JP2002035581A - Adsorbent for hormone-like acting substance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adsorbent specifically adsorbing a hormone-like acting substance in a highly efficient manner, having a high mechanical strength and an excellent adsorption reproducibility and capable of being simply manufactured. SOLUTION: The adsorbent for the hormone-like acting substance comprises a crosslinked polymer and the mean pore volume thereof is 0.0001-0.1 mL/g.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an adsorbent capable of adsorbing hormone-like substances efficiently.

[0002]

2. Description of the Related Art Some biologically-derived steroid hormones and chemical substances discharged into the environment include substances that exhibit hormone-like actions when taken into a living body. These chemicals are called endocrine disrupting chemicals and generally have low water solubility, so their concentration in large amounts of environmental water or air is low. However, these steroid hormones and hormone-like substances (hereinafter collectively referred to as hormone-like substances) have been found to have an adverse effect on the reproductive function of animals, even in extremely small amounts. Leaving these emissions is a serious problem.

In general, as a method for removing harmful substances from the environment, a technique for removing harmful substances from an adsorbent by adsorbing the harmful substances is well known. However, there are very few techniques relating to adsorbents that specifically adsorb hormone-like agents.

[0004] On the other hand, it is also important to measure a hormone-like substance in an environment or a biological component with high accuracy. In general, a gas chromatography (GC) method, a liquid chromatography (HPLC) method, or any of these methods can be used. It is performed by a method combining mass spectrometry (MS) analysis or a highly sensitive measurement method such as an immunoassay based on an antigen-antibody reaction. In these analytical methods, extraction / concentration operations are performed by pretreatment by a solid phase extraction method using an adsorbent in order to improve measurement sensitivity.

As described above, the removal of harmful substances or the pretreatment in high-sensitivity measurement of trace substances requires an adsorbent that efficiently adsorbs the target substance, and the removal result or measurement result depends on the performance. Depends on
Strict control of the adsorption performance is required.

Conventionally, as an adsorbent for a hormone-like substance, for example, as an adsorbent for removing dioxins, which are a kind of hormone-like substance, using a gas as a target sample, an inorganic substance such as activated carbon or zeolite is used. A series of adsorbents are known. However, these inorganic adsorbents are not preferred because common drawbacks such as difficulty in regeneration treatment, risk of ignition, and high material cost are pointed out.
In particular, the difficulty of the reproduction processing causes an increase in processing cost, which is a practical obstacle.

On the other hand, synthetic polymer adsorbents are generally excellent adsorbents having less of the above-mentioned disadvantages than inorganic adsorbents. For example, in Japanese Patent Application Laid-Open No. 9-168737,
A surfactant adsorbent containing an acrylic crosslinked polymer having a polyoxyalkylene chain is disclosed. Also,
Japanese Patent Application Laid-Open No. Hei 10-244152 discloses fine particles having oil absorption properties, which are made of a hydrophobic cross-linked polymer. However, these synthetic polymer-based adsorbents are not only specific for hormone-like agents,
Since the mechanical strength is small, there is a drawback that the durability is inferior in large-scale processing and repeated use.

In particular, in the field of synthetic polymer adsorbents
In order to improve the adsorption performance, the pore volume and
Technology for controlling surface properties such as surface area and pore size is also known
Have been. For example, Japanese Patent Application Laid-Open No. 9-192563 discloses
Has a specific surface area of 10 to 1000 m ^Two/ G of polystyrene
The porous body is disclosed in JP-A-4-18436.
Specific surface area is 100m^Two/ G or more, pore volume 0.2mL
/ G or more and an average pore radius of 10 nm or more
Coalescing is disclosed. However, any of these
Adsorbents also have large mechanical processing due to insufficient mechanical strength
Also, there is a disadvantage that durability during repeated use is low. Sa
Furthermore, because there is no specificity for hormone-like agents,
For removing hormone-like substances or hormone-like substances
It cannot be used for high-sensitivity measurement of quality.

[0009]

The inventors of the present invention have conducted various studies to solve the above problems, and as a result, even if the adsorbent has a similar composition, the average pore volume or the specific surface area of the adsorbent is specified in a specific range. By doing so, it has been found that the adsorption performance for hormone-like acting substances is dramatically improved. The present invention
An object of the present invention is to provide an adsorbent which adsorbs a hormone-like substance with high efficiency and specificity, has high mechanical strength, has excellent adsorption reproducibility, and can be produced by a simple production method.

[0010]

According to the first aspect of the present invention,
A hormone-like substance adsorbent comprising a crosslinked polymer, wherein the average pore volume is 0.0001 to 0.1 mL / g.

The invention according to claim 2 is a hormone-like substance adsorbent comprising a crosslinked polymer, wherein the specific surface area is:
It is a hormone-like substance adsorbent characterized by being 0.01 to 10 m ² / g.

The invention described in claim 3 is the first or second invention.
The hormone-like active substance adsorbent according to the above, wherein the average pore diameter is 0.1 to 30 nm.

The details of the present invention will be described below.

The average pore volume of the adsorbent of the present invention is 0.0
001 to 0.1 mL / g, preferably 0.00
01 to 0.01 mL / g. This is because if the average pore volume is less than 0.0001 mL / g, production and control of physical properties are difficult, resulting in poor production reproducibility. On the other hand, if the average pore volume exceeds 0.1 mL / g, the mechanical strength decreases, and the adsorption performance decreases during large-scale treatment or repeated use. Further, when the value is out of this numerical range, swelling and shrinkage occur, and the reproducibility of the adsorption performance is reduced, so that it is not used. The above average pore volume can be easily determined for the dried hormone-like active substance adsorbent by a BET method utilizing adsorption of an inert gas or a mercury intrusion method.

Further, in the adsorbent of the present invention, the specific surface area is specified without specifying the average pore volume as described above, and even if the range is 0.01 to 10 m ² / g. Good. A preferable range of the specific surface area is 0.02 to 8
m ² / g, and a more preferred range is 0.05 to 7 m ^2.
/ G. This is because if the specific surface area is less than 0.01 m ² / g, production and control of physical properties are difficult, and production reproducibility is poor. Further, in order to obtain an adsorbent having a specific surface area of more than 10 m ² / g, the pore size must be increased, and as a result, the mechanical strength is reduced, and the adsorption performance is reduced during large-scale treatment or repeated use. Further, the reproducibility of the adsorption performance is deteriorated due to swelling / shrinking, which is not preferable. The specific surface area can be easily determined for the dried hormone-like substance adsorbent by the BET method utilizing the adsorption of an inert gas or the mercury intrusion method.

Of course, in the adsorbent of the present invention, the physical properties of both the above average pore volume and the specific surface area may be specified, and it is more preferable that each of these physical property values satisfies the above range.

Further, in the present invention, the average pore diameter is preferably 0.1 to 30 nm. A more preferred average pore diameter is 0.5 to 25 nm, and a particularly preferred average pore diameter is 1 to 20 nm. If the average pore diameter is less than 0.1 nm, production and control of physical properties are difficult and production reproducibility is poor, which is not preferable. On the other hand, if the average pore diameter exceeds 30 nm, the mechanical strength is reduced, and the adsorption performance is deteriorated during mass processing or repeated use, which is not preferable. In addition, the reproducibility of the adsorption performance is deteriorated due to the swelling / shrinking, which is not preferable. The average pore diameter can be easily obtained by a BET method utilizing the adsorption of an inert gas or a mercury intrusion method.

The average particle size of the adsorbent of the present invention is not particularly limited, but is preferably appropriately selected in the range of 1 μm to 100 mm depending on the use of the adsorbent. Any deviation from these ranges is inappropriate for handling during use. For example, when the adsorbent of the present invention is used for pretreatment for measurement of a hormone-like active substance, it is preferably 1 to 200 μm, more preferably 10 to 100 μm.
It is. When used to remove a hormone-like substance from a sample, 100 μm to 10 μm is used for mass processing.
0 mm is preferable, and 500 μm to 80 mm is more preferable.

Further, the specific gravity of the adsorbent of the present invention is preferably 0.5 to 3.0, and more preferably 0.7 to 2.0. Outside of these ranges, it is unsuitable for handling at the time of use, especially for handling large amounts of samples.

The adsorbent of the present invention comprises a crosslinked polymer.
This crosslinked polymer can be obtained by performing a polymerization reaction on a crosslinkable monomer or a mixture of a crosslinkable monomer and a non-crosslinkable monomer so as to conform to the above-mentioned physical properties.

The crosslinkable monomer includes at least 2
There is no particular limitation as long as the monomer has two polymerizable functional groups, and a known crosslinkable monomer can be used. As such a crosslinkable monomer, for example, ethylene glycol di (meth) acrylate (hereinafter, “acrylate or methacrylate” is abbreviated as “(meth) acrylate”), diethylene glycol di (meth) acrylate (Meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth)
Alkylene glycols such as acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate Di (meth) acrylates; trimethylolethanetri (meth) acrylate, trimethylolpropanetri (meth) acrylate, tetramethylolpropanetri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethyllolmethanetetra ( (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate; hydroxypiva Neopentyl glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol Di (meta)
Acrylate, 2-hydroxy-1,3-di (meth) acryloxypropane, 2-hydroxy-1-acryloxy-3-methacryloxypropane, urethane (meth) diacrylate, glycerol di (meth) acrylate,
Glycerol acrylate methacrylate, 1,10-
Di (meth) acryloxy-4,7-dioxadecane-
2,9-diol, 1,10-di (meth) acryloxy-5-methyl-4,7-dioxadecane-2,9-diol, 1,11-di (meth) acryloxy-4,8-dioxaoundegan And (meth) acrylate crosslinkable monomers such as 2,6,10-triol; and aromatic monomers such as divinylbenzene, divinyltoluene, trivinylbenzene, and divinylnaphthalene.
These may be used as a mixture of two or more.

In the adsorbent of the present invention, a non-crosslinkable monomer may be used as a part of the structural unit in addition to the above-mentioned crosslinkable monomer. The non-crosslinkable monomer is not particularly limited as long as it is a monomer having one polymerizable functional group, and a known non-crosslinkable monomer can be used. For example, methyl (meth)
Acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate,
Alkyl (meth) acrylates such as lauryl (meth) acrylate and stearyl (meth) acrylate; hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, and methoxypolyethylene glycol (meth) acrylate (Meth) acrylic esters; and aromatic monomers such as styrene, methylstyrene, and ethylstyrene. These may be used as a mixture of two or more.

The proportion of the monomer constituting the crosslinked polymer is preferably 0 to 20 parts by weight, more preferably 100 parts by weight of the crosslinkable monomer. Is from 0 to 10 parts by weight, and is most preferably composed of only a crosslinkable monomer. Non-crosslinkable monomers present as contaminants in commercially available crosslinkable monomers are not included in this ratio.

When a (meth) acrylic acid ester monomer is used, (meth)
The ratio of the acrylate monomer is 80 to 100% by weight.
Is more preferable, and more preferably, it is more preferably composed of only a (meth) acrylate monomer. This is because when the (meth) acrylic acid ester content is 80% by weight or less, it is difficult to conform to the above-mentioned physical property values, and the adsorption performance for hormone-like active substances may be reduced.

As the monomers constituting the crosslinked polymer,
It is not preferable to use the following monomers a) to d). a) Monomer having an ion exchange group Monomer having an ion exchange group; for example, a monomer having a carboxyl group such as (meth) acrylic acid, and a monomer having a sulfonic acid group and a tertiary and quaternary amino group It is not preferable to use a polymer obtained by using the polymer, because the ion-exchange group lowers the ability to adsorb a hormone-like substance. Also, when used, the content is preferably within 10% by weight based on the total amount of the monomers.

B) A monomer having a similar structure to the hormone-like active substance A monomer having a similar structure to the hormone-like active substance is obtained by using an unpolymerized product of the monomer as an adsorbent. It is not preferable because there is a possibility of elution when it is performed. Examples of such a monomer include 2,2-bis {4-[(meth) acryloxyethoxy] phenyl} propane having a bisphenol A structure and 2,2-bis {4-[(meth) acryloxy diethoxy). Phenyl｝ propane,
Examples thereof include 2,2-bis {4-[(meth) acryloxy.polyethoxy] phenyl} propane and nonylphenoxypolyethylene glycol (meth) acrylate having an alkylphenol structure.

C) Olefin-based monomers and diene-based monomers Olefin-based monomers such as ethylene and propylene; and diene-based monomers such as butadiene are strongly hydrophobic and desorb the adsorbed hormone-like substance. It is not preferable to use it because it is difficult to perform the reproduction process. Even when it is used, it is preferably within 10% by weight based on the total amount of monomers.

D) Monomer having a halogen group Monomer having a halogen group such as chlorine or bromine is not preferable to be used because of its high hydrophobicity similarly to the above-mentioned c) and difficulty in desorption treatment. Even when it is used, it is preferably within 10% by weight based on the total amount of monomers.

The above-mentioned crosslinked polymer is obtained by
It is obtained by performing a polymerization reaction in the presence of a polymerization initiator. Examples of the polymerization method include known polymerization methods such as a suspension polymerization method, a dispersion polymerization method, and an emulsion polymerization method. Among them, it is preferable to use the suspension polymerization method from the viewpoint of simplicity of operation and controllability of particle diameter. On the other hand, energy ray polymerization such as ultraviolet polymerization is preferably not used. In the ultraviolet polymerization method, it is considered that unpolymerized substances are eluted when the adsorbent is used, and this is because it is difficult to remove the unpolymerized substance even by washing or the like. When the suspension polymerization method is used, for example, a mixture of the above monomer and initiator is dispersed in an aqueous dispersion medium in which a water-soluble dispersant is dissolved, and after stirring, the temperature is raised under a nitrogen atmosphere to perform a polymerization reaction. It can be performed.

The reaction conditions for the above suspension polymerization vary depending on the type and amount of the monomer and the polymerization initiator to be used, the physical properties to be set, and the like.
Preferably, the reaction is carried out for up to 50 hours.

As the water-soluble dispersant, known ones can be used, for example, polyvinyl alcohol, polyvinylpyrrolidone, cellulose derivatives, sodium polyacrylate and the like.

The polymerization initiator is not particularly limited, and a known water-soluble or oil-soluble radical polymerization initiator is used. Specific examples of the polymerization initiator include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate; cumene hydroperoxide, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, o-chlorobenzoyl. Peroxide, acetyl peroxide, t-butyl hydroperoxide, t-butyl peroxyacetate,
organic peroxides such as t-butylperoxyisobutyrate, 3,5,5-trimethylhexanoyl peroxide, t-butylperoxy-2-ethylhexanoate, di-t-butyl peroxide; 2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 4,4'-azobis (4-cyanopentanoic acid), 2,2'-azobis (2-methyl Azo compounds such as butyronitrile) and azobiscyclohexanecarbonitrile.

The amount of the polymerization initiator used is preferably 0.05 to 5 parts by weight based on 100 parts by weight of the crosslinkable monomer. If the amount of the polymerization initiator is less than 0.05 part by weight, the polymerization reaction may be insufficient or the polymerization may take a long time. Things may occur.

Further, at the time of polymerization of the crosslinked polymer, known additives such as a chain transfer agent and a pH adjuster may be added, if necessary. However, it is preferable not to add an organic solvent generally used as a porosifying agent (also referred to as a diluent or a phase separator). The use of the porosifying agent causes an increase in the pore diameter and the pore volume, and it may be difficult to adjust the pore diameter and the pore volume within the range of the physical properties of the present invention.

After the polymerization, the obtained crosslinked polymer is washed and dried to obtain the hormone-like substance adsorbent of the present invention. It is necessary to wash multiple times with an organic solvent. Further, preferably, washing is performed a plurality of times with a plurality of types of organic solvents. The organic solvent used for washing varies depending on the monomer used. For example, known organic solvents such as alcohols such as methanol and ethanol; acetone, hexane and dichloroethane are used.

The "hormone-like substance" in the present invention includes:
Biologically-derived steroid hormones, substances reported to have a hormone-like effect or suspected hormone-like effects in vivo, and also include so-called endocrine disrupting chemicals. Examples of such substances include dioxins including polyhalogenated biphenyls; 4-t-butylphenol, 4-n-
Alkylphenols such as heptylphenol, nonylphenol and 4-t-octylphenol; bisphenol A; 2,4-dichlorophenol;
Phthalates such as 2-ethylhexyl, di-n-butyl phthalate and diethyl phthalate; di-adipate
2-ethylhexyl; aromatic compounds such as benzo (a) pyrene, benzophenone, 4-nitrotoluene, styrene, styrene dimer and styrene trimer; estrogens such as estradiol; Among these, the adsorbent of the present invention is suitably used as an adsorbent especially for alkylphenols, bisphenol A, phthalates, dioxins, estrogens, and the like. The sample containing the hormone-like substance is not particularly limited, for example, extracts from liquids, gases, or solids such as various environmental waters, air, and biological components.

Since the adsorbent of the present invention efficiently adsorbs hormone-like substances and easily desorbs them, it can be suitably used, for example, for pretreatment in measurement of environmental or biological components. In addition, exhaust from incineration and various manufacturing processes, environmental air in general, or wastewater including sewage and industrial wastewater,
It can be used for the removal of hormone-like substances from environmental water such as lake water, river water, seawater, etc., or extracted water of soil, sediment or sludge. However, it is not limited to only these uses.

[0038]

Examples of the present invention will be described below. However, the present invention is not limited to only these examples. [Example 1] (Preparation of adsorbent) 1.0 g of benzoyl peroxide (polymerization initiator: manufactured by Kishida Chemical Co., Ltd.) was dissolved in 500 g of triethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.). This is mixed with a 3% by weight aqueous solution of polyvinyl alcohol 250
Disperse the mixture in 0 mL with stirring, and at 80 ° C under a nitrogen atmosphere.
The temperature rose. After polymerization at 80 ° C. for 24 hours, the contents were washed three times with ion-exchanged water, once with acetone, and four times with ethanol. After washing and drying, an adsorbent was obtained.

[Examples 2 to 7] In the same manner as in Example 1, except that 500 g of triethylene glycol dimethacrylate in Example 1 was replaced by monomers of the types and amounts shown in Table 1. The operation was performed to obtain the adsorbents of Examples 2 to 7.

[0040]

[Table 1]

Comparative Example 1 100 g of N-vinyl-2-pyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.) and 180 g of divinylbenzene (manufactured by Kishida Chemical Co., Ltd.) were mixed with toluene (porous agent: Wako Pure Chemical Industries, Ltd.). Was dissolved in 250 g). In this solution, 1.0 g of benzoyl peroxide was dissolved, dispersed in 2500 mL of a 4% by weight aqueous solution of polyvinyl alcohol while stirring, and heated to 80 ° C. under a nitrogen atmosphere. 8
After polymerizing at 0 ° C. for 24 hours, the contents were washed with ion-exchanged water for 3 hours.
Washed once, once with acetone and four times with ethanol. After washing and drying, an adsorbent was obtained.

[Comparative Examples 2 to 6] Instead of 100 g of N-vinyl-2-pyrrolidone and 180 g of divinylbenzene in Comparative Example 1, monomers of the type and amount shown in Table 1 were used, and instead of toluene, The operation was performed in the same manner as in Comparative Example 1 except that the porous agent shown in Table 1 was used, and adsorbents of Comparative Examples 2 to 6 were obtained.

[Comparative Example 7] 80 g of urethane acrylate oligomer (V-4263: manufactured by Dainippon Ink) and 20 g of 2,2-bis [(4-acryloxydiethoxy) phenyl] propane (BPE-4: manufactured by Shin-Nakamura Chemical) ,
110 g of methyl caprate and 50 of methyl laurate
g, polymerization initiator 2,2-dimethoxy-2-phenylacetophenone (Irgacure 651: manufactured by Ciba-Geigy) 4
g were mixed. The mixed solution was extruded from a nozzle having a diameter of 0.16 mm, and the extruded droplet was irradiated with ultraviolet rays of 365 nm to perform polymerization, thereby obtaining an adsorbent.

(Measurement of Physical Properties) The average pore volume, average pore diameter and specific surface area of the adsorbents obtained in the above Examples and Comparative Examples were measured by the BET method (specific surface area pore distribution measuring apparatus).
NOVA-1200: Yuasa Ionics Co., Ltd.). The average particle size was measured with a Coulter Multisizer (Coulter Co., Ltd.) or an optical microscope (Olympus Co., Ltd.). Table 2 shows the measurement results.

[0045]

[Table 2]

(Adsorption Performance Test) Using the adsorbents obtained in the above Examples and Comparative Examples, the adsorption performance of various hormone-like substances was evaluated. Bisphenol A (BPA)
BPA concentration of 1 μg from standard solution (Wako Pure Chemical Industries)
/ ML of a 10% by weight aqueous methanol solution was prepared, and 0.1 g of the adsorbent was dispersed in the aqueous solution, followed by thorough stirring. The obtained dispersion was centrifuged at 3000 rpm for 10 minutes, and the supernatant was collected. The supernatant was evaporated to dryness by a centrifugal evaporator, and then dissolved in a phosphate buffer for ELISA.
Measurements were taken on the system. The analysis in the ELISA system was performed by the following method. Sample 50μ on anti-BPA antibody-immobilized plate
L and add HRP (horse radish peroxidase)
) 50 μL of labeled BPA was added and reacted at room temperature for 2 hours. After washing the plate, o-phenyldiamine (OPD) was added and reacted for 15 minutes, and the absorbance was measured at 492 nm. The amount of BPA adsorbed on the adsorbent was calculated from the amount of BPA in the supernatant. The same operation was performed using a solution containing no BPA, and a blank test was performed. In addition, other hormone-like substances were evaluated in the same manner,
The adsorption rate was calculated.

Table 3 shows the results of the blank test. The adsorbents of the examples exhibited almost the same values as those in the case where no adsorbent was used, indicating that the elution of interfering substances from the adsorbent itself was small. In particular, the blank values of Examples 1 to 3 obtained by the adsorption composed only of the (meth) acrylic acid ester were low and good. On the other hand, in the comparative example, the blank value is generally high,
The possibility of interference with the measurement was great. In particular, it was high in Comparative Example 7, and it was judged that measurement was impossible.

[0048]

[Table 3]

Table 4 shows the results of the adsorption rate test. In each of the adsorbents, the adsorption rate after subtracting the blank value was as good as 85% or more. Especially in Example 1, 95%
As described above, high adsorption performance was exhibited. Example 1 is a polymer having a composition similar to that of Comparative Example 4, but the average pore diameter and the specific surface area are extremely small as compared with Comparative Example 4. However, no decrease in the adsorption rate was observed, indicating a high adsorption capacity. Similarly, when Example 4 was compared with Comparative Example 6, Example 6 was compared with Comparative Example 2, and Example 7 was compared with Comparative Example 1, no decrease in adsorption ability was observed in the Example. Good results were also obtained for Examples 2, 3 and 5.

[0050]

[Table 4]

(Evaluation of Adsorption Reproducibility) 0.2 g of the adsorbent obtained in the above Examples and Comparative Examples was applied to an inner diameter of 9 mm.
65mm long polypropylene column (20μm pore size)
With a polyethylene filter). The BPA standard solution used in the above “adsorption performance test” was added to this column. After suction filtration, methanol was added to
After desorption and recovery of methanol, the mixture was concentrated by the same method as in the above "adsorption performance test", and BPA was measured by ELISA. 20 columns were prepared using each adsorbent, and the same operation was performed to confirm the reproducibility of the adsorption rate.

Table 5 shows the obtained results. Each of the adsorbents of the examples showed a very good reproducibility with a CV value (standard deviation ÷ average value × 100) of 2% or less. On the other hand, each of the adsorbents in the comparative example had a large variation of 5% or more in CV value, and it was found that it was difficult to use the adsorbent in the pretreatment of high-precision measurement.

[0053]

[Table 5]

(Change in Adsorbing Ability Due to Regeneration Treatment) The change in the adsorbing ability of the above-prepared adsorbent upon repeated adsorption and desorption of the hormone-like substance was evaluated. 0.1 g of adsorbent
Was packed in the same column as the column used in the above “Evaluation of adsorption reproducibility”. The BPA standard solution (100 ng /
mL of a 10% aqueous methanol solution) was added. The effluent from the column was subjected to EL in the same manner as in the above “Adsorption performance test”.
BPA was measured by the ISA method. Further, a regeneration treatment was performed by passing 5 mL of methanol through the column, and an eluate was collected. Then, again, a BPA standard solution was added,
Similarly, BPA in the eluate was measured. These operations were repeated, and the adsorption capacity was measured.

The results are shown in Table 6. It was found that the adsorbents of Examples 1, 4, 6, and 7 did not change the adsorption ability, and could be repeatedly used by a simple regeneration treatment with methanol. On the other hand, Comparative Examples 1 and 2, which have similar compositions to these,
It was found that the adsorbents Nos. 4 and 6 had a significantly reduced adsorption rate due to the difference in their physical property values, were difficult to regenerate, and could not be used repeatedly. Note that the adsorbents of Examples 2, 3 and 5 also showed good regenerating performance, and that of Comparative Examples 3 and 5, the adsorption rate was greatly reduced.

[0056]

[Table 6]

(Practical test of wastewater treatment) A test for removing hormone-like active substances from river water was conducted. General river water 10
0 L was collected. Since BPA was not detected in the used river water, a BPA standard solution was added to the river water so as to be 100 ng / mL. Using the adsorbent obtained in Example 3 as a stainless steel column (diameter 10 cm x length 50 cm)
Was filled. 100 L of the above river water was added to this at a flow rate of 1 L /
The whole amount of water was passed in minutes. BPA in the obtained treated water was measured by the same ELISA method as described above. As a result, the adsorption rate was restored to 100%, and the removal rate was restored to 99% or more by the regeneration treatment by washing with methanol.

[0058]

The hormone-like substance adsorbent of the present invention comprises:
Because it can specifically and efficiently adsorb hormone-like substances in samples, it is not only useful as a solid phase extraction adsorbent for extracting and concentrating hormone-like substances, but also has excellent adsorption reproducibility. In particular, it is useful as a pretreatment filler for high-precision measurement. Furthermore, since the regeneration treatment can be performed by desorption with an organic solvent, it is advantageous in terms of cost especially in large-scale treatment such as removal of a hormone-like substance from the environment.

Claims (3)

[Claims] 1. A hormone-like active substance adsorbent comprising a crosslinked polymer, wherein the average pore volume is 0.0001 to 0.1 mL / g. 2. A hormone-like active substance adsorbent comprising a crosslinked polymer, having a specific surface area of 0.01 to 10 m ² / g. 3. The adsorbent for a hormone-like active substance according to claim 1, wherein the average pore diameter is 0.1 to 30 n.
m. A hormone-like substance adsorbent characterized by the formula m.