatic compound by suction is immobilized on a solid carrier, and the above-mentioned 7? The method as described in any one of 9.

11. Said halogen atom aromatic compound is dioxins, polychloro biphenyls, or polychlorobenzenes; The method according to any one of 10.

12. The organic medium is selected from the group consisting of organic liquids, insulating oils, machine oils, heating mediums, lubricants, plasticizers, paints and inks, and mixtures thereof. The method according to any one of 11.

13. A cyclodextrin dissolved in an organic solvent is added dropwise and stirred with an organic dibasic acid or organic dibasic acid halide-containing organic solvent, followed by esterification by adding alcohols, aryl alcohols, or phenols. Method 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 halides thereof. The method described in.

15. Alcohol is 1? The method according to 13 or 14 above, wherein the aryl alcohols are selected from benzyl alcohol or substituted benzyl alcohol, and the phenols are selected from phenol or substituted phenols.

16. The organic solvent which dissolves cyclodextrin is selected from pyridine, dimethyl sulfoxide, dimethylformamide, and 1-methylimidazole, and the organic solvent which dissolves organic dibasic acid or organic dibasic acid halide is tetrahydro. 13? Selected from furan, dichloromethane, 1,4-dioxane, xylene, dimethylformamide and toluene; The method according to any one of 15.

Hereinafter, the present invention will be described in detail.

In this invention, a "halogenated aromatic compound" refers to the whole compound in which one or more fluorine, chlorine, bromine, and iodine were substituted by the aromatic compound. In the present invention, for example, polychlorobiphenyls (PCB), dioxins, freons, polychloronaphthalenes, polychlorobenzenes, and the like. PCB is a general term for a compound in which several chlorine atoms are substituted in the biphenyl skeleton, and a large number of isomers exist depending on the substitution position and the number of substitution of the chlorine atom. Dioxins refer to specific compounds designated by the dioxin countermeasures Special Measures Act in the sense of consultation. In the present invention, all of the halogenated compounds suspected as endocrine disrupting substances (environmental hormones) are included.

In the present invention, the "organic medium" containing a halogenated aromatic compound generally refers to an organic solvent generally, and especially the organic solvent which melt | dissolves a halogenated aromatic compound favorably, More specifically, in a use aspect, it contains a halogenated aromatic compound. It means insulating oil, mechanical oil, heat medium, lubricating oil, plasticizer, paint and ink which are highly likely to be used, and mixtures thereof. In the present invention, the "organic medium" means most of the organic medium described above (for example, 60% or more), and in some cases water may be contained, but the whole organic medium containing the halogenated aromatic compound is used. The property as is not an aqueous solution but the organic solution itself.

In addition, in order to decompose the halogenated aromatic compounds contained in the solid material (for example, paper, wood, incineration ash, rock, soil, etc.), the halogenated aromatic compounds contained in these solid materials are extracted and transferred to the organic medium. It can become the "organic medium containing a halogenated aromatic compound" which is the process target of the selective fixing agent of this invention.

As used herein, the term "interacting with a halogenated aromatic compound by suction" means interacting with the above-mentioned halogenated aromatic compound by suction (that is, not by repulsive force), and such characteristics. The compound which has a general formula is called "compound which interacts with a halogenated aromatic compound by suction." Such compounds have cyclic moieties, substituents, sequences and the like that interact with the halogenated aromatic compounds by suction. In this specification, the "compound which interacts with a halogenated aromatic compound by suction" may be abbreviated as "aspirating interaction compound", "interaction compound", or "interaction compound" in some cases. have.

In the present invention, "selectively fixing" a halogenated aromatic compound means that only the halogenated aromatic compound contained by dissolving, dispersing, etc. in the organic medium or the association of the organic medium molecule which contains the said halogenated aromatic compound inside is mutually. It acts and introduces or fixes this. In this specification, "fixing" does not necessarily mean that the adhesive is normally performed, including all of chemical bonding and adhesion, physical adsorption and suction, or simply caught. For example, in the case of a state in which the halogenated aromatic compound is in a state of being interacted with the halogenated aromatic compound at a very close distance for a predetermined time or in a state of being in contact with the predetermined time by aspirational interaction, the term "sticking" in a broad sense is referred to herein. It shall correspond to the state which became. That is, the "selective fixing agent" of the present invention means that the active ingredient contained in the selective fixing agent interacts strongly with the halogenated aromatic compound contained in the organic medium so as to properly introduce or fix the halogenated aromatic compound into the active component molecular structure. In addition to a medicament, it is meant a medicament which is capable of at least temporarily contacting such an active ingredient with a halogenated aromatic compound or being able to remain very near.

Thus, the selective fixing agent of the present invention includes compositions capable of fixing them by aspirating interaction with halogenated aromatic compounds. As an active ingredient of such a composition, a porous cyclodextrin polymer obtained by reacting alcohols, aryl alcohols or phenols at the terminal of a polymer obtained by condensation of cyclodextrin with an organic dibasic acid is mentioned. The compound which aspirates by interacting with the halogenated aromatic compound illustrated here is a compound which has in a molecule the cyclic part of the cyclodextrin which can aspirate to interact with a halogenated aromatic compound in a molecular structure, and this interaction compound is At least in an organic medium. The aspiratingly interacting moiety present in the interacting compound molecule, ie the cyclic moiety of the cyclodextrin, interacts with the halogenated aromatic compound, thereby fixing the halogenated aromatic compound to or near the interacting moiety.

The selective fixing agent of the present invention may contain, as an active ingredient, a compound which interacts with the above-mentioned halogenated aromatic compound as an active ingredient, and may contain auxiliaries such as a carrier, a substrate, a diluent and the like as necessary. Moreover, the compound which aspirates | interacts with the halogenated aromatic compound which is an active component may be immobilized to the support | carrier or a base material as needed. For example, aspirable interactions with halogenated aromatic compounds on solid carriers such as silica gel, polymer beads, ion exchange resins, glass, filters, membranes, various network structures or lattice structures, foams, porous materials, etc. The compound can be immobilized. Immobilization of the carrier or substrate of the compound that aspirates interacting with the halogenated aromatic compound is relatively weak, such as hydrophobic interaction, van der Waals forces, in addition to relatively strong chemical bonds, for example, represented by covalent or ionic bonds. It can also be done by physical interaction by force.

As a compound which interacts with a halogenated aromatic compound by suction, the polymer which made alcohol, aryl alcohol, or phenol react at the terminal of the polymer which condensed cyclodextrin and organic dibasic acid is mentioned. Cyclodextrin is a cyclic oligosaccharide in which six, seven or eight glucoses are cyclically bonded, and are called α-, β- or γ-cyclodextrins, respectively. Organic dibasic acids include, for example, aliphatic dicarboxylic acid, aromatic dicarboxylic acid, alicyclic dicarboxylic acid, fatty acid, and in the present invention, react with a -CH ₂ OH group in a cyclodextrin molecule It is a compound which can be condensed in order and 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. Organic dibasic acid halide refers to the acid halide of said organic dibasic acids. Especially in this invention, it is preferable to use terephthalic acid which is an organic dibasic acid, or terephthalic acid dichloride (terephthaloyl dichloride) which is an organic dibasic acid halide.

The reaction of alcohols, aryl alcohols or phenols at the polymer terminal means that the carboxyl group derived from the organic dibasic acid remaining at the terminal of the condensation polymer is end capped with a specific substituent. In order to end cap a carboxyl group, alcohol, aryl alcohol, or phenol can be made to react and esterify. In the present invention, alcohols, aryl alcohols or phenols are reacted at the terminals, for example, having 1 to 3 carbon atoms. Alcohols selected from the alcohol of 10, aryl alcohols selected from benzyl alcohol or substituted benzyl alcohols, or phenols selected from phenols or substituted phenols are reacted with carboxyl end groups to form alkyl esters, aryl esters or phenyl esters. Means that. For example, when the condensation polymer is reacted with methanol, the end group is methyl ester (-COOMe), when it is reacted with ethanol, it is ethyl ester (-COOEt), and when it is reacted with benzyl alcohol, it is benzyl ester (-COOBz).

Here, when a plurality of cyclodextrins and organic dibasic acids are condensed in order, and the terminals are treated with alcohols, aryl alcohols or phenols, for example, how many cyclodextrins and organic dibasic acids are in total? Even what is called generally "oligomer" which was condensed about 10 pieces, in this specification, all shall be generically called "polymer." 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 by this invention can be represented by the following formula, for example:

[Formula 1]

In this formula, the part of cyclodextrin is represented by cone trapezoid, and terephthalic acid is used as organic dibasic acid. The hydroxyl group and organic dibasic acid in a cyclodextrin are couple | bonded alternately by the ester bond, and forms the mesh-like structure. And the terminal of a polymer is capped by the methyl group as a result of reaction with methanol.

For example, when condensation of terephthaloyl dichloride as γ-cyclodextrin and an organic dibasic acid halide, followed by methanol reaction at the end, the reaction proceeds in the following scheme to obtain a polymer:

[Formula 2]

One acid chloride group (-COCl) of terephthaloyl dichloride reacts with the —CH ₂ OH group of γ-cyclodextrin to be ester-bonded. And again, the acid chloride group of the other one, the reaction of the -CH ₂ OH group and the other γ- cyclodextrin. This is repeated to obtain a condensation polymer. Cyclodextrins have a number of hydroxyl groups, the substituents involved in condensation being part of -CH ₂ OH, such groups being 6 for α-cyclodextrin, 7 for β-cyclodextrin, and γ-cyclodextrin Is present in eight molecules. The condensate obtained may have a crosslinked structure or a three-dimensional network structure in addition to alternating condensation of cyclodextrin and organic dibasic acid. When methanol is reacted at the end of the condensation reaction, the terminal acid chloride group is -COOCH ₃ .

Here, by vigorously stirring during the condensation reaction of cyclodextrin and organic dibasic acid (or organic dibasic acid halide), it was found that a spherical porous polymer suitable as the selective fixing agent of the present invention finally obtained can be obtained. Stirring is performed using a magnetic stirrer, a stirring rod, or the like, in particular, using a stirring rod provided with stirring blades, and using a stirring apparatus that can stir evenly so that the stirring speed does not differ between the upper and lower portions of the reaction solution. It is suitable to carry out by. For example, as shown in FIG. 4, when the max blend with 4 blade | wings attached to the upper part is used, it can stir uniformly in the upper part and the lower part in a reactor. In addition, the stirring blade of various shapes can be used, if it is a stirring blade which can raise stirring efficiency. In order to use it as a selective fixing agent of a halogenated aromatic compound, it turned out that it is important to obtain a polymer of porous shape, especially spherical porous shape. Here, a porous shape generally means the shape which has a small hole in a polymer. A spherical porous shape means that the minute lumps of a spherical shape aggregate and form the shape with the small hole as a whole. As an example, the electron micrograph of the spherical porous cyclodextrin polymer (The methyl group end capped to the condensation polymer of (gamma) -cyclodextrin and a terephthalo dichloride) used for this invention manufactured by the synthesis example 1 is illustrated in FIG. do. According to FIG. 1, it turns out that the polymer used for this invention has the porous shape which the fine spherical crystal gathered. Generally as a method of obtaining an organic polymer porous body, chemical methods, such as acid and alkali treatment, the foaming method at the time of manufacture, etc. are well known. The polymer used as the selective fixing agent of the present invention may have a special shape by stirring during condensation.

In addition, the electron micrograph of the condensation polymer (gamma which does not end-cap end with alcohol etc.) of (gamma)-cyclodextrin and diterephthaloyl dichloride manufactured by the comparative synthesis example 1 for the comparison is shown in FIG. It can be seen that the polymer of FIG. 2 also has a porous shape, but the spheres of the spherical crystal are incomplete. The polymer of FIG. 2 is in the shape of spherical fusion, and the surface area of the polymer of FIG. 2 is narrower than that of the polymer of FIG. 1. In addition, the electron micrograph of the polymer synthesize | combined by the comparative synthesis example 2 is shown in FIG. It is surprising that, due to the slight difference in the microstructure of the polymer, a difference in performance as a selective fixing agent of the halogenated aromatic compound contained in the organic medium is observed.

1 is an electron micrograph of the porous cyclodextrin polymer (terephthalic acid γ-CD-methyl polymer) of the present invention.
2 is an electron micrograph of a condensation polymer (Comparative Synthesis Example 1) produced by the method according to JP-A-2009-95792.
3 is an electron micrograph of a polymer (comparative synthesis example 2) produced by the method according to Japanese Patent No. 3010602.
It is a schematic diagram of an example of the stirring blade used for the method of this invention. 4A is a side view of the stirring vane that can be used in the method of the present invention. 4B is a view of the stirring vane that can be used in the method of the present invention as viewed from above.

The cyclodextrin polymer obtained by condensing cyclodextrin as an active ingredient of the selective fixing agent of the present invention and organic dibasic acids and reacting alcohols, aryl alcohols or phenols at the terminals can be produced, for example, by the following method. :

γ-cyclodextrin is dissolved in an organic solvent (for example, pyridine, dimethylsulfoxide, dimethylformamide, etc., preferably dry pyridine). On the other hand, terephthaloyl dichloride is dissolved in an organic solvent (e.g., tetrahydrofuran, dichloromethane, 1,4-dioxane, etc., preferably dry tetrahydrofuran), and this is dissolved in the prepared γ-cyclodextrin solution. Dropping At this time, heat is generated by the condensation reaction, and therefore, it is preferable to drop the γ-cyclodextrin solution while cooling with an ice bath or the like. After that 50? The reactor is immersed in a 70 ° C hot water bath, and the reaction solution is vigorously stirred. After completion of the reaction, the temperature inside the reaction vessel was lowered slightly (approximately 5 to 10 ° C.), and alcohols (alcohols having 1 to 10 carbon atoms such as methanol, ethanol, propanol, butanol and octanol) and aryl alcohols (benzyl alcohol or alkyl) , Benzyl alcohol substituted with aryl or acyl group) or phenols (phenols substituted with phenol, alkyl, aryl or acyl group) are added, and further stirring is continued. When the obtained crystals are washed with a cleaning liquid such as alcohol, water or acetone and dried, a cyclodextrin polymer obtained by condensing γ-cyclodextrin and terephthalic acid and reacting alcohols, aryl alcohols or phenols at the terminal can be obtained. . In addition to γ-cyclodextrin, α- and β-cyclodextrin can also form the same condensation polymer. In the present specification, the polymer thus obtained is referred to as "terephthalic acid-γ-CD-methyl polymer" (when the end is treated with methanol), "terephthalic acid-γ-CD-ethyl polymer" (when the end is treated with ethanol), Terephthalic acid-γ-CD-benzyl polymer ”(when the end is treated with benzyl alcohol),“ terephthalic acid-γ-CD-phenyl polymer ”(when the end is treated with phenol) and the like are sometimes abbreviated. It is a porous cyclodextrin polymer which is a compound which interacts with a halogenated aromatic compound by suction.

Next, a polymer obtained by treating a terminal of a polymer obtained by condensation of a commercially available γ-cyclodextrin (hereinafter referred to as "γ-CD") with a terephthaloyl dichloride (hereinafter, "terephthalic acid-γ-CD-methyl polymer" Or "TPGCDM polymer").

First, gamma -CD is dissolved in an organic solvent (for example, pyridine, dimethyl sulfoxide, dimethylformamide, 1-methylimidazole and the like). The concentration of γ-CD in the organic solvent is 5? It is preferable that it is 20 weight%. On the other hand, 4? Of the prepared γ-CD? 12 times (mol) of dichloride terephthaloyl is concentrated in an organic solvent (for example, tetrahydrofuran, dichloromethane, 1,4-dioxane, xylene, dimethylformamide, toluene, etc.). It is melt | dissolved in 40 weight%, it is dripped at the previously prepared gamma-CD solution, and it is stirred vigorously. Stirring is performed using a magnetic stirrer, a stirring rod, or the like, in particular, using a stirring rod provided with stirring blades, and using a stirring apparatus that can stir evenly so that the stirring speed does not differ between the upper and lower portions of the reaction solution. It is suitable to carry out. For example, as shown in FIG. 4, when the max blend with 4 blade | wings attached to the upper part is used, it can stir uniformly in the upper part and the lower part in a reactor. In addition, the stirring blade of various shapes can be used, if it is a stirring blade which can raise stirring efficiency. Since condensation reaction between γ-CD and terephthaloyl dichloride proceeds, heat is generated. Therefore, it is preferable to perform dropping while cooling the γ-CD solution in an ice bath or the like. Preferably the temperature in the reaction vessel is about 0? Maintain a range of 20 ° C. After dropping, the temperature in the reaction vessel was adjusted to about 40? It raises to the range of 70 degreeC, and stirs. Next, lower the temperature slightly in the reaction vessel to about 60? 65 ° C, and then 30? Alcohols in an amount of 80% by weight (preferably aliphatic alcohols having 1 to 10 carbon atoms), aryl alcohols (preferably benzyl alcohol or substituted benzyl alcohol), or phenols (preferably phenol or substituted phenols) Add. For example, when methanol is added as alcohol, it is about 1? Stirring can be continued for 24 hours. In this way, the crystals of the cyclodextrin polymer end capped with a methyl group are precipitated, so that the precipitated crystals are collected by filtration and washed with water and acetone to obtain the cyclodextrin polymer (terephthalic acid-γ-CD-methyl polymer) of the present invention. . Identification of the obtained polymer can be performed by infrared absorption, and observation of the form can be performed by an electron microscope.

Comparing the cyclodextrin polymer of the present invention to the conventional condensed polymer which does not end cap and the cyclodextrin polymer produced by the conventional method, the cyclodextrin polymer of the present invention has a form in which fine spherical crystals are collected. It can be seen. The cyclodextrin polymer of the present invention is more spherical in shape of a sphere, and is not crushed or deformed. The cyclodextrin polymer of the present invention has a larger surface area than conventional polymers and can be contacted with more organic liquids. Therefore, the compound which aspirates interacting with the halogenated aromatic compound obtained by such a method can be used as a selective fixing agent as it is, and can be set as the selective fixing composition which added various additives or adjuvant as needed. In the case where the cyclodextrin polymer of the present invention is used for separation of a compound contained in an organic liquid, the cyclodextrin polymer can be easily separated by filling the cyclodextrin polymer with a column, for example, and circulating the organic liquid therein. .

Next, the method of selectively removing a halogenated aromatic compound from an organic medium using the selective fixing agent of this invention is demonstrated concretely.

The organic medium containing the halogenated aromatic compound used for this invention contains the halogenated aromatic compound mentioned above at least 1 sort (s). The halogenated aromatic compound may be dissolved at any concentration in the organic medium. Particularly, when the content of the halogenated aromatic compound is about 0.5-1%, the halogenated aromatic compound is said to contain "extreme", "trace" or "low concentration". In particular, an organic medium containing a low concentration of halogenated aromatic compounds has a very small amount of halogenated aromatic compounds to be treated, but the volume of the organic medium itself becomes very large, thus causing difficulty in storage and requiring a large amount of time for chemical treatment. do. Therefore, if the halogenated aromatic compound dissolved in a trace amount can be concentrated and separated from the organic medium to be divided into the halogenated aromatic compound to be treated and the organic medium to be recycled, the treatment efficiency of the halogenated aromatic compound is increased, and the storage problem of such organic medium is increased. Can also be solved.

Organic media which are particularly likely to contain halogenated aromatic compounds are, in addition to various organic liquids, insulating oils, machine oils, heat mediums, lubricants, plasticizers, paints, inks and mixtures thereof. The organic medium containing the 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, a selective fixing agent of the present invention containing a compound which interacts with the halogenated aromatic compound 10 times-50 times, preferably 50-200 times (molar basis) with respect to the halogenated aromatic compound contained therein is introduced. And stir sufficiently. The compound or composition containing such a compound that interacts with the halogenated aromatic compound as an active ingredient in the selective fixing agent of the present invention or is dispersed in the organic medium is brought into contact with the halogenated aromatic compound contained in the organic medium. The halogenated aromatic compound is fixed to or near the suctioned interaction part by the interaction with the suction interaction part in the compound which interacts with the halogenated aromatic compound by suction. Depending on the amount of organic medium to be treated, the concentration of the halogenated aromatic compound, and the amount of the selected fixing agent of the present invention, generally 5 hours? It can be contacted by stirring etc. over several days. A fixing reaction can be performed suitably at normal temperature, and can also heat as needed.

In this way, after the halogenated aromatic compound contained in the organic medium is fixed to the compound which interacts with the halogenated aromatic compound by suction, only the suctionable interacting compound (or the composition containing the compound) to which the halogenated aromatic compound is fixed is separated. do. Separation may be performed using the existing solid-liquid separation technique, and the method of using a centrifugal separator and a pressure filter is mentioned, for example. The filter at the time of separation can be performed using a commercially available filter, a glass filter, a membrane | film | coat, cotton wool, a metal, resin, etc. Any filter or membrane may be used as long as the pore diameter to separate clathrate compounds contained in the selective fixing agent of the present invention can be used. However, in consideration of the particle size of a general interaction compound, a pore diameter of about 0.1-100 μm is used. It is preferable.

The suction interaction compound to which the halogenated aromatic compound obtained by the separation is fixed is dehaled only the halogenated aromatic compound fixed as necessary, and the halogenated aromatic compound fixed to the suction interaction compound or the halogenated aromatic compound obtained by the desorption operation. After diluting as needed, decomposition treatment can be performed by chemical processing methods, such as a chemical extraction decomposition method, for example.

In the organic medium obtained after separating the suction interaction compound in which the halogenated aromatic compound is fixed, the halogenated aromatic compound is substantially completely removed. Therefore, because the halogenated aromatic compound is contained, the organic medium that had to be stored in the past can be reused or disposed of by an ordinary method such as incineration disposal.

As the selective fixing agent of the present invention, a compound which suction-interacts with the halogenated aromatic compound as the active ingredient is, for example, silica gel, polymer beads, ion exchange resins, foams, films, membranes, various lattice structures and network structures, porous What has been immobilized on a carrier such as a substance can be preferably used. For example, a solid carrier such as silica gel, polymer beads, or ion exchange resin, on which the suction-interacting compound of the present invention is supported, is laminated in a column, and the organic medium containing a halogenated aromatic compound is subjected to atmospheric pressure or pressure. By making it flow, it interacts with the said suction interaction compound, and it becomes possible to remove the halogenated aromatic compound contained in an organic medium effectively. Alternatively, the organic medium containing the halogenated aromatic compound is subjected to atmospheric pressure or reduced pressure filtration using a substance in which the suction-interacting compound of the present invention is supported on a solid carrier such as a filter or a membrane, so that the halogenated aromatic compound contained in the organic medium is membrane or By sticking to a filter, it becomes possible to remove a halogenated aromatic compound. Alternatively, the organic solvent containing a halogenated aromatic compound is introduced into a solid carrier such as a foam, a network structure, a lattice structure, or a porous material in an organic medium containing a halogenated aromatic compound to form a network portion or a lattice shape of the solid support. The organic medium is absorbed in the portion or the hole portion, and the contained halogenated aromatic compound is fixed, and then, if necessary, pressure is applied to the solid carrier (for example, by weaving or the like) to remove the halogenated aromatic compound. Organic medium can be obtained.

Thus, the composition which immobilized the compound which aspirates interacting with the halogenated aromatic compound of this invention to a solid carrier is used for the method of removing a halogenated aromatic compound by the batch process from the organic medium containing a halogenated aromatic compound, It is also very preferably used for a method of treating continuously.

As the selective fixing agent of the present invention, the porous polymer itself which interacts with the halogenated aromatic compound as an active ingredient by suction is filled with a column or the like, and the organic medium containing the halogenated aromatic compound is allowed to flow under normal pressure or under pressure to halogenate from the organic medium. It is also possible to remove aromatic compounds.

Thus, the selective fixing agent of this invention can selectively fix the halogenated aromatic compound contained in the organic medium, and can remove this from an organic medium. By using the selective fixing agent of the present invention, since only a small amount of halogenated aromatic compounds that require strict decomposition treatment can be removed and concentrated from the organic medium that has been stored because a small amount of halogenated aromatic compounds are dissolved, the decomposition treatment efficiency of the halogenated aromatic compounds is increased. On the other hand, the organic solvent recovered efficiently can be treated or reused in a conventional manner. The method of removing the halogenated aromatic compound contained in the organic medium by using the selective fixing agent of the present invention is a relatively easy method of adding and dispersing the selective fixing agent in the organic medium to fix the halogenated aromatic compound by stirring or the like, and separating it. In addition, since it can be performed at normal temperature, it is a safe method in which a halogenated aromatic compound does not spread to air | atmosphere. As the selective fixing agent of the present invention, by using a substance immobilized on various solid carriers of a compound which interacts with the halogenated aromatic compound by suction, it is possible to continuously remove the halogenated aromatic compound contained in the organic medium.

Example

Synthesis Example 1 A polymer obtained by treating a terminal of a polymer obtained by condensing γ-cyclodextrin (hereinafter referred to as "γ-CD") with a terephthaloyl dichloride (hereinafter, "terephthalic acid-γ-CD-methyl polymer" Or `` TPGCDM polymer ''

To a 1 l four-necked separable flask equipped with a dropping funnel, a three-way cock with a balloon, a valve and a stirring rod (stirred by agitator), dry γ-CD (50 g, 0.039 mol, 1% or less of water content) Ind.) And a special pyridine (660 ml, Wako Pure Chemical Industries, Inc.) were added and stirred at room temperature for 1 hour. After the flask was immersed in an ice bath, terephthaloyl dichloride (78.3 g, 0.39 mol, Tokyo Chemical Industry) dissolved in special tetrahydrofuran (220 mL, Wako Pure Chemical Industries, Ltd.) was added dropwise over 1 hour. After dripping, the ice bath was released and stirred for 3 hours at 70 degreeC of internal temperature by the hot water bath (70 degreeC). After completion | finish of reaction, internal temperature was lowered to 65 degreeC, primary methanol (100 ml, Chesei Chemical Industry) was added, and it stirred for 2 hours. After the crystals were suction filtered, the obtained crystals were washed in the order of water (400 mL x 3) and primary acetone (400 ml x 1, Junsei Chemical Industry), and the obtained solid was vacuum dried overnight at 120 deg. 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") by TPGCDM polymer Choice of fastness

A stainless steel column (inner diameter 4 mm × length 10 mm) filled with TPGCDM polymer (240 mg) was mounted in an oven equipped with temperature control, and the 2,2 ＇, 3,3＇, 5,5＇-HECBP was placed in the column. The containing insulating oil (concentration: 100 ppm, total weight: 400 mg, the insulating oil as high pressure insulating oil of Taniguchi Petroleum Refining Co., Ltd.) was poured into nitrogen gas, and it poured out at 130 degreeC, and 349 mg of insulating oil was obtained. Internal standard method by SIM (selective ion monitoring) method using QCMS-QP5050 (SHIMADZU) and M / Z 360 for 2,2 ＇, 3,3＇, 5,5＇-HECBP concentration of the insulating oil Internal standard: 2,2 ', 4,4', 5,5'-hexachlorobiphenyl), and 2,2 ', 3,3', 5,5'-HECBP was not contained. . The results are shown in Table 1.

Example 2 Selective Fixation of Polychlorobiphenyl (hereinafter referred to as "PCB") by TPGCDM Polymer

A stainless steel column (inner diameter of 8 mm × length of 300 mm) filled with TPGCDM polymer (1.5 g) was mounted in an oven with temperature control, and the PCB was actually dissolved in the column, leaving the insulating oil (hereinafter, “real liquid”). PCB concentration: 26.5 ppm, total weight: 2.6 g) was poured into nitrogen gas, and it injected out at 130 degreeC, and 1.6 g of insulating oil was obtained. PCB concentration of the insulating oil was measured by the gas chromatography method by the method of the 1st table of Table 3 of the publication no. The results are shown in Table 2.

Synthesis Example 2 Synthesis of a polymer (hereinafter referred to as "terephthalic acid-β-CD-methyl polymer" or "TPBCDM polymer") treated with a methyl group at the terminal of a polymer obtained by condensing β-CD with terephthaloyl dichloride

In a 1 L four-necked separable flask with a dropping funnel, a three-cock cocked balloon, a valve and a stirring rod (stirred by agitator), dry β-cyclodextrin (hereinafter abbreviated as β-CD, 50 g, 0.044 mol, water content 1% or less, Junsei Chemical Co., Ltd., and a high-grade pyridine (660 mL, Wako Pure Chemical Industries, Ltd.) were added, and the mixture was stirred at room temperature for 1 hour. After the flask was immersed in an ice bath, terephthaloyl dichloride (89.4 g, 0.44 mol, Tokyo Chemical Industry) dissolved in special tetrahydrofuran (230 mL, Wako Pure Chemical Industries, Ltd.) was added dropwise over 1 hour. After dripping, the ice bath was released and stirred for 4 hours at 70 degreeC of internal temperature by the hot water bath (70 degreeC). After completion of the reaction, the internal temperature was lowered to 65 占 폚, and primary methanol (35.6 mL, 0.88 mmol, Junsei Chemical) was added and stirred for 4 hours. After suction filtration of the crystals, the obtained crystals were washed in the order of primary methanol (400 ml × 2, Vonsei Chemical), water (400 mL × 3), and primary acetone (400 ml × 2, Vonsei Chemical). The solid was vacuum dried at 120 ° C. overnight. 98.7 g of TPBCDM polymer were obtained.

IR (KBr): 3448, 1718, 1277, 1105, 1018, 731 cm ^-1

Synthesis Example 3 6]

In Synthesis Example 2, a terephthalic acid-β-CD-ethyl polymer (hereinafter referred to as "TPBCDE") was synthesized in the same manner as in Synthesis Example 2 except that primary ethanol (Josesei Chemical) was used instead of primary methanol. Synthesis Example 3

IR (KBr) 3448, 1717, 1277, 1105, 1018, 731 cm ^-1

Similarly, terephthalic acid (beta) -CD-propyl polymer (henceforth "TPBCDP") was synthesize | combined using the special 2-propanol (Tokyo Chemical Industry) (synthesis example 4).

IR (KBr) 3448, 1718, 1276, 1103, 1018, 732 cm ^-1

Similarly, terephthalic acid (beta) -CD-benzyl polymer (henceforth "TPBCDB") was synthesize | combined using the special 2-benzyl alcohol (Bussey Chemical) (synthesis example 5).

IR (KBr) 3448, 1718, 1274, 1104, 1018, 731 cm ^-1

Similarly, terephthalic acid (beta) -CD-octyl polymer (henceforth "TPBCDO") was synthesize | combined using the special grade 1-octanol (Jansei 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 by TPBCDM Polymer

A stainless steel column (inner diameter 4 mm × length 10 mm) filled with the TPBCDM polymer (350 mg) obtained in Synthesis Example 2 was mounted in an oven with temperature control, and the column was equipped with 2,2 kPa, 3,3 kPa. 2,69 mg of insulating oil was obtained by pouring the insulating oil containing 5,5＇-HECBP (concentration: 100 ppm, total weight: 350 mg, high pressure insulating oil from Taniguchi Petroleum Refining Co., Ltd.) with nitrogen gas and pouring it at 130 ° C. lost. The 2,2 ', 3,3', 5,5'-HECBP concentration of the insulating oil was measured by gas chromatography, and 2,2 ', 3,3', 5,5'-HECBP was not contained. . The results are shown in Table 1.

Example 4 7] Synthesis Example 3? Selective Fixation of 2,2＇3,3＇5,5＇-HECBP by Polymers Synthesized in 6

Synthesis Example 3? Using TPBCDE, TPBCDP, TPBCDB and TPBCDO synthesized in 6, the selective fixation test of 2,2'3,3'5,5'-HECBP was performed in the same manner as in Example 3. The results are listed in Table 1 and described.

Example 8 Selective Fixation of PCB by TPBCDM Polymer

A stainless column (inner diameter 8 mm × length 300 mm) filled with the TPBCDM polymer (2.0 g) obtained in Synthesis Example 2 was mounted in an oven equipped with temperature control, and the actual liquid used in Example 2 in the column (PCB concentration: 26.5 ppm and total weight: 2.0 g) were poured into nitrogen gas and poured out at 130 degreeC, and 962 mg of insulating oil was obtained. As a result of measuring the PCB concentration of the insulating oil by gas chromatography, no PCB was contained. The results are shown in Table 2.

[Example 9? 12] Synthesis Example 3? Selection of PCB by Polymer Synthesized in 6

Synthesis Example 3? Using TPBCDE, TPBCDP, TPBCDB and TPBCDO synthesized in 6, the selective fixation test of the PCB was carried out in the same manner as in Example 8. The results are listed in Table 2 and described.

[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, terephthalic acid γ-CD whose end is not treated with alcohol or the like was synthesized according to the method described in Synthesis Example 1 of JP-A-2009-95792.

Dry γ-cyclodextrin (50 g, 0.039 mol, water content 1% or less, Huxey) in a 1 L four-necked separable flask equipped with a dropping funnel, a triangular cock with a balloon, a valve and a stirring rod (stirred by agitator) Chemical industry) and a high-grade pyridine (660 ml, Wako Pure Chemical Industries) were added and stirred at room temperature for 1 hour. After the flask was immersed in an ice bath, terephthaloyl dichloride (78.3 g, 0.39 mol, Tokyo Chemical Industry) dissolved in special tetrahydrofuran (220 mL, Wako Pure Chemical Industries, Ltd.) was added dropwise over 1 hour. After dripping, the ice bath was released and stirred for 3 hours at 70 degreeC of internal temperature by the hot water bath (70 degreeC). After completion | finish of reaction, water (100 ml, Chesei Chemical Industry) was added, and it stirred in the warm water bath (70 degreeC) for 2 hours. After the crystals were suction filtered, the obtained crystals were washed in the order of water (400 mL x 3) and primary acetone (400 ml x 1, Junsei Chemical Industry), and the obtained solid was vacuum dried overnight at 120 deg. 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 by TPGCD (hereinafter referred to as “2,2 ′, 3,3 ′, 5,5′-HECBP '' Optional)

A stainless steel column (inner diameter 4 mm × length 10 mm) filled with TPGCD (450 mg) synthesized in Comparative Synthesis Example 1 was mounted in an oven equipped with temperature control, and the inside of the column was equipped with 2,2 kV, 3,3 kPa. , 5,5'-HECBP-containing insulating oil (100 ppm, 450 mg) was poured into nitrogen gas and extracted at 130 ° C to obtain 374 mg of insulating oil. The 2,2 ', 3,3', 5,5'-HECBP concentration of the insulating oil was measured by gas chromatography, and 2,2 ', 3,3', 5,5'-HECBP was not contained. . As is apparent from Table 1, in Example 1 of the present invention, 2,2 절연, 3,3 ＇, 5,5＇-HECBP, even under the condition that the insulating oil having a weight ratio of insulating oil: adsorption material is 400: 240 is excessive. Was able to be adsorbed almost completely, but in Comparative Example 1, in order to obtain the result equivalent to Example 1, insulating oil (450 mg) and the same amount of adsorption material (450 mg) were required. In other words, it was found that the TPGCDM polymer (porous cyclodextrin polymer according to the present invention reacted with methanol at the terminal) has better adsorption performance than the TPGCD polymer (polymer not reacting with methanol at the end).

[Comparative Example 2] Selection Fixation of PCB by TPGCD

A stainless steel column (inner diameter 2 cm × length 25 cm) filled with TPGCD polymer (11 g) synthesized in Comparative Synthesis Example 1 was mounted in an oven with temperature control, and the liquid solution (26.5 ppm, 9.0 g) was added to the column. Was injected with nitrogen gas and poured out at 130 ° C., 3.0 g of insulating oil was obtained. As a result of measuring the PCB concentration of the insulating oil by gas chromatography, no PCB was contained. In Example 2 of the present invention, even when the insulating oil: absorbent material weight ratio of 2.6: 1.6 was excessive, the PCB could be almost completely adsorbed, but in Comparative Example 2, the same result as in Example 2 was obtained. In order to do this, more adsorptive material (11.0 g) was needed than insulating oil (9.0 g). In other words, it was found that the TPGCDM polymer (porous cyclodextrin polymer according to the present invention reacted with methanol at the terminal) has better adsorption performance than the TPGCD polymer (polymer not reacting with methanol at the end).

Comparative Synthesis Example 2 Synthesis of Polymer According to Japanese Patent No. 3010602

The polymer was synthesized approximately 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, Junsei Chemical) and dimethyl terephthalate (1.7 g, 8.8 mmol, Kishida Chemical) (10-fold equivalent of β-CD, synthesis Same as Example 1), and DMF (18 mL, Junsei Chemical) solution of calcium acetate dihydrate (3.5 mg, Canto Chemicals) and antimony trioxide (7.0 mg, Wako Pure Chemical Industries, Ltd.) were put into a homogeneous solution. The mixture was heated, the capillary was placed at the bottom of the reaction tube and the nitrogen flowed. Methanol in the mixture was distilled off at 110 ° C. for 6 hours, and then heated at 150 ° C. for 6 hours. Then, the mixture was heated under reduced pressure, and further heated for 12 hours. After completion of the reaction, the mixture was allowed to cool under nitrogen stream. The DMF solution was directly reprecipitated in a large amount of water, and the resulting precipitate was filtered, sufficiently washed with water, and dried to obtain 196 mg of a polymer (hereinafter referred to as "Comparative Synthesis Example 2 polymer").

[Comparative Example 3]

Comparative Synthesis Example 2 A stainless steel column (inner diameter 4 mm × length 10 mm) filled with a polymer (350 mg) was mounted in an oven equipped with temperature control, and in this column 2,2 kPa, 3,3 kPa, 5,5 298 mg of insulating oil was obtained by pouring an insulating oil (100 ppm, 350 mg) containing X-hexachlorobiphenyl (2,2 ＇, 3,3＇, 5,5 ＇-HECBP) with nitrogen gas. Was obtained. The 2,2,3,3,5,5'-HECBP concentration of the insulating oil was measured by gas chromatography, and the concentration of 2,2,3,3,3,5,5'-HECBP was 96.1 ppm. . That is, it turned out that the polymer synthesize | combined in the comparative synthesis example 2 cannot adsorb | suck a halogenated aromatic compound effectively.

[Comparative Example 4]

Comparative Synthesis Example 2 A stainless steel column (inner diameter 8 mm × length 300 mm) filled with a polymer (2.0 g) was mounted in an oven equipped with temperature control, and a real liquid (26.5 ppm, 2.0 g) was poured into the column with nitrogen gas. Injecting and pouring out at 130 ° C, 0.96 g of insulating oil was obtained. The PCB concentration of the insulating oil was measured by gas chromatography, and the PCB concentration was 26.2 ppm. That is, it turned out that the polymer synthesize | combined in the comparative synthesis example 2 cannot adsorb | suck PCB in a real liquid effectively.

The result of the said Example and a comparative example is put together in Table 1 and Table 2.

Industrial availability

According to the present invention, an organic medium represented by an insulating oil, a heat medium, a lubricating oil, a plasticizer, a paint, an ink, and the like which may contain halogenated aromatic compounds, which are toxic substances such as dioxins and polychlorobiphenyls, which are not easily released to the environment. In industries that require the storage of solids and solid materials represented by paper, wood, incineration, rocks, soil, etc., which may contain these compounds, Saving of storage space can be realized at the same time.

Claims (17)

A porous cyclodextrin polymer which interacts with a halogenated aromatic compound by reacting alcohols, aryl alcohols or phenols at a terminal of a polymer obtained by condensing cyclodextrin with an organic dibasic acid or an organic dibasic acid halide. Selective fixing agent of halogenated aromatic compounds contained in an organic medium. The method of claim 1,
Selective fixing agent wherein 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 halides thereof. The method according to claim 1 or 2,
Alcohol has 1? Selected from alkyl groups of 10, aryl alcohols selected from benzyl alcohols or benzyl alcohols substituted with alkyl, aryl, or acyl groups, and phenols selected from phenols or phenols substituted with alkyl, aryl, or acyl groups Fixing agent. The method according to any one of claims 1 to 3,
The selective fixing agent in which the porous cyclodextrin polymer which aspirates | interacts with a halogenated aromatic compound by immobilization to a solid support | carrier. The method according to any one of claims 1 to 4,
The selective fixing agent whose halogenated aromatic compound is dioxins, polychloro biphenyls, or polychlorobenzenes. 6. The method according to any one of claims 1 to 5,
A selective fixing agent wherein the organic medium is selected from the group consisting of organic liquids, insulating oils, heating mediums, lubricants, plasticizers, paints and inks, and mixtures thereof. A porous cyclodextrin polymer which interacts with a halogenated aromatic compound by reacting alcohols, aryl alcohols or phenols at a terminal of a polymer obtained by condensing cyclodextrin with an organic dibasic acid or an organic dibasic acid halide. Selecting a Halogenated Aromatic Compound A halogenated aromatic compound contained in the organic medium is brought into contact with a fixing agent and a halogenated aromatic compound, and the halogenated aromatic compound is adhered to a porous cyclodextrin polymer that attracts and interacts with the halogenated aromatic compound. An organic medium containing no aromatic compound is obtained. The method of claim 7, wherein
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 halides thereof. 9. The method according to claim 7 or 8,
Alcohol has 1? The aryl alcohols are selected from benzyl alcohols or benzyl alcohols substituted with alkyl, aryl, or acyl groups, and the phenols are selected from phenols or phenols substituted with alkyl, aryl, or acyl groups . 10. The method according to any one of claims 7 to 9,
A porous cyclodextrin polymer which interacts with a halogenated aromatic compound by suction is immobilized on a solid carrier. The method according to any one of claims 7 to 10,
The halogenated aromatic compound is dioxins, polychlorobiphenyls, or polychlorobenzenes. 12. The method according to any one of claims 7 to 11,
The organic medium is selected from the group consisting of organic liquids, insulating oils, machine oils, heating mediums, lubricants, plasticizers, paints and inks and mixtures thereof. An organic dibasic acid or organic dibasic acid halide-containing organic solvent is added dropwise to the cyclodextrin dissolved in the organic solvent, followed by esterification by adding alcohols, aryl alcohols, or phenols. Process for the preparation of cyclodextrin polymer. The method of claim 13,
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 halides thereof. The method according to claim 13 or 14,
Alcohol has 1? 10 selected from aliphatic alcohols having 10, aryl alcohols selected from benzyl alcohol or substituted benzyl alcohol, and phenols selected from phenol or substituted phenols. 16. The method according to any one of claims 13 to 15,
The organic solvent which dissolves cyclodextrin is chosen from pyridine, dimethyl sulfoxide, dimethylformamide, and 1-methylimidazole, and the organic solvent which dissolves an organic dibasic acid or an organic dibasic acid halide is tetrahydrofuran, Dichloromethane, 1,4-dioxane, xylene, dimethylformamide and toluene. A porous cyclodextrin polymer prepared by the method according to any one of claims 13 to 16.

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