JP2002059000A - Hydrophobic material adsorbent and column for hydrophobic material adsorption - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adsorbent which adsorbs hydrophobic materials, more particularly hormone-like acting materials with high efficiency, has high mechanical strength and excellent adsorption reproducibility and is prepared by a simple preparation method. SOLUTION: This hydrophobic material adsorbent consists of a crosslinked polymer and the amount of elution of the hydrophobic materials when the hydrophobic materials are eluted from the adsorbent by using an organic solvent is <=100 pg per 1 g of the adsorbent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrophobic substance adsorbent capable of efficiently adsorbing a hydrophobic substance and a column for adsorbing a hydrophobic substance.

[0002]

2. Description of the Related Art Various hydrophobic harmful substances are present in the environment. These have low initial solubility in a large amount of wastewater or exhaust gas due to low water solubility, but increase in concentration due to concentration in the environment and have a great effect on ecosystems.
In particular, some steroid hormones and chemical substances derived from living organisms have a hormone-like effect when taken into a living body, and are called endocrine disrupting chemicals. 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 very small amounts. Leaving the emissions is a serious problem.

In general, as a method of removing harmful substances in the environment, a removal technique by adsorbing harmful substances to an adsorbent is known. On the other hand, high-precision measurement of these hydrophobic substances is also important, and generally, a gas chromatography (GC) method, a liquid chromatography (LC) method, or a method combining these methods with a mass spectrum (MS) analysis method Or a highly sensitive measurement method such as an immunization method 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 pretreatment in the removal of the hydrophobic substance or the high-sensitivity measurement requires an adsorbent that efficiently adsorbs the target hydrophobic substance, and the performance of the adsorbent affects the measurement result and the removal result. Therefore, strict control of adsorption performance is required

As an adsorbent for a hydrophobic substance, an inorganic adsorbent such as activated carbon or zeolite has been used. 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 in the reproduction processing also causes an increase in processing cost.

[0005] On the other hand, an adsorbent made of an organic synthetic polymer is an excellent adsorbent that generally has less of the above-mentioned disadvantages than an inorganic adsorbent. Many sorbents based on styrene or acrylic polymers are disclosed as materials. For example, JP-A-7-246334 discloses an adsorbent for a ketone solvent using a chloromethylstyrene copolymer (containing 8% or less of a crosslinkable monomer). A carrier for adsorbing a surfactant by an acrylic cross-linked polymer having an alkylene chain (containing 1 × 10 ^{−5 to} 5 × 10 ⁻² mol of a cross-linkable monomer) is disclosed. Japanese Patent Application Laid-Open No. 9-192653 discloses a chlorinated organic solvent adsorbent comprising a non-crosslinkable copolymer of a styrene polymer and a methyl (meth) acrylate polymer. However, these low-crosslinkable or non-crosslinkable polymers have low mechanical strength, and it is difficult to treat or repeatedly use a large amount of samples. Also, JP-A-10-244
No. 152 discloses an adsorbent that absorbs an oily component into a swellable crosslinked polymer. However, the adsorbent of this application has a large amount of oily components absorbed due to its large swelling property, but on the other hand, its mechanical strength is small due to its swelling property, and it is inferior in durability during mass processing and repeated use. There is a disadvantage that the property is low.

[0006] The mechanical strength can be easily improved by increasing the degree of crosslinking. The degree of cross-linking is determined by selecting and increasing the amount of a cross-linkable monomer, which is a polymer material, or optimizing polymerization conditions. However, in general, an increase in the amount of the crosslinkable monomer causes a decrease in the pore diameter, and as a result, the specific surface area decreases,
It is said that the adsorption efficiency decreases. Therefore, the setting of the polymerization composition or the polymerization conditions in consideration of the balance between the improvement in mechanical strength and the adsorption efficiency has a very large effect on the performance as an adsorbent. As an adsorbent with a relatively high degree of crosslinking,
For example, JP-A-60-090040 discloses an adsorbent for an organic compound which is a styrene-based copolymer.
JP-A-258203 discloses a solid phase extraction filler which is a divinylbenzene-acrylate copolymer, and JP-A-06-212135 discloses a (meth) acrylate ester-containing water-soluble filler. Medium and high molecular weight sorbents are disclosed. However, in each of the techniques, there is a problem that an interfering substance of the target hormone-like action substance elutes from the adsorbent itself. Further, JP-A-06-3
The electron beam polymerization method disclosed in Japanese Patent No. 12135 has a problem in terms of polymerization efficiency, and when used as an adsorbent, elution of the remaining unreacted monomer becomes a problem. In particular, when used as a hormone-like substance adsorbent, if a monomer having a bisphenol A structure, which is a kind of hormone-like substance, is used as in this technique, the elution may have a direct adverse effect. is there. Furthermore, none of the above disclosed techniques is specific for the adsorption of hormone-like agents among hydrophobic substances.

[0007]

As described above, in order to measure or remove a hydrophobic substance such as a hormone-like substance present in various samples, the hydrophobic substance is specifically and efficiently used. An adsorbent to adsorb is required. However, the inorganic adsorbents disclosed to date have problems in safety, cost, and the like. On the other hand, styrene-based or acrylic-based adsorbents are disclosed as organic polymer-based adsorbents, but some of these are low-crosslinkable or non-crosslinkable polymers, making mass processing and reuse difficult. It is. Although an adsorbent having a higher degree of crosslinking is also disclosed, there is a drawback that impurities are eluted during use. In addition, columns packed with the above-mentioned packing materials are commercially available.Each of these commercially available columns shows elution of a hydrophobic substance, and is particularly useful for measurement of a sample containing a hormone-like substance at a low concentration. Was disturbed and could not be measured accurately. The present inventor has conducted various studies to solve the above-mentioned problems, and as a result, it has been found that impurities such as impurities are restricted due to conditions such as restrictions on monomer species to be used, restrictions on a porosifying agent, restrictions on a polymerization method and restrictions on a washing method. It has been found that an adsorbent with little elution of the compound can be obtained. The present invention provides an adsorbent that adsorbs a hydrophobic substance, particularly a hormone-like substance with high efficiency, has high mechanical strength, has excellent adsorption reproducibility, and can be produced by a simple production method, and a column filled with the adsorbent. Is what you do.

[0008]

The invention according to claim 1 (hereinafter referred to as the present invention 1) is a hydrophobic substance adsorbent comprising a crosslinked polymer, wherein the hydrophobic substance is converted from the adsorbent using an organic solvent. Is a hydrophobic substance adsorbent, wherein the amount of the hydrophobic substance eluted is 100 pg or less per 1 g of the adsorbent when eluted.

[0009] The invention according to claim 2 (hereinafter referred to as "invention 2") is a column for adsorbing a hydrophobic substance, wherein the column adsorbent for hydrophobic substance according to claim 1 is packed in an organic solvent. When the hydrophobic substance is eluted from the column by using, the amount of the hydrophobic substance eluted is 100 per column.
pg or less, which is a column for adsorbing a hydrophobic substance.

First, the adsorbent of the present invention 1 will be described in detail.

[0011] The hydrophobic substance adsorbent of the present invention 1 comprises a crosslinked polymer. The crosslinked polymer is a polymer obtained by, for example, a suspension polymerization reaction using a known crosslinkable monomer.

The crosslinkable monomer is not particularly limited, and a known crosslinkable monomer having at least two polymerizable functional groups can be used. For example, ethylene glycol di (meth) acrylate (hereinafter, acrylate or methacrylate is abbreviated as (meth) acrylate), diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol Di (meth) acrylate, polyethylene glycol di (meth) acrylate,
Alkylene glycol di () such as 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, etc. (Meth) acrylates; trimethylolethanetri (meth) acrylate, trimethylolpropanetri (meth) acrylate, tetramethylolpropanetri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate; neopentyl hydroxypivalate Rikoruji (meth) acrylate,
1,3-butylene glycol di (meth) acrylate,
1,6-hexanediol di (meth) acrylate,
1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-hydroxy-1,3-di (meth) acryloxypropane,
-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, 1,1
0-di (meth) acryloxy-5-methyl-4,7-dioxadecane-2,9-diol, 1,11-di (meth) acryloxy-4,8-dioxaoundegan-2,
Crosslinkable monomers of (meth) acrylic acid esters such as 6,10-triol; aromatic monomers such as divinylbenzene, divinyltoluene, trivinylbenzene, and divinylnaphthalene;

In the crosslinked polymer as the adsorbent of the present invention 1, if necessary, 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, and a known non-crosslinkable monomer having one polymerizable functional group can be used. Non-crosslinkable monomers used include, 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.

In the present invention 1, when a non-crosslinkable monomer is used, the amount of the monomer is not more than 20 parts by weight based on 100 parts by weight of the above-mentioned crosslinkable monomer. And more preferably 10 parts by weight or less. The most preferred embodiment consists of only crosslinkable monomers. Non-crosslinkable monomers present as contaminants in commercially available crosslinkable monomers are not included in this ratio.

In the case where a (meth) acrylate monomer is used, the amount of the monomer constituting the crosslinked polymer as the adsorbent of the present invention 1 is ( The ratio of the (meth) acrylate monomer is 80
% Or more, and more preferably 100% (meth) acrylic acid ester monomer.
When the (meth) acrylate is less than 80% by weight,
Adsorption performance for hydrophobic substances decreases.

Most preferably, the monomer constituting the crosslinked polymer as the adsorbent of the present invention 1 is composed of only one kind of crosslinkable monomer. When a plurality of types of crosslinkable monomers are used, one of the plurality of types is preferably 90% by weight or more of the total crosslinkable monomers. However, impurities contained in the monomer are not included in this ratio.

The crosslinkable monomers used include:
A crosslinkable monomer that is a (meth) acrylate monomer and a crosslinkable monomer that is a styrene monomer are preferable, and an acrylate monomer is particularly preferable.

It is not preferable to use the following monomers a) to d) as the monomers constituting the crosslinked polymer which is the adsorbent of the present invention 1.

A) a monomer having an ion exchange group; for example, a monomer having a carboxyl group such as (meth) acrylic acid, or a monomer having a sulfonic acid group or a tertiary or quaternary amino group. It is not preferable to use the obtained polymer because its ion exchange group lowers the adsorption performance of a hydrophobic substance. Also, when used, the content is preferably 10% by weight or less based on the total amount of the monomers.

B) A monomer having a structure similar to that of a hormone-like substance; particularly, a monomer having a structure similar to that of a hormone-like substance, an unpolymerized product of the monomer, When used as, it is not preferable because it may elute. Examples of such a monomer include 2,2-bis {4-[(meth) acryloxyethoxy] phenyl} propane and 2,2-bis {4-[(meth) acryloxy. Diethoxy] phenyl} propane and 2,2-bis {4-[(meth) acryloxy.polyethoxy] phenyl} propane.

C) Diene-based monomers: Diene-based monomers such as butadiene have a high hydrophobicity, making it difficult to desorb the adsorbed hydrophobic substance, and it is difficult to regenerate them. Even when it is used, the content is preferably 10% by weight or less based on the total amount of the monomers.

D) Monomer having a halogen group; Monomer having a halogen group such as chlorine and 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 used, 1 to the total amount of monomers
The content is preferably 0% by weight or less.

The crosslinked polymer as the adsorbent of the present invention 1 can be easily obtained by carrying out a polymerization reaction using the above-mentioned monomer in the presence of a polymerization initiator. The polymerization reaction includes known polymerization methods, for example, a method 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, controllability of particle size, and suppression of eluted substances. On the other hand, energy ray polymerization such as ultraviolet polymerization is not used. In the polymerization method, unpolymerized substances may be eluted when the adsorbent is used, which is difficult to remove even by washing or the like.

When the suspension polymerization method is used, for example, a mixture of the above-mentioned crosslinkable monomer (non-crosslinkable monomer) and a polymerization initiator is dispersed in an aqueous dispersion medium in which a water-soluble dispersant is dissolved. After the stirring, the polymerization reaction can be carried out by raising the temperature under an inert gas atmosphere. The reaction conditions for suspension polymerization are as follows:
Depending on the type and amount of the monomer and polymerization initiator to be used, the polymerization temperature is 20 to 100 ° C and 0.5 to 50 ° C.
It is preferable to react for a time.

As the water-soluble dispersant, known ones can be used, for example, high molecular compounds such as polyvinyl alcohol, polyvinyl pyrrolidone, cellulose derivatives, sodium polyacrylate, and various surfactants. Can be

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-
Azo compounds such as cyanopentanoic acid), 2,2′-azobis (2-methylbutyronitrile), and azobiscyclohexanecarbonitrile.

The amount of the polymerization initiator to be 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.

In producing the adsorbent of the present invention 1, when using a suspension polymerization method, it is preferable not to use a porosifying agent (also called a diluent or a phase separation agent). The porosifying agent generally means that the monomer used for the suspension polymerization is easily soluble but the polymer is hardly soluble, and is mainly a water-insoluble or low-water-soluble organic solvent or an inert linear polymer. It is a molecular compound and is used to make the polymer porous with a large pore size. However, the organic solvents mentioned here do not include organic solvents mixed as impurities into commercially available monomers. The use of the porosifying agent, when used as an adsorbent, may cause the remaining porosifying agent to elute as an interfering substance. , More preferably 20 parts by weight or less.

After the polymerization, the obtained crosslinked polymer is washed and dried to obtain the adsorbent of the present invention 1. 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. As the organic solvent used for washing, an organic solvent that is a good solvent for the polymerization raw materials and possible contaminants is used. Examples of the organic solvent include alcohols such as methanol, ethanol, and isopropanol; and known organic solvents such as acetone, hexane, dichloroethane, toluene, and xylene. The washing method is not particularly limited, and can be performed by a method such as immersing the crosslinked polymer in an organic solvent and stirring. At that time, heating or ultrasonic irradiation may be performed.

Further, the adsorbent according to the first aspect of the present invention is characterized in that the elution amount of the hydrophobic substance per unit weight of the adsorbent is less than a predetermined amount. That is, when a hydrophobic substance is eluted using an organic solvent, the elution amount of the hydrophobic substance is set to 100 pg or less per 1 g of the adsorbent. This is because if the elution amount of the hydrophobic substance exceeds 100 pg per 1 g of the adsorbent, it becomes an obstacle when measuring a small amount of the hydrophobic substance, and accurate measurement cannot be performed.
More preferably, the elution amount of the hydrophobic substance per 1 g of the adsorbent is 50 pg or less.

The organic solvent is not particularly limited as long as it is a known organic solvent, and examples thereof include alcohols such as methanol and ethanol; and aromatic hydrocarbons such as toluene and xylene.

The method for measuring the elution amount of the hydrophobic substance is not particularly limited. For example, about 1 g of an adsorbent is collected, and added and dispersed in about 1 to 100 mL of an organic solvent at room temperature. After stirring for ５０50 hours to elute the hydrophobic substance, centrifuging to sediment the filler, concentrating the resulting supernatant, and quantifying the amount of the hydrophobic substance by chromatography-mass spectrometry or immunoassay It can be done by doing.

In the present invention 1, in order to limit the amount of the hydrophobic substance eluted from the adsorbent within the above range, the type and grade of the monomer and the polymerization initiator to be used, or the washing solvent for the crosslinked polymer is used. Can be appropriately selected.

The hydrophobic substance referred to in the present invention is a substance having a water solubility of 10 g / L or less. The adsorbent of the present invention 1 efficiently adsorbs the above-mentioned hydrophobic substances, particularly “hormone-like substance”. The hormone-like acting substance is a biologically-derived steroid hormone, a substance whose hormone-like action is reported in a living body or a substance suspected of having a hormone-like action, and includes a so-called endocrine disrupting chemical substance. Examples of such substances include dioxins including polyhalogenated biphenyls; 4-t-butylphenol, 4-n-heptylphenol, nonylphenol,
Alkylphenols such as 4-t-octylphenol; bisphenol A; 2,4-dichlorophenol;
Phthalates such as di-2-ethylhexyl phthalate, di-n-butyl phthalate and diethyl phthalate; di-2-ethylhexyl adipate; benzo (a) pyrene, benzophenone, 4-nitrotoluene, styrene,
Aromatic compounds such as styrene dimer and styrene trimer;
Estrogens such as estradiol; and the like.

The adsorbent of the present invention 1 is preferably used as an adsorbent for alkylphenols, bisphenol A, phthalates, dioxins and estrogens among others. The target sample containing these hydrophobic substances is not particularly limited, for example, extracts from liquids, gases, or solids such as various types of environmental water, air, and biological components.

The average particle size of the adsorbent of the present invention 1 is not particularly limited, but is preferably appropriately selected within 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. When the adsorbent of the present invention is used for pretreatment for measurement of a hormone-like substance, it is preferably from 1 to 200 µm, more preferably from 10 to 100 µm. When a hormone-like substance is to be removed from a sample, it is preferably 100 μm to 100 mm, more preferably 5 μm for large-scale treatment.
00 μm to 80 mm.

Further, the specific gravity of the adsorbent of the present invention 1 is preferably 0.5 to 3.0, 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 1 efficiently adsorbs a hydrophobic substance, particularly a hormone-like substance, and easily desorbs it. Therefore, the adsorbent is used for pretreatment in measuring the substance in the environment or in biological components, for example. Can be. Furthermore, it can be used to remove hormone-like active substances from exhaust gas from incineration processes and various manufacturing processes, environmental air in general, or wastewater including sewage and industrial wastewater, environmental water such as lake water, river water, and seawater. However, it is not limited to these uses.

Next, the column of the present invention 2 will be described in detail.

The column of the present invention 2 is constituted by packing the above-mentioned adsorbent of the present invention 1 into a column housing.

The shape and size of the column housing are not particularly limited. Generally, a diameter of 0.1 to 10
A cylindrical shape having a size of about 1 cm to 50 cm can be suitably used.

As the material of the column housing, it is preferable to use a synthetic resin such as polyethylene or polypropylene, or a material such as ceramic or glass which does not elute the interfering substance.

In the column according to the second aspect of the present invention, it is preferable that after the column housing is filled with the adsorbent, filter materials are provided at both ends of the cylindrical column housing to hold the adsorbent. As the material of the filtering material, the same material as that of the column housing can be used.

It is preferable that the column housing and the filtering material are washed with an organic solvent which is a good solvent for the eluting substance considered in advance. Although the washing method is not particularly limited, a method of immersing the column in an organic solvent for washing, a method of passing the organic solvent through the column, and the like can be considered. Further, washing may be performed before filling the adsorbent, or washing may be performed after filling. During washing, heating or ultrasonic irradiation may be performed.

In the column of the present invention 2, the elution amount of the hydrophobic substance per column is less than a predetermined amount. That is, when the hydrophobic substance is eluted using the organic solvent, the amount of the eluted hydrophobic substance is 1 column per column.
00 pg or less. This is because if the amount of eluted hydrophobic substance exceeds 100 pg per column, it interferes with the measurement of a very small amount of hydrophobic substance, and accurate measurement cannot be performed. More preferably, the elution amount of the hydrophobic substance per column is 50 pg or less.

As the organic solvent, the same organic solvents as those used in the present invention 1 can be used. Examples thereof include alcohols such as methanol and ethanol; and aromatic hydrocarbons such as toluene and xylene.

The method for measuring the elution amount of the hydrophobic substance is not particularly limited. For example, in the case of a column having an internal volume of about 5 mL, one column has one open end at room temperature at room temperature. After passing about 100 mL of organic solvent, the eluate eluted from the other end is concentrated and then chromatographed.
It can be carried out by quantifying the amount of the hydrophobic substance by mass spectrometry or immunoassay.

The column of the present invention 2 is also similar to the adsorbent of the present invention 1 in that it contains hydrophobic substances in the environment or biological components.
In particular, it can be used for pretreatment in the measurement of hormone-like active substances, and for removing hydrophobic substances from exhaust gas, general ambient air, and environmental water. However, it is not limited to only these uses.

[0049]

Examples of the present invention will be described below. However, the present invention is not limited to only these examples. (1) Preparation of adsorbent Example 1 500 g of diethylene glycol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) and 1.0 g of benzoyl peroxide (polymerization initiator: manufactured by Kishida Chemical Co.) were isoamyl alcohol (porous agent) Dissolved in 200 g. This was dispersed in 2500 mL of a 3% by weight aqueous solution of polyvinyl alcohol while stirring, and the temperature was raised to 80 ° C. under a nitrogen atmosphere. 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 5] The procedure was carried out in the same manner as in Example 1 except that the monomers and the porogen shown in Table 1 were used (the blanks in Table 1 were not used). Was performed to obtain each adsorbent.

[Comparative Examples 1 to 5] Operations were performed in the same manner as in Example 1 except that the monomers and the porogens shown in Table 1 were used to obtain each adsorbent.

[0052]

[Table 1]

Comparative Example 6 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, 2,2-dimethoxy-2-phenylacetophenone (polymerization initiator: 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.

(2) Bisphenol A elution from adsorbent
Measurement of Amount With respect to the adsorbents obtained in the above Examples and Comparative Examples, the elution amount of bisphenol A was measured.

(Method) 0.1 g of the adsorbent was dispersed in 10 mL of methanol (for HPLC: Wako Pure Chemical Industries, Ltd.) and stirred well. The resulting 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 dissolved in a phosphate buffer to obtain bisphenol A, a hormone-like substance. (BPA) ELIS
The measurement by the method A was performed.

The analysis in the ELISA system was performed by the following method. 50 μL of the sample was added to the anti-BPA antibody-immobilized plate, and 50 μL of HRP (horse radish peroxidase) -labeled BPA was further added, followed by reaction 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. A blank test was performed under the condition where the adsorbent was not used, and the measured value in the blank test was subtracted from the above measured value to obtain the amount of eluate from the adsorbent.

(Results) The results of the BPA dissolution test are shown in Table 2. It was found that the adsorbents of the examples showed less elution of interfering substances from the adsorbents themselves. On the other hand, in the comparative example, BPA
Elution of the substance that interfered with the measurement was confirmed, indicating the possibility of interfering with the high-precision measurement. In Comparative Examples 1 and 5, since a large amount of the porosifying agent was used, Comparative Examples 2 to 4 were used.
It is considered that the elution amount was increased in the case of using a non-crosslinkable monomer. In Comparative Example 6, it is considered that the elution of the interfering substance was increased by the electron beam polymerization method or by using a monomer similar to a hormone-like substance.

[0058]

[Table 2]

(3) Elution of bisphenol A from the column
Measurement of Amount In the above (2), the adsorbent of Example 2 which was confirmed to have a small amount of eluate was packed in a column, and an elution test from the entire column was performed.

(Method) 0.2 g of the adsorbent of Example 2 was packed in a column (volume: 3 mL) of each material shown in Table 3 below. The filtering material used was made of polyethylene (pore diameter 20 μm). To each column, add 3 mL of each organic solvent described in Table 3 to 3
The solution was passed once and dried to obtain a washed column.

10 mL of methanol was passed through the obtained column, and the methanol solution was operated in the same manner as in the above (2).
BPA in methanol was measured by an ELISA method.

(Results) The results are shown in Table 3. When the washing operation was not performed, any interfering substance was confirmed, and it was found that washing was necessary even for a glass column.

[0063]

[Table 3] (4) Performance evaluation The performance of the adsorbents obtained in the above Examples and Comparative Examples was evaluated as follows. (A) Adsorption test Using the adsorbents obtained in Examples and Comparative Examples, the adsorption performance of various hormone-like active substances was evaluated. (Method) From BPA standard solution (manufactured by Wako Pure Chemical Industries), BPA1μ
g / mL of a 10% by weight methanol solution was prepared, and 0.1 g of an adsorbent was dispersed in the solution and stirred well. The obtained dispersion is treated in the same manner as in the above (2), and B
PA was measured to determine the adsorption rate.

(Results) The results of the adsorption rate test are shown in Table 4.
The adsorption rate of each adsorbent was as good as 85% or more.

[0065]

[Table 4]

(B) Evaluation of adsorption reproducibility The adsorbent 0.2 obtained in the above Examples and Comparative Examples
g was packed in a polypropylene column having an inner diameter of 9 mm and a length of 65 mm (with a polyethylene filter having a pore diameter of 20 μm). After washing this column with methanol, the BPA standard solution used in the above (a) was added. After suction filtration, methanol was added to desorb the BPA, and methanol was recovered. The methanol was concentrated by the same method as in the above (2).
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.

(Results) The results obtained are shown in Table 5 below.
Each of the adsorbents in the examples has a CV value (standard deviation / average value × 10).
0) showed very good reproducibility of 1% or less. On the other hand, in the comparative example, the reproducibility was low.

[0068]

[Table 5]

(C) Change in adsorbability due to regeneration treatment The change in the adsorbability of the above-prepared adsorbent upon repeated adsorption / desorption of a hydrophobic substance was evaluated. (Method) The same column as in (b) was packed with 0.2 g of the adsorbent. To this was added a BPA standard solution (100 ng / mL of a 10% aqueous methanol solution). The effluent from the column was analyzed by ELISA in the same manner as in (2) above.
PA was measured. Further, a regeneration treatment was performed by passing 5 mL of methanol through the column, and an eluate was collected.
Thereafter, a BPA standard solution was added again, and BPA in the eluate was measured in the same manner. These operations were repeated, and the adsorption capacity was measured. (Results) The results are shown in Table 6. It was found that the adsorbents of the examples did not change the adsorbing ability, and could be repeatedly used by a simple regeneration treatment with methanol. On the other hand, it was found that the adsorbent of the comparative example had a significantly reduced adsorption rate, was difficult to regenerate, and could not be used repeatedly.

[0070]

[Table 6]

(D) Practical test of wastewater treatment A test was conducted to remove hormone-like substances from river water. (Method) 100 L of general river water was collected. Since BPA was not detected in the river water used, 1 BPA standard solution was used.
It was added to this river water so as to be 00 ng / mL. The adsorbent obtained in Example 2 was applied to a stainless steel column (diameter 1).
(0 cm × length 50 cm). To this, 100 L of the above river water was entirely passed at a flow rate of 1 L / min. 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.

[0072]

Industrial Applicability The hydrophobic substance adsorbent and hydrophobic substance adsorption column of the present invention can specifically and efficiently adsorb a hydrophobic substance, particularly a hormone-like substance, in a sample, and less elute an interfering substance. Therefore, it is useful as an adsorbent for solid-phase extraction for extracting and concentrating the hydrophobic substance. Particularly, since it has excellent adsorption reproducibility, it is useful for pretreatment of high-precision measurement. Furthermore, since the regeneration treatment can be performed by desorption with an organic solvent, it is advantageous in terms of cost during a large-scale treatment such as removal of a hydrophobic substance from the environment.

Claims (2)

[Claims] 1. A hydrophobic substance adsorbent comprising a crosslinked polymer, wherein when the hydrophobic substance is eluted from the adsorbent using an organic solvent, the amount of the hydrophobic substance eluted per 1 g of the adsorbent 100
pg or less. 2. A column for adsorbing a hydrophobic substance, wherein the hydrophobic substance adsorbent according to claim 1 is filled in a column housing, wherein the hydrophobic substance is eluted from the column using an organic solvent. The elution amount of the hydrophobic substance is 100 per column.
pg or less.