JP6935281B2 - Adsorbent composition and method of adsorbing harmful substances using it - Google Patents

Description

The present invention relates to an adsorbent composition and a method for adsorbing harmful substances using the adsorbent composition. More specifically, the present invention relates to an adsorbent composition containing a cyclic polyether ester, and a method for adsorbing harmful substances using the same.

Environmentally harmful compounds such as malodorous substances diffused in the indoor or outdoor atmosphere have been adsorbed by an adsorbent, and an adsorbent and an adsorption method that efficiently adsorb the compound to be removed are being investigated. Has been done.
For example, since cyclodextrin can encapsulate molecules such as malodorous substances inside its cyclic structure, it is filled with a treatment as a purification method capable of efficiently adsorbing a compound to be adsorbed in the indoor air atmosphere. A method of adsorbing harmful substances by bringing the indoor air atmosphere into contact with an aqueous cyclodextrin is known (see Patent Document 1).

In the adsorption of harmful substances using cyclodextrin, improvement studies have been conducted to increase the adsorption efficiency, and in particular, as a compound capable of satisfactorily removing phenol compounds in wastewater, cyclodextrin has a specific polymerization function. Cyclodextrin derivatives to which a group is bonded, polymers thereof, and the like are known (see Patent Document 2).
However, although the cyclodextrin derivative described in Patent Document 2 and its polymer can adsorb phenol compounds contained in water well, there is a problem that the adsorption efficiency of amines and the like, which are malodorous substances, is not sufficient.

Japanese Unexamined Patent Publication No. 64-46466

Japanese Unexamined Patent Publication No. 2016-069652

An object of the present invention is to provide an adsorbent composition capable of satisfactorily adsorbing malodorous substances volatilized in water and indoor or outdoor atmospheric atmosphere, and a method for adsorbing harmful substances using the same.

The present inventors have arrived at the present invention as a result of studies for achieving the above object. That is, the present invention is an adsorbent composition containing a cyclic polyether ester represented by the general formula (1), and is used for adsorption of at least one selected from the group consisting of ammonia, hydrogen sulfide, methyl mercaptan and trimethylamine. This is an adsorbent composition and a method for adsorbing a harmful substance using the same, wherein the harmful substance is at least one selected from the group consisting of ammonia, hydrogen sulfide, methyl mercaptan and trimethylamine .

［一般式（１）において、Ｒ¹は炭素数２〜２１の２価の炭化水素基である。Ｒ¹の水素原子は少なくとも１つがハロゲノ基、アセチル基、アルコキシ基又はフェノキシ基で置換されていてもよい。Ｒ²は炭素数２〜８の２価の炭化水素基である。ｍは１〜３の整数である。ｎは１〜５００の整数であり、ｍ個あるＲ¹は同じであっても異なっていてもよく、ｍ×ｎ個あるＲ２は同じであっても異なっていてもよい。］

[In the general formula (1), R ¹ is a divalent hydrocarbon group having 2 to 21 carbon atoms. At ^{least one hydrogen atom of R 1} may be substituted with a halogeno group, an acetyl group, an alkoxy group or a phenoxy group. R ² is a divalent hydrocarbon group having 2 to 8 carbon atoms. m is an integer of 1-3. n is an integer of 1 to 500, m number is R ¹ may be different even in the same, m × n pieces is R2 may be different even in the same. ]

The adsorbent composition of the present invention satisfactorily adsorbs harmful substances such as malodorous substances dissolved in water and harmful substances such as malodorous substances volatilized in indoor or outdoor air atmosphere, and adsorbs them from water and indoor or outdoor air atmosphere. can do.

The adsorbent composition of the present invention contains the cyclic polyether ester (A) represented by the above general formula (1).

In the above general formula (1), R ¹ is a hydrocarbon group having 2 to 21 carbon atoms in which at least one hydrogen atom may be substituted with a halogeno group, an acetyl group, an alkoxy group or a phenoxy group.

Examples of the hydrocarbon group having 2 to 21 carbon atoms include an alkylene group having 2 to 21 carbon atoms, an alkenylene group having 2 to 21 carbon atoms, an arylene group having 6 to 21 carbon atoms, and an aralkylene group having 7 to 21 carbon atoms. Be done.

Examples of the alkylene group having 2 to 21 carbon atoms include a linear alkylene group having 2 to 21 carbon atoms (ethylene group, trimethylene group, tetramethylene group, pentamethylene group and n-henicosanylene group) and a branched alkylene group having 3 to 21 carbon atoms. Groups (1-methylethylene group, 2-methylethylene group, 1-ethylethylene group, 2-ethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1,1-dimethyltrimethylene group, 1 -N-Butyl trimethylene group, 1-n-hexyl trimethylene group, 1-n-propyl trimethylene group, 1-n-heptilt methylene group, 1-n-octyl methylene group, 1-n-heptyl tetramethylene group Methylene group and 1-n-octylethylene group, etc.) and cycloalkylene group having 4 to 21 carbon atoms (cyclobutylene group, cyclopentylene group, 2-methylcyclopentylene group, cyclohexylene group, 1,3-dimethylcyclohexyl) Silen group, cycloheptylene group, 1-ethylcyclopentylene group, cyclooctylene group, cyclononylene group, cyclodecylene group, cycloundecylene group, cyclododecylene group, cyclotriderene group, cyclotetradecylene group, cyclopentadecylene group, cyclohexyl Sadecylene group, cycloheptadecylene group, cyclooctadecylene group, cyclononadesilene group, cycloeicocilene group, norbornylene group, dicyclopentylene group, isopropyridene dicyclohexylene group, cyclohexanedimethylene group, etc.) Can be mentioned.

Examples of the alkenylene group having 2 to 21 carbon atoms include a linear alkenylene group having 2 to 21 carbon atoms (etenylene group, propenylene group, henicosenylene group, etc.) and a branched alkenylene group having 3 to 21 carbon atoms (1-ethylethenylene group, 1, 2-Dimethyl ethenylene group, 1-butyl ethenylene group, 1-hexyl ethenylene group, 1-octyl ethenylene group, etc.) and the like can be mentioned.

Examples of the arylene group having 6 to 21 carbon atoms include an o-, p- or m-phenylene group, a 2,4-naphthylene group, a biphenylene group, a terphenylene group, an anthylene group, a phenylene group, a fluorenylene group, a pyrenylene group and a group. Can be mentioned.

Examples of the aralkylene group having 7 to 21 carbon atoms include a phenylmethylene group, a diphenylmethine group, a 1-phenylethylene group, an o-phenylene ethyl group and a naphthylmethylene group.

Examples of the group in which at least one of the hydrogen atoms of these groups is substituted with a halogeno group, an acetyl group, an alkoxy group or a phenoxy group include a 1-bromo-trimethylene group, a 1-acetyl-trimethylene group and a 1-methoxy-trimethylene group. And 1-phenoxy-trimethylene group and the like.

Of these, R ¹ is preferably a linear or branched alkylene group having 3 to 16 carbon atoms, and is a trimethylene group, a tetramethylene group, a pentamethylene group, a tetradecamethylene group, a methylethylene group, 1-n−. Propyltrimethylene group, 1-n-heptil methylene group, 1-n-octyl methylene group, 1-n-heptyl tetramethylene group, 1-n-hexyl trimethylene group, 1-n-hexyl tetramethylene group, A 1-n-undecyl trimethylene group and a 1-n-undecyltetramethylene group are more preferred.

In the general formula (1), R ² is a divalent hydrocarbon group having 2 to 8 carbon atoms. Among the divalent hydrocarbon groups having 2 to 8 carbon atoms, preferred ones include a phenylethylene group and an alkylene group having 2 to 4 carbon atoms, and more preferably a linear alkylene group having 2 to 4 carbon atoms (ethylene). Groups, propylene groups, butylene groups, etc.) and branched alkylene groups having 3 or 4 carbon atoms (methylethylene group, ethylethylene group, methylpropylene group, 2-methylpropylene, etc.) are mentioned, and particularly preferably 2 to 4 carbon atoms. Is a linear alkylene group and a branched alkylene group having 3 to 4 carbon atoms, most preferably an ethylene group and a methylethylene group.

In the above general formula (1), m means the number of repetitions of the unit represented by ^{[R 1} CO (OR ² ) _n O], and n is the number of added moles of the oxyalkylene group represented by ^{(OR 2).} Means.
m is an integer of 1 to 3, preferably 1.
n is an integer of 1 to 500, and the number of added moles (n) of the oxyalkylene group of the cyclic polyether ester (A) can be adjusted according to the adsorption target, but is preferable from the viewpoint of adsorption efficiency and the like. Is an integer of 1 to 500, more preferably 5 to 100, and particularly preferably 5 to 20.
When m is 2 or 3, m R ^1s may be the same or different, and are preferably the same. Further, when m is 2 or 3 and / or n is an integer of 2 or more, m × n R ^2s may be the same or different, and are preferably the same.

The composition of m × n R ² is Polymer. Chem., 2014, 5, 6905. It can be measured and analyzed by time-of-flight mass spectrometry (also referred to as MALDI-TOF MS) by the matrix-assisted laser desorption / ionization method described in 1.

As the cyclic polyether ester (A) contained in the adsorbent composition of the present invention, if m is 1 to 3, the number of added moles of the oxyalkylene group represented by n in the general formula (1) is specific. The cyclic polyether ester (A) which is a value may be used, or a plurality of cyclic polyether esters (A) having different values of n may be used in combination.
When a plurality of cyclic polyether esters (A) having different values (n) of the number of added moles of the oxyalkylene group represented by n in the general formula (1) are used in combination, the oxy of the cyclic polyether ester (A) to be used is used. The value and ratio of the number of added moles of the alkylene group can be adjusted according to the type of adsorption target and the like.

The adjustment of the value of m and the value of n in the general formula (1) is the adjustment of the ratio of the lactone having no active hydrogen-containing group and the alkylene oxide having 2 to 8 carbon atoms used in the alkoxylation reaction described later. This can be done by changing the method of adding the alkylene oxide.
The cyclic polyether ester obtained by the synthetic method described later is a mixture of cyclic polyether esters having different m and different n, but the cyclic polyether ester (A) having a specific n contained in the mixture. The content of the alkylene oxide can be adjusted by changing the method of adding the alkylene oxide. For example, when an alkylene oxide that reacts with a lactone having no active hydrogen-containing group is reacted stepwise, a cyclic poly having a specific value of n is obtained. The content of the ether ester (A) can be increased.
The m value and n value of the cyclic polyether ester (A) are shown in Polymer. Chem., 2014, 5, 6905. It can be analyzed and confirmed by the MALDI-TOF MS described in.

The number average molecular weight (hereinafter abbreviated as Mn) of the cyclic polyether ester (A) contained in the adsorbent composition of the present invention is the type of harmful substances such as malodorous substances targeted by the adsorbent composition of the present invention. However, from the viewpoint of adsorptivity and the like, it is preferably 200 to 30,000, more preferably 200 to 10000, and particularly preferably 200 to 6000. The Mn of the cyclic polyether ester (A) can be set in a preferable range by adjusting the number of moles of oxyalkylene groups added.

Here, examples of harmful substances to be adsorbed by the present invention include vehicle exhaust gas, tobacco odor, pet odor, and formaldehyde, which is a causative substance of chemical substance hypersensitivity released from building materials. Substances include malodorous substances that give off odors that make people uncomfortable due to odors.

Specific examples of malodorous substances are substances such as ammonia, hydrogen sulfide, methyl mercaptan, and trimethylamine, and if they are released into the atmosphere as they are, they may have an adverse effect on the human body.

The Mn of the cyclic polyether ester (A) can be measured by gel permeation chromatography (hereinafter abbreviated as GPC) under the following conditions.
-Device: "Waters Alliance 2695" [manufactured by Waters]
-Column: "Guardcolum SuperH-L" (1), "TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 connected 1 each" [all manufactured by Tosoh Corporation]
-Sample solution: 0.25 wt% tetrahydrofuran solution-Solution injection amount: 10 μL
・ Flow rate: 0.6mL / min ・ Measurement temperature: 40 ℃
・ Detector: Refractive index detector ・ Reference substance: Standard polyethylene glycol

As the cyclic polyether ester (A) used in the adsorbent composition of the present invention, preferably, R ¹ is a tetradecamethylene group, R ² is an ethylene group and a propylene group, and m is 1-3. Examples thereof include cyclic polyether esters in which n is 1 to 500.

The cyclic polyether ester (A) used in the adsorbent composition of the present invention has the above-mentioned active hydrogen-containing group by using a lactone having no active hydrogen-containing group and an alkylene oxide having 2 to 8 carbon atoms. It can be obtained by carrying out a reaction (also referred to as an alkoxylation reaction) in which an oxyalkylene group is inserted between the carbonyl of the oxycarbonyl group of the non-lactone and the oxygen atom. In the alkoxylation reaction, a lactone having no active hydrogen-containing group and an alkylene oxide having 2 to 8 carbon atoms are used, and a catalyst used for the ring-opening addition reaction and the alkoxylation reaction of the alkylene oxide is used as a catalyst for the alkoxylation reaction. It may be used as.
The active hydrogen-containing group means a functional group to which an alkylene oxide can be ring-opened and added, and examples thereof include a hydroxyl group, a carboxyl group, a mercapto group and an amino group.

In the alkoxylation reaction, the cyclic polyether ester represented by the general formula (1) produced in the alkoxylation reaction is further different from the cyclic polyether ester represented by the general formula (1). A side reaction of insertion and addition occurs.
Therefore, in addition to the cyclic polyether ester (A) in which m = 1 in the general formula (1), the reaction product obtained in the above-mentioned alkoxylation reaction includes [R ¹ CO (1) in the general formula (1). oR ²⁾ include _n O] cyclic having two in one molecule a unit represented by the polyether ester (i.e. m = 2) and / or 3 have a cyclic polyether ester (i.e. m = 3), the reaction product The product is a polyether composition containing a cyclic polyether ester having 1 to 3 units represented by ^{[R 1} CO (OR ² ) _n O] in the general formula (1) as a main component.
The composition of the cyclic polyether contained in the reaction product is described in Polymer. Chem., 2014, 5, 6905. It can be analyzed and confirmed by the MALDI-TOF MS described in.

The reaction product of the alkoxylation reaction [that is, the mixture containing the cyclic polyether ester (A)] is further fractionated and purified by a known method such as a gel permeation method or silica gel column chromatography. A cyclic polyether ester (A) having m and n can be obtained. The cyclic polyether ester (A) contained in the adsorbent composition of the present invention was obtained by fractionating and purifying the reaction product even if the reaction product of the alkoxylation reaction was used as it was. Cyclic polyether ester (A) may be used.

The lactone having no active hydrogen-containing group used to obtain the cyclic polyether ester (A) has one hydroxyl group and one carboxyl group, and excludes the above-mentioned one hydroxyl group and one carboxyl group. A cyclic ester obtained by intramolecularly dehydrating a hydroxyl group and a carboxyl group of a monohydroxycarboxylic acid having 4 to 22 carbon atoms which does not have another active hydrogen-containing group can be used. As a method for synthesizing a lactone by intramolecular dehydration, a method of heat dehydration by a known method, J.A. S. Nimitz, R.M. H. Wollemberg, Terahedron Lett. A known synthetic method can be used as described in 1978, 19, 3523, and a method using an enzyme such as lipase.

As a monohydroxycarboxylic acid having 4 to 22 carbon atoms which does not have another active hydrogen-containing group other than one hydroxyl group and one carboxyl group, a linear hydroxycarboxylic acid having 4 to 22 carbon atoms (3-hydroxy) Propanic acid, 4-hydroxybutyric acid, 5-hydroxypentanoic acid, 6-hydroxyhexanoic acid, 15-hydroxypentadecanoic acid, 16-hydroxyhexadecanoic acid, 4-hydroxy-2-butenoic acid, etc.) and branches with 3 to 22 carbon atoms. Hydroxycarboxylic acids (3-hydroxybutanoic acid, 5-hydroxytridecanoic acid, 2-methylene-4-hydroxybutyric acid, 4-phenyl-4-hydroxybutyric acid, 2,2-dimethyl-4-hydroxybutyric acid, 4-hexyl- 4-Hydroxybutyric acid, 4-hydroxy-2-methyl-2-butenoic acid, etc.) and the like.

As the lactone having no active hydrogen-containing group, at least one hydrogen atom among the hydrogen atoms bonded to the carbon atom of the hydroxycarboxylic acid having 4 to 22 carbon atoms is a halogeno group, an acetyl group, an alkoxy group or a phenoxy. A lactone having a structure in which a hydroxycarboxylic acid substituted with a group is dehydrated intramolecularly can also be used.
Among the monohydroxycarboxylic acids having 4 to 22 carbon atoms, examples of the hydroxycarboxylic acid in which at least one of the hydrogen atoms bonded to the carbon atom is replaced with a halogeno group include 2-bromo-4-hydroxybutyric acid. , Examples of the hydroxycarboxylic acid substituted with an acetyl group include 2-acetyl-4-hydroxybutanoic acid, and examples of the hydroxycarboxylic acid substituted with an alkoxy group include 2-methoxy-4-hydroxybutyric acid. Examples of the hydroxycarboxylic acid substituted with a phenoxy group include 2-phenyl-4-hydroxybutyric acid.

Preferred lactones having no active hydrogen-containing group are β-lactone (β-propiolactone, β-butyrolactone, etc.), γ-lactone (γ-butyrolactone, etc.), δ-lactone (δ-valerolactone, etc.). Etc.), ε-lactone (ε-caprolactone, etc.), lactone having a long-chain alkyl group (γ-enant lactone, γ-undecanolactone, γ-dodecalactone, δ-dodecanolactone, etc.), large cyclic lactone (15) -Pentadecanolactone), aromatic lactone (3,4-dihydrocmarin) and the like.
These lactones may be used alone or in combination of two or more.

Examples of the alkylene oxide having 2 to 8 carbon atoms used in the alkoxylation reaction (hereinafter, may be abbreviated as AO) include ethylene oxide, 1,2-propylene oxide, oxetane, 1,2-, 1,3-1, 1. , 4- or 2,3-butylene oxide, styrene oxide and the like, and alkylene oxides having 2 to 3 carbon atoms (ethylene oxide, 1,2-propylene oxide and oxetane) are preferable, and ethylene oxide and 1,2-propylene oxide are preferable. Oxides are even more preferred.
The alkylene oxide may be used alone or in combination of two or more. When two or more kinds are used in combination, the binding form may be random, block, or both.
When two or more kinds as alkylene oxides, resulting circular polyetherester (A) are the compounds of formula (1) as the n is R ^2, different types of R ² corresponding to the type of alkylene oxide used It is a cyclic polyether ester having.

The alkoxylation reaction is preferably carried out in the presence of a catalyst.
As the catalyst used in the reaction step, hydroxides of metals (boron, tin, nickel, zinc, aluminum, etc.), inorganic acids (sulfuric acid, phosphoric acid, etc.), alkali metals (lithium, sodium, potassium, cesium, etc.) are hydroxylated. Two types of metals such as substances, amine compounds (diethylamine, triethylamine, etc.), phosphazene, composite metal cyanide complex catalysts (Japanese Patent Laid-Open No. 2005-53952, JP-A-2016-6203, etc.) (Metal complex catalyst containing in the molecule, etc.), oxide composites described in JP-A-2000-354763, composite oxides of Al and Mg (B1), layered compound hydroxides (B2), and them. It can be carried out by using the fired product (B3) or the like.

The layered double hydroxide used in the production method of the present invention is a divalent metal (Mg, Fe, Zn, Ca, Li, Ni, Co, Cu, etc.) and a trivalent metal (Al, Fe, Mn, etc.). It means an inorganic layered compound in which the above hydroxides are combined to form a laminated structure, and the general formula is [M ²⁺ _1-h M ³⁺ _h (OH) ₂ ] [(W ^i- ) _{h / i.} · jH ₂ O] [wherein, M ²⁺ is a divalent metal, M ³⁺ is a trivalent metal, W ^i-i-valent anion _{^{(HCO 3 -, CO 3 2-}} , PO 4 3- _{^{, SO 4 2-, Cl -,}} NO 2 - and NO ₃ ^-, etc.), h, i and j are each independently a positive number. ], And includes hydrotalcite, motuchoreite, manaseito, stichtite, pyroaulite, tacobite, eardrite, meixenelite and the like. These layered double hydroxides are known as clay minerals and may be contained in naturally occurring minerals or synthetically obtained.

One type of catalyst may be used alone, or two or more types may be used in combination. Of these, preferred from the viewpoint of reaction efficiency are a composite oxide of Al and Mg (B1), hydrotalcite having Al and Mg (B2-1), and a calcined product (B3) thereof.

The composite oxide (B1) used in the present invention is not particularly limited as long as it is an oxide having Al and Mg, but preferred composite oxides include compounds represented by the following general formula (2) or (3). Can be mentioned.
[AMGO ・ Al ₂ O ₃・ bH ₂ O] (2)
[Mg _s Al _t O _u] (3)
In the general formula (2), a and b are independent positive numbers. In the general formula (3), s, t and u are independent positive numbers. From the viewpoint of reactivity, s / t is preferably 0.1 or more and less than 5.
Examples of the composite oxide (B1) include 2.5 MgO, Al ₂ O ₃ , bH ₂ O, Mg _0.7 Al _0.3 O _1.15, etc., respectively, Kyoward 300 [manufactured by Kyowa Chemical Industry Co., Ltd.] and Kyoward 2000, respectively. It can be obtained from the market as [manufactured by Kyowa Chemical Industry Co., Ltd.].

Examples of the hydrotalcite (B2-1) used in the present invention include compounds represented by the following general formula (4).
[Mg _1-c Al _c (OH) ₂ ] ^{c +} [CO _{3c / 2} · dH ₂ O] ^c- (4)

Further, in the general formula (4), c is a number satisfying 0 <c ≦ 0.33, and d is a number satisfying 0 <d ≦ 1.0.

The hydrotalcite _{(B2-1), Mg 6 Al 2} (OH) 16 CO 3 · 4H 2 O [c = 0.25] and _{Mg 4.5 Al 2 (OH) 13} CO 3 · 3.5H 2 O [C = 0.31] and the like, which can be obtained from the market as Kyoward 500 [manufactured by Kyowa Chemical Industry Co., Ltd.] and Kyoward 1000 [manufactured by Kyowa Chemical Industry Co., Ltd.], respectively.

As the hydrotalcite (B2-1) used in the present invention, in addition to the above compounds, known minerals described in West German Patent Publication No. 1592126 and European Patent Publication No. 0207811 can also be used.

As for (B1) and (B2-1), one type may be used alone or two or more types may be used in combination.
Of these, the composite oxide (B1) is preferable from the viewpoint of reactivity, and 2.5 MgO · Al ₂ O ₃ · nH ₂ O (n is a positive number) and Mg _0.7 Al _0.3 O _{1.15 are more preferable.} Is.

The calcined product of the composite oxide (B1) of Al and Mg or the calcined product of hydrotalcite (B2-1) having Al and Mg (B3) is the composite oxide of Al and Mg (B1) or Hydrotalcite (B2-1) can be obtained by heat treatment in an air atmosphere, preferably in a nitrogen stream, preferably at 400 to 1500 ° C. (more preferably 600 to 1000 ° C.) for 1 to 4 hours. can.

In the alkoxylation reaction step, the content of the catalyst is not particularly limited, but from the viewpoint of reaction rate and filtration efficiency, it is preferably 0.01 to 10% by weight, more preferably 0, based on the total weight of the lactone and the alkylene oxide. It is 0.01 to 1.0% by weight.

Further, in the lactone alkenylation reaction step, a solvent may be added in addition to the lactone, the alkylene oxide and the catalyst from the viewpoint of handling.
Solvents include toluene, xylene, benzene, dimethyl sulfoxide, diglyme, triglyme, 1,4-dioxane, cyclohexane, hexane, diethyl ether, tetrahydrofuran, dimethylformamide, carbon tetrachloride, N-methylpyrrolidone, 1,2-dimethoxyethane. , 1,2-Dichloroethane, chloroform and the like. As the solvent, one type may be used alone, or two or more types may be used in combination. Of these, toluene and xylene are preferable from the viewpoint of miscibility with lactones and alkylene oxides.
The weight of the solvent used in the alkoxylation reaction is preferably 0 to 99% by weight, more preferably 0 to 90% by weight, based on the total weight of the cyclic compound, the cyclic ether and the catalyst from the viewpoint of the reaction rate and the like. ..

In the alkoxylation reaction, the temperature of the lactone, the alkylene oxide and, if necessary, the mixture of the catalyst and the solvent is preferably 90 to 250 ° C, more preferably 100 to 190 ° C.
The time for setting the above temperature is preferably 1 to 200 hours.

In the alkoxylation reaction, lactone, alkylene oxide, and if necessary, a catalyst and solvent are placed in the reaction apparatus, the inside of the system is replaced and sealed with an inert gas (nitrogen, argon, etc.), and the reaction temperature and reaction time are adjusted. This can be done by stirring and mixing.
As the reaction device, a known reaction device such as a mixing vessel (flask with stirrer, autoclave, etc.) to which a stirring device and a heating device are attached can be used.

In the production method of the present invention, the cyclic polyether ester composition obtained in the alkoxylation reaction step is further filtered (method described in JP-A-2011-213864, etc.), gel permeation method, silica gel column chromatography, etc. A step of purifying by a known method (hereinafter abbreviated as a purification step) may be included.
By the above purification step, a cyclic polyester composition having a specific structure can be extracted.

The step of producing the cyclic polyether ester composition of the present invention may include a catalyst removal operation. A known method can be used as a method for removing the catalyst. Specifically, in addition to the method described in JP-A-2010-6964, diatomaceous earth (Daicalite 6000, Radiolite # 700, etc.), which is a filtering agent, can be used. ), Silica gel (Wakogel, etc.), magnesium silicate (Kyoward 600, Kyoward 700), and the like. In the filtration operation, the filtration agent may be used alone or in combination of two or more, but it is preferable to use a plurality of types from the viewpoint of filtration efficiency.
Further, from the viewpoint of improving the filtration rate, it is preferable to use diatomaceous earth, and in order to improve the removal efficiency of the catalyst, it is preferable to use magnesium silicate.
The filtration operation can be performed by a known method, and examples thereof include a method in which the cyclic polyether ester composition or a solution thereof is passed through a filter layer in which diatomaceous earth and magnesium silicate are laminated in layers. The solvent used for filtration is not limited as long as it dissolves the cyclic polyether ester composition, but THF, DMF, ethyl acetate, toluene and the like are preferable from the viewpoint of dissolution efficiency.

The adsorbent composition of the present invention may further contain water or an organic solvent from the viewpoint of handleability and the like.
When the adsorbent composition of the present invention contains water, examples of the water include tap water, distilled water, ion-exchanged water, pure water and the like, and among them, ion-exchanged water is preferable from the viewpoint of storage stability.

When the adsorbent composition of the present invention contains an organic solvent, an organic solvent capable of dissolving or dispersing the cyclic polyether ester (A) can be used without limitation, and among them, alcohols (methanol, ethanol, isopropanol and butanol) can be used. Etc.) is preferable.

When the adsorbent composition of the present invention further contains water or an organic solvent, the weight of the water and the organic solvent is 50 to 99% by weight based on the total weight of the adsorbent composition from the viewpoint of storage stability and the like. It is preferable to have.

If necessary, the adsorbent composition of the present invention further comprises other known components, for example, other surfactants (nonionic surfactants) described in JP-A-2014-122331 and JP-A-2016-37525. Agents, anionic surfactants, amphoteric surfactants, etc.), and builders, chelating agents, enzymes, defoaming agents, disinfectants, fragrances, etc. described in JP-A-2004-27181 may be contained. ..

As the nonionic surfactant (C), an alkylene oxide (carbon number 2 to 8) adduct (polymerization degree = 1 to 100) of an aliphatic monoalcohol (carbon number 8 to 24); (poly) oxyalkylene (2 to 8 carbon atoms, degree of polymerization = 1 to 100) aliphatic hydrocarbons (8 to 24 carbon atoms) diether; (poly) oxyalkylene (2 to 8 carbon atoms, degree of polymerization = 1 to 100) higher fatty acids ( 8 to 24 carbon atoms) Ester [polyethylene glycol monostearate (polymerization degree = 20), polyethylene glycol distearate (polymerization degree = 30), etc.]; Polyvalent (divalent to 10-valent or higher) alcohol fatty acid (carbon number) 8 to 24) Esters [glycerin monostearate, ethylene glycol monostearate, sorbitan monolaurate, etc.]; (poly) oxyalkylene (2 to 8 carbon atoms, degree of polymerization = 1 to 100) polyvalent (divalent to 10 valent) Or more) Alcohol higher fatty acid (8 to 24 carbon atoms) ester [polyoxyethylene monolaurate (polymerization degree = 10) sorbitan, polyoxyethylene (polymerization degree = 50) methyl glucoside dioleate, etc.]; fatty acid alkanolamide [1 1: Type coconut oil fatty acid diethanolamide, 1: 1 type lauric acid diethanolamide, coconut oil fatty acid monoethanolamide, etc.]; (Poly) oxyalkylene (2-8 carbon atoms, degree of polymerization = 1-100) alkyl (carbon number) 1-22) phenyl ether; (poly) oxyalkylene (2-8 carbon atoms, degree of polymerization = 1-100) alkyl (8-24 carbon atoms) amino ether; and alkyl (8-24 carbon atoms) dialkyl (carbon number) 1-6) Amine oxide [lauryldimethylamine oxide, etc.] and the like can be mentioned.

Among the nonionic surfactants (C), (poly) oxyalkylene (2 to 12 carbon atoms, degree of polymerization = 1 to 100) alkyl (8 to 24 carbon atoms) from the viewpoint of maintaining the adsorptive capacity even after addition. Amino ethers are preferable, and specific examples thereof include an ethylene oxide 10 mol addition of n-dodecyl alcohol described in JP2013-12204.

When the adsorbent composition of the present invention contains other known components, the content of the other known surfactant is preferably 10% by weight based on the total weight of the adsorbent composition from the viewpoint of adsorption efficiency and the like. % Or less, more preferably 5% by weight or less. The content of the builder and the chelating agent is preferably 10% by weight or less based on the total weight of the adsorbent composition. The content of the enzyme, disinfectant, and fragrance is preferably 5% by weight or less based on the total weight of the adsorbent composition.

When the adsorbent composition of the present invention further contains water or an organic solvent, a predetermined amount of the cyclic polyether ester (A), water or an organic solvent and other components used as necessary are uniformly mixed using a known mixing device. It can be obtained by mixing, and there is no limitation on the order of mixing. For example, in a mixing tank equipped with a stirrer and a heating / cooling device, the cyclic polyether ester (A) and water are charged in any particular order, and the mixture is stirred at 10 to 50 ° C. until uniform. Obtainable.

The method for adsorbing harmful substances such as malodorous substances according to the present invention includes a step of bringing the adsorbent composition into contact with the object to be treated.

The object to be treated is preferably water or gas, and the water includes natural water, domestic wastewater, factory wastewater, etc., and the gas is from air and factory, etc. held in a certain space such as a room. Exhaust is included. The interior when the object to be processed is a gas includes the interior, the interior of the vehicle, the interior of the refrigerator, the interior of the ship, the interior of the aircraft, and the like.

The method for adsorbing a harmful substance of the present invention can be carried out by bringing the adsorbent composition and the object to be treated into contact with each other. When the object to be treated is water, the above-mentioned adsorbent composition is added to an aqueous solution in which harmful substances are dissolved, and the mixture is stirred overnight using a magnetic stirrer, an ultrasonic processor, etc., and the odor of the obtained aqueous solution is confirmed. The adsorption performance of the adsorbent composition can be evaluated by the sensory test.

As the method for adsorbing harmful substances of the present invention, when the object to be treated is a gas, a method of bubbling the gas in the adsorbent composition, a method of spraying the gas with a spray or the like, or the like is used. Can be done with.
As the device used for the bubbling method and the spraying method, a known device described in JP-A-64-46466 can be used.
Further, a method of placing the adsorbent composition on which the above-mentioned adsorbent composition is supported on inorganic particles or the like in a room filled with the object to be treated can also be used.

The adsorbent composition of the present invention can be used for adsorbing harmful substances contained in water such as natural water, domestic wastewater, and factory wastewater, and for adsorbing harmful substances contained in indoor air and exhaust from factories and the like. can. In addition, since the cyclic polyether ester (A) has an excellent ability to include other compounds that cause odors, oral compositions (toothpaste, etc.), household appliances (adhesive layer in cleaning adhesive sheets, etc.), It can also be mixed with building materials (wall materials, etc.) and applied.

Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited thereto. In addition, the part in an Example shows a part by weight.

<Manufacturing example 1>
In a stainless steel autoclave with a stirrer and temperature control function, 240 parts (1 mol) of 15-pentadecanolactone, "Kyoward 500" [Kyowa Chemical Industry Co., Ltd .: Mg ₆ Al ₂ (OH) ₁₆ CO ₃ · 4H ₂ O] 24.2 parts (0.04 mol) and aluminum perchlorate nonahydrate 1 parts (0.002 mole) after sealing put, 3 hours at 160 ° C. in vacuo It was heated and dehydrated. Next, the temperature was raised to 180 ° C., and 88 parts (2 mol) of ethylene oxide (hereinafter abbreviated as EO) was placed in the autoclave while adjusting the gauge pressure to be within the range of 0.1 to 0.5 MPa at 180 ° C. Introduced. After introducing the total amount of EO, stirring was continued until the pressure reached 0.1 MPa. Then, 0.3 part of potassium hydroxide was added, and 176 parts (4 mol) of EO was further introduced so that the gauge pressure was 0.1 to 0.5 MPa at 180 ° C. After introducing the total amount of EO, stirring was continued until the pressure reached 0.01 MPa, and the reaction between 15-pentadecanolactone and EO was carried out. The total time required for the EO addition reaction was 8 hours. Then, the catalyst was filtered off from the reaction mixture obtained by the addition reaction of EO to obtain a cyclic polyether ester composition (A1).
The obtained cyclic polyether ester composition (A1) was analyzed by MALDI-TOF MS.
The cyclic polyether ester composition (A1) is a cyclic polyether containing 90% by weight in total of the cyclic polyether esters represented by the general formula (1) in which m is 1 to 3 and n is 1 to 30. It is a mixture of esters, the average value of n (that is, the average number of moles of EO added) of the cyclic polyether ester composition (A1) is 6, and the total weight of the cyclic polyether esters in which n is 5 to 10 is It was 85% by weight based on the total weight of the cyclic polyether ester (A1).

<Manufacturing example 2>
240 parts (1 mol) of 15-pentadecanolactone, 24.2 parts (0.04 mol) of "Kyoward 500", and aluminum perchlorate in an autoclave made of stainless steel with a stirrer and temperature control function. After adding 1 part (0.002 mol) of hydrate and sealing, the mixture was heated at 160 ° C. for 3 hours under reduced pressure to dehydrate. Next, the temperature was adjusted to 150 ° C., and 61 parts (1.05 mol) of propylene oxide (hereinafter abbreviated as PO) ^{was placed in the autoclave while adjusting the gauge pressure to 1 to 3 kgf / cm 2 G at 150 ° C.} Introduced. After introducing the total amount of PO, stirring was continued until the pressure reached 0.01 MPa, and the reaction between 15-pentadecanolactone and PO was carried out. The time required for the addition reaction of PO was 12 hours. Then, the temperature was adjusted to 180 ° C., and 220 parts (5 mol) of EO was introduced into the autoclave while adjusting the gauge pressure to 0.1-0.5 MPa at 180 ° C. After introducing the total amount of EO, stirring was continued until the pressure became 0.01 MPa, and the EO reaction was carried out. The time required for the EO addition reaction was 7 hours. The catalyst was filtered off from the reaction mixture obtained after completing the EO addition reaction to obtain a cyclic polyether ester composition (A2). The obtained cyclic polyether ester composition (A1) was analyzed by MALDI-TOF MS.
The cyclic polyether ester composition (A2) contains 90% by weight in total of the cyclic polyether esters represented by the general formula (1), wherein m is 1 to 3 and n is 1 to 30, respectively. It is a mixture, and the average value of n of the cyclic polyether ester composition (A2) is 6, of which the average number of added moles of PO is 1, the average number of added moles of EO is 5, and n is 5 to 5. The total weight of the cyclic polyether ester represented by the general formula (1), which is 10, was 90% by weight based on the total weight of the cyclic polyether ester (A2).

<Manufacturing example 3>
240 parts (1 mol) of 15-pentadecanolactone and "Kyoward 500" [Kyowa Chemical Industry Co., Ltd .: Mg ₆ Al ₂ (OH)) in a stainless steel autoclave with a stirrer and temperature control function. ₁₆ CO ₃ · 4H ₂ O] 24.2 parts (0.04 mol) was sealed put, and heated 3 hours at 160 ° C. under reduced pressure and dehydrated. Then, the temperature was adjusted to 180 ° C., and 264 parts (6 mol) of EO was introduced into the autoclave while adjusting the gauge pressure to be within the range of 0.1 to 0.5 MPa at 180 ° C. After adding the entire amount of EO, stirring was continued until the pressure reached 0.01 MPa, and the reaction between 15-pentadecanolactone and EO was carried out. The time required for the EO addition reaction was 10 hours. Then, the catalyst was filtered off from the reaction mixture obtained by the addition reaction of EO to obtain a cyclic polyether ester composition (A3).
The obtained cyclic polyether ester composition (A3) was analyzed by MALDI-TOF MS.
In the cyclic polyether ester composition (A3), the cyclic polyether esters (A3) represented by the above general formula (1) in which m is 1 to 3 and n is 1 to 30, respectively, are totaled to 85. It is a mixture containing% by weight, and the average value of n (that is, the average number of added moles of EO) of the cyclic polyether ester composition (A3) is 10, and the total weight of the cyclic polyether ester in which n is 5 to 10 is It was 28% by weight based on the total weight of the cyclic polyether ester (A3).

<Manufacturing example 4>
In a stainless steel autoclave with a stirrer and temperature control function, 240 parts (1 mol) of 15-pentadecanolactone, "Kyoward 500" [Kyowa Chemical Industry Co., Ltd .: Mg ₆ Al ₂ (OH) ₁₆ CO ₃ · 4H ₂ O] 24.2 parts (0.04 mol) and aluminum perchlorate nonahydrate 1 parts (0.002 mole) after sealing put, 3 hours at 160 ° C. in vacuo It was heated and dehydrated. Next, the temperature was raised to 180 ° C., and 88 parts (2 mol) of ethylene oxide (hereinafter abbreviated as EO) was placed in the autoclave while adjusting the gauge pressure to be within the range of 0.1 to 0.5 MPa at 180 ° C. Introduced. After introducing the total amount of EO, stirring was continued until the pressure reached 0.01 MPa. Then, 0.3 part of potassium hydroxide was added, and 352 parts (8 mol) of EO was further introduced at 180 ° C. so that the gauge pressure was 0.1 to 0.5 MPa. After introducing the total amount of EO, stirring was continued until the pressure reached 0.01 MPa, and the reaction between 15-pentadecanolactone and EO was carried out. The total time required for the EO addition reaction was 8 hours. Then, the catalyst was filtered off from the reaction mixture obtained by the addition reaction of EO to obtain a cyclic polyether ester composition (A4). The obtained cyclic polyether ester composition (A4) was analyzed by MALDI-TOF MS.
The cyclic polyether ester composition (A4) contains 90% by weight of the cyclic polyether ester (A4) represented by the general formula (1) in which m is 1 to 3 and n is 1 to 30. It is a mixture of cyclic polyether esters, and the average value of n (that is, the average number of moles of EO added) of the cyclic polyether ester composition (A4) is 10, and the total number of cyclic polyether esters in which n is 8 to 13. The weight was 85% by weight based on the total weight of the cyclic polyether ester composition (A4).

<Manufacturing example 5>
In a stainless steel autoclave with a stirrer and temperature control function, 240 parts (1 mol) of 15-pentadecanolactone, "Kyoward 500" [Kyowa Chemical Industry Co., Ltd .: Mg ₆ Al ₂ (OH) ₁₆ CO ₃ · 4H ₂ O] 24.2 parts (0.04 mol) and aluminum perchlorate nonahydrate 1 parts (0.002 mole) after sealing put, 3 hours at 160 ° C. in vacuo It was heated and dehydrated. Next, the temperature was raised to 180 ° C., and 88 parts (2 mol) of ethylene oxide (hereinafter abbreviated as EO) was placed in the autoclave while adjusting the gauge pressure to be within the range of 0.1 to 0.5 MPa at 180 ° C. Introduced. After introducing the total amount of EO, stirring was continued until the pressure reached 0.01. Then, 0.3 part of potassium hydroxide was added, and 1232 parts (28 mol) of EO was further introduced at 180 ° C. so that the gauge pressure was 0.1 to 0.5 MPa. After introducing the total amount of EO, stirring was continued until the pressure reached 0.01 MPa, and the reaction between 15-pentadecanolactone and EO was carried out. The total time required for the EO addition reaction was 8 hours. Then, the catalyst was filtered off from the reaction mixture obtained by the addition reaction of EO to obtain a cyclic polyether ester composition (A5). The obtained cyclic polyether ester composition (A5) was analyzed by MALDI-TOF MS.
The cyclic polyether ester composition (A5) contains 90% by weight of the cyclic polyether ester (A5) represented by the general formula (1) in which m is 1 to 3 and n is 1 to 30. It is a mixture of cyclic polyether esters, and the average value of n (that is, the average number of moles of EO added) of the cyclic polyether ester composition (A5) is 30, and the total number of cyclic polyether esters in which n is 28 to 33. The weight was 85% by weight based on the total weight of the cyclic polyether ester composition (A5).

<Manufacturing example 6>
"KYOWAAD 300" [Chemical _{Formula: 2.5MgO · Al 2 O 3 ·} nH 2 O (n is a positive number), Kyowa Chemical Industry Co., Ltd.] 24 hours of heat treatment under a nitrogen stream 900 ° C. in an electric furnace And the fired product was adjusted.

<Manufacturing example 7>
30 parts of 15-pentadecanolactone [manufactured by Tokyo Chemical Industry Co., Ltd.] and 1 part of the fired product obtained in Production Example 6 were put into a stainless steel autoclave equipped with a stirrer and a temperature control function. After aeration with nitrogen for 1 hour, the pressure was reduced (gauge pressure −0.1 MPa). Then, the temperature was raised to 150 ° C., and 27.5 parts of ethylene oxide was press-fitted at 150 ° C. over 10 hours. Then, it was aged for 10 hours to obtain a mixture (PA6-1) containing the cyclic polyether ester compound (A).
The obtained mixture (PA6-1) was cooled to 50 ° C., 100 parts of ethanol was added to adjust the temperature to 50 ° C., and then 5 parts of Radiolite # 700 [manufactured by Showa Chemical Industry Co., Ltd.] as a filtration aid. And Kyoward 600 [manufactured by Kyowa Chemical Industry Co., Ltd.] 5 parts were filtered through a suction funnel packed in layers to separate the catalyst. Then, ethanol was distilled off under reduced pressure to obtain a cyclic polyether ester compound (PA6-2).
5 parts of a mixture (PA6-2) containing a cyclic polyether ester compound (A) and a cyclic polyester calcined product (A1) 2 obtained in Production Example 1 in a stainless steel autoclave equipped with a stirrer and a temperature control function. 25 parts and 25 parts of xylene were added. After aeration with nitrogen for 1 hour, the pressure was reduced (gauge pressure −0.1 MPa). Then, the temperature was raised to 150 ° C., and 45.4 parts of ethylene oxide was press-fitted at 150 ° C. over 10 hours. Then, it was aged for 10 hours to obtain a mixture (PA6-3) containing the cyclic compound (A).
10 parts of the mixture (PA6-3) containing the cyclic compound (A1) and 1 part of the fired product (A1) obtained in Production Example 1 were put into a stainless steel autoclave equipped with a stirrer and a temperature control function. .. After aeration with nitrogen for 1 hour, the pressure was reduced (gauge pressure −0.1 MPa). Then, the temperature was raised to 150 ° C., and 37.9 parts of ethylene oxide was press-fitted at 150 ° C. over 10 hours. Then, it was aged for 10 hours to obtain a mixture (PA6-4) containing a cyclic polyether ester compound.
The obtained mixture (PA6-4) was cooled to 50 ° C., 100 parts of ethanol was added to adjust the temperature to 50 ° C., and then 5 parts of Radiolite # 700 [manufactured by Showa Chemical Industry Co., Ltd.] as a filtration aid. And Kyoward 600 [manufactured by Kyowa Chemical Industry Co., Ltd.] 5 parts were filtered through a suction funnel packed in layers to separate the catalyst. Then, ethanol was distilled off under reduced pressure to obtain a cyclic polyether ester compound (A6).
The obtained cyclic polyether ester compound (A6) was analyzed by MALDI-TOF MS [MALDI mass analyzer AXIMA-Permanence, manufactured by Shimadzu Corporation, the same applies hereinafter], and as a result, the cyclic polyether ester compound (A6) was analyzed. ) Is the cyclic polyether ester compound of the present invention in which ^{R 1} is a pentamethylene group, R ² is an ethylene group, and n = 500 in the general formula (1), and ^{[R 1} CO (OR ^2). ) It was a mixture containing a cyclic polyether ester compound having two repeating units represented by [ _{n O] and a cyclic compound cyclic polyether ester compound having three.}

<Manufacturing example 7>
30 parts of the cyclic polyether ester compound (PA6-1) obtained in Production Example 6 and 1 part of the calcined product obtained in Production Example 1 were put into an autoclave made of stainless steel having a stirrer and a temperature control function. After aeration with nitrogen for 1 hour, the pressure was reduced (gauge pressure −0.1 MPa). Then, the temperature was raised to 150 ° C., and 28.7 parts of ethylene oxide was press-fitted at 150 ° C. over 10 hours. Then, it was aged for 10 hours to obtain a mixture (PA7-1) containing a cyclic polyether ester compound.
The obtained mixture (PA7-1) was cooled to 50 ° C., 100 parts of ethanol was added to adjust the temperature to 50 ° C., and then 5 parts of Radiolite # 700 [manufactured by Showa Chemical Industry Co., Ltd.] as a filtration aid. And Kyoward 600 [manufactured by Kyowa Chemical Industry Co., Ltd.] 5 parts were filtered through a suction funnel packed in layers to separate the catalyst. Then, ethanol was distilled off under reduced pressure to obtain a cyclic polyether ester compound (PA7-2).
20 parts of the mixture (PA7-2) containing the cyclic polyether ester compound and 3 parts of the calcined product obtained in Production Example 1 were put into an autoclave made of stainless steel having a stirrer and a temperature control function. After aeration with nitrogen for 1 hour, the pressure was reduced (gauge pressure −0.1 MPa). Then, the temperature was raised to 150 ° C., and 24.4 parts of ethylene oxide was press-fitted at 150 ° C. over 5 hours and then aged for 10 hours. Next, 12.8 parts of propylene oxide was press-fitted over 5 hours and then aged for 10 hours to obtain a mixture (PA7-3) containing a cyclic polyether ester compound.
The obtained mixture (PA7-3) was cooled to 50 ° C., 100 parts of ethanol was added to adjust the temperature to 50 ° C., and then 5 parts of Radiolite # 700 [manufactured by Showa Chemical Industry Co., Ltd.] as a filtration aid. And Kyoward 600 [manufactured by Kyowa Chemical Industry Co., Ltd.] 5 parts were filtered through a suction funnel packed in layers to separate the catalyst. Then, ethanol was distilled off under reduced pressure to obtain a cyclic polyether ester compound (A7).
The obtained cyclic polyether ester compound (A7) was analyzed by MALDI-TOF MS [MALDI mass analyzer AXIMA-Permanence, manufactured by Shimadzu Corporation, the same applies hereinafter], and as a result, the cyclic polyether ester compound (A7) was analyzed. ^{) Is a cyclic polyether ester of the present invention in which R 1} is a pentamethylene group, R ² is an ethylene group and a methyl ethylene group, and n = 50 (EO 40 mol, PO 10 mol) in the general formula (1). It was a mixture containing a compound, a cyclic polyether ester compound having two repeating units represented by [R ¹ CO (OR ² ) _{n O], and a cyclic polyether ester compound having three.}

<Manufacturing example 8>
A nonionic surfactant (C1) used in a comparative composition in which ethylene oxide and propylene oxide were added to n-hexadecylamine was obtained in the same manner as in Production Example 1 of JP2013-122047.

<Manufacturing example 9>
An ethylene oxide adduct (HA1) of n-dodecyl alcohol, which is a surfactant (straight-chain polyether ester) used in the composition for comparison, was obtained in the same manner as in Production Example 8 of JP2013-12204. ..

<Manufacturing example 10>
A polymer (HA2) of a cyclodextrin derivative used in an adsorption composition for comparison was obtained in the same manner as in Example 6-1 of JP-A-2016-069652.

The odor was evaluated on the following 6-point scale.

<Examples 1 to 12, Comparative Examples 1 to 3>
The raw materials constituting the adsorbent composition were put into a mixing tank equipped with a stirrer and a temperature control function in the amounts shown in Table 1, and stirred at 20 to 30 ° C. for 10 minutes for comparison with Examples 1 to 12. The adsorbent composition according to Example 1 was prepared.

The adsorptivity of the adsorbent compositions of Examples 1 to 12 and Comparative Examples 1 to 3 was evaluated by the following methods, and the results are shown in Table 1.
Ammonia (2.5 mg), methyl mercaptan (2.5 mg), hydrogen sulfide (2.5 mg) and trimethylamine (2.5 mg), which are substances to be adsorbed, are added to purified water (10 g) to dissolve them, and further in Examples 7-14 or Comparative Example 1. 1 g of the obtained adsorbent composition was added, the mixture was filled in a brown glass container, capped, and stored in a thermostat adjusted to 25 ° C. for 24 hours. 1 mg of the stored solution was placed in a 50 mL beaker as a sample, and a sensory evaluation test of odor was carried out by 5 panelists (2 males and 3 females). Smell was scored according to the following evaluation criteria. The evaluation results of the five panelists are averaged to obtain a score, and the results are shown in Table 1.

Evaluation 1: No unpleasant odor is felt ・ ・ ・ 5 points Evaluation 2: Finally unpleasant odor can be detected ・ ・ ・ 4 points Evaluation 3: Unpleasant odor is weak ・ ・ ・ 3 points Evaluation 4: Unpleasant odor can be easily detected ・・ ・ 2 points evaluation 5: Strong unpleasant odor ・ ・ ・ 1 point evaluation 6: Strong unpleasant odor ・ ・ ・ 0 points Of these, the average value is 4 points or more ◎, 3 points or more and less than 4 points ○, 2 Points or more and less than 3 points were marked with Δ, and 1 point or less was marked with x.

The cleaning agent composition of the present invention can be used for adsorbing harmful substances contained in water such as natural water, domestic wastewater, and factory wastewater, and for adsorbing harmful substances contained in indoor air and exhaust from factories and the like. can. In addition, since the cyclic polyether ester (A) has an excellent ability to include other compounds that cause odors, oral compositions (toothpaste, etc.), household appliances (adhesive layer in cleaning adhesive sheets, etc.), It can also be mixed with building materials (wall materials, etc.) and applied.

Claims (4)

An adsorbent composition containing a cyclic polyether ester (A) represented by the general formula (1), which is used for adsorption of at least one selected from the group consisting of ammonia, hydrogen sulfide, methyl mercaptan and trimethylamine. Agent composition .

[In the general formula (1), R ¹ is a divalent hydrocarbon group having 2 to 21 carbon atoms. At ^{least one hydrogen atom of R 1} may be substituted with a halogeno group, an acetyl group, an alkoxy group or a phenoxy group. R ² is a divalent hydrocarbon group having 2 to 8 carbon atoms. m is an integer of 1-3. n is an integer of 1 to 500, R ¹ to m pieces there may be different even in the same, m × n pieces is R ² may be the same or different. ] The adsorbent composition according to claim 1, wherein R ¹ is a linear or branched alkylene group having 3 to 16 carbon atoms and R ² is an alkylene group having 2 to 4 carbon atoms. A method for adsorbing a harmful substance, which comprises a step of contacting the adsorbent composition according to claim 1 or 2 with an object to be treated , wherein the harmful substance is selected from the group consisting of ammonia, hydrogen sulfide, methyl mercaptan and trimethylamine. At least one adsorption method . The method for adsorbing a harmful substance according to claim 3, wherein the object to be treated is water or gas.