JP4946466B2 - Gas adsorbent - Google Patents

Description

  The present invention relates to a gas adsorbent used in a gas filter or devices for removing harmful gases, and includes, as applications, harmful gases contained in building materials, odors generated at kitchens, muffler filters for automobiles, interiors, indoors. , Toilet deodorant, sewage treatment plant, garbage incineration plant, garbage truck, waste truck, storage warehouse, air conditioner, refrigerator, furniture, cushion, stuffed animal, disposable diaper, sewer pipe, sewage plant The present invention relates to a gas adsorbent that is suitably used for gas filters of equipment that is required to remove odorous components, particularly tobacco filters, air purifiers, and harmful gases in tobacco smoke such as car air conditioners.

In recent years, with the great development of the living environment, a very small amount of chemical substances present in living space has been attracting attention as a cause of environmental pollution, endocrine disrupting substances (environmental hormones), and chemical sensitivity.
On the other hand, when tobacco is burned, a particulate phase and a vapor phase are generated in the smoke. In the vapor phase, for example, in addition to carbon monoxide, nitrogen oxide (NOx), ammonia, etc., carbonyl compounds and It contains harmful substances such as organic acids, phenol derivatives such as phenol, cresol and catechol, sulfides such as hydrogen cyanide and hydrogen sulfide. Among these, carbonyl compounds are known as chemical substances that are harmful to the human body, such as recently attracting attention as a main causative substance of chemical substance hypersensitivity.

Here, the carbonyl compound refers to a compound having a carbonyl group (C═O) such as an aldehyde or a ketone. These are one of the harmful gas components that are likely to be encountered in the living environment. For example, aliphatic aldehydes are a major component of various harmful gas components contained in tobacco smoke, and formaldehyde has recently been known as a major causative component of sick house syndrome released from building materials. Yes. Of the harmful gas components contained in tobacco, carbonyl compounds such as formaldehyde, acetaldehyde, acrolein, propionaldehyde, butyraldehyde, crotonaldehyde, acetone, methyl ethyl ketone, and benzaldehyde derivatives of aromatic aldehyde compounds have been reported.
In order to remove such harmful gas components and maintain a comfortable living environment, gas adsorbents with high adsorptivity to harmful gas components are required, and various gas adsorbents are also used in home life. Is used.

  In general, many of the gas absorbents are widely used porous materials such as activated carbon, silica gel, alumina, bentonite, sepiolite, and zeolite that adsorb gas in a physical porous structure. However, among these porous materials, for example, silica gel and alumina easily adsorb harmful substances such as carbonyl compounds and hydrogen cyanide, while adsorbing components also easily desorb. It is known that the adsorbent has low retention (low adsorbability). In addition, when a gas flow having a flow rate equivalent to that when passing through a tobacco filter is brought into contact with the surface of a porous material such as activated carbon, silica gel, or zeolite, compared with a case where a gas flow having a relatively low flow rate is passed. In addition, there is a problem that gas adsorbability is lowered.

  It is known that the gas flow through the tobacco filter when smoking tobacco is very fast, the approximate flow rate is 10 to 30 m / second, and the residence time is within 1 second. Therefore, when a gas adsorbent is used in a tobacco filter, it is required that a sufficient gas adsorbability can be exhibited with respect to a gas flow having a flow velocity when passing through the tobacco filter. Furthermore, high-speed gas is also used when the gas adsorbent is not used for cigarette filters, but is used for gas filters of equipment that is required to remove harmful gases in cigarette smoke such as air purifiers and car air conditioners. It is required from the viewpoint of improving the processing capability that a sufficient gas adsorptivity to the flow can be exhibited.

In Patent Document 1, a cigarette filter comprising a reactant consisting essentially of at least one reactive functional group covalently bonded to a non-volatile inorganic support, said reactant being chemically coupled with the gaseous component of the smoke stream. A cigarette filter is disclosed that removes the gaseous components from the smoke stream in response to
Patent Document 1 is a tobacco filter containing 3-aminopropylsilyl group bonded to silica gel as the most preferable form of the reactant, and the primary amino group of 3-aminopropylsilyl group is hydrogen cyanide or aldehydes. It has been proposed that it can be removed selectively because it chemically reacts with a harmful substance such as a covalent bond. However, the tobacco filter containing 3-aminopropylsilyl group bonded to this silica gel has a low amino group content, so it cannot be said that the amount of adsorption of harmful substances such as hydrogen cyanide is sufficient, and aldehydes are also removed. Hateful. Moreover, when preparing the silica gel which the propylsilyl group which is a gas adsorbent couple | bonded from 3-aminopropyl triethoxysilane and a silica gel, unreacted 3-aminopropyl triethoxysilane remains. The obtained gas adsorbent is dried in an oven, but if a large amount of unreacted 3-aminopropyltriethoxysilane or the like remains in the gas adsorbent, an amine odor is released even after drying, which affects odor and flavor. There is a fear.

On the other hand, in order to remove harmful substances, the use of ion exchange resins as gas adsorbents has also been studied. For example, in Patent Document 2, in a multi-section filter for cigarettes, a selective adsorbent section containing a selective adsorbent substance dispersed in a fibrous material and having an affinity for a predetermined class of chemical compounds, and a large surface area And having a general adsorbent section containing a general adsorbent material that can adsorb smoke components without high specificity, and the selective adsorbent section and the adsorbent section are arranged in tandem in the axial direction. Disclosed cigarette filters. Patent Document 2 discloses activated coconut charcoal as a general adsorbent material having a large surface area and capable of adsorbing smoke components without high specificity, and a selective adsorbent having affinity for the above chemical compounds. It has been proposed to use Duolite A7 (trade name, manufactured by Rohm and Haas) as a substance.
Duolite A7 is an anion exchange resin having a primary amine group and a secondary amine group on a phenol formaldehyde resin base material, and is intended to increase the specificity for adsorption of aldehydes. However, since duolite A7 uses a phenol derivative to form a resin skeleton, free harmful components such as aromatic compounds derived therefrom are released. Moreover, when the experimental result described in this patent document 2 is seen, it cannot be said that the adsorption amount of acetaldehyde is favorable.

In Patent Document 3, a first component which is an adsorbent which is quick but weak in retentivity with respect to a gas phase component of tobacco smoke containing an aldehyde, and an amino group are included and chemically bonded to the gas phase component. In particular, a tobacco filter is disclosed in which a second component that generates a non-volatile reaction product is mixed or closely dispersed. Patent Document 3 describes, as a specific example of the second component, an amino group type such as Diaion CR20 (trade name, manufactured by Mitsubishi Chemical Corporation) in addition to Duolite A7 (trade name) also described in Patent Document 2. Listed are anion exchange resins.
Furthermore, Patent Document 4 discloses a gas adsorbent which is a crosslinked polymer having a structure mainly composed of vinylamine and polyvinyl compound in which the nitrogen atom may be alkylated. Patent Document 4 is a vinylamine ion exchange resin having an aromatic divinyl compound as a crosslinkable component, and is a gas adsorbent containing a large amount of vinylamine components directly related to gas adsorption ability.

  The gas adsorbent composed of Diaion CR20 (trade name, manufactured by Mitsubishi Chemical Corporation) described in Patent Document 3 and the vinylamine ion exchange resin described in Patent Document 4 is intended to increase the adsorptivity of aldehydes. However, these gas adsorbents are amino group-type anion exchange resins, and amine odors are generated by the release of amine impurities contained therein, which greatly affects odor and flavor. In addition, since styrene and divinylbenzene compounds are used as crosslinkable components, free harmful components such as monocyclic aromatic compounds derived therefrom are released.

On the other hand, Patent Document 4 is characterized in that a gas containing an acidic gas is brought into contact to adsorb the acidic gas, and then the adsorbed acidic gas is desorbed by heating the gas adsorbent adsorbing the acidic gas. A method for removing the acidic gas from the gas containing the acidic gas is also disclosed.
However, these methods cannot sufficiently suppress the release of the above-mentioned free harmful components and amine-based impurities, and when the basic aqueous solution is washed, even the amino groups in the gas adsorbent are removed. Therefore, the effect of the gas adsorbent is reduced. Furthermore, when washed with an acid or an alkali, formalin which is a hydrolyzate of vinylformamide is generated and remains in the finally obtained vinylamine ion exchange resin. It is very difficult to achieve industrial mass production by solving these problems by the method described in Patent Document 4.

In Patent Document 5, a gas using a monodispersed spherical aminomethylated polymer having an average pore diameter of 100 to 900 angstroms obtained by aminomethylating spherical particles made of a styrene-divinylbenzene copolymer or the like. An adsorption method is disclosed.
However, in these methods, as in Patent Document 4, the release of the above-mentioned free harmful components and amine impurities cannot be sufficiently suppressed. In particular, in the method in paragraph 0034, a monocyclic aromatic compound derived from phthalimide is produced, or in Example 1, polymerization is performed by a temperature program that ends at 95 ° C. in paragraph 0047, so that the polymerization is incomplete. Produces divinylbenzene, ethylstyrene, and monocyclic aromatic compounds derived from styrene. Further, in the production of the monodispersed spherical aminomethylated polymer of Example 1 by washing only with sodium hydroxide solution and deionized water, there is a problem that amine impurities remain.

  Patent Documents 6 and 7 disclose gas adsorbents having anion exchange groups. However, these gas adsorbents have no description or suggestion about the pores, and since no porosizing agent is used in the examples, the so-called gel-type ions that have almost no pores (porous). Since an exchange resin is used, the amount of acetaldehyde adsorbed cannot be said to be good.

  As is clear from the above, those skilled in the art have conceived what kind of adsorbent can solve the above-mentioned problems, and it is not possible to select and improve a good adsorbent among many adsorbents including commercial products. Even if the knowledge of Patent Documents 1 to 7 without specific motivation is considered together, it cannot be easily achieved.

Japanese translation of PCT publication No. 2002-528106 Special table 2004-53801 gazette JP 54-151200 A JP-A-6-190235 JP 2002-52340 A JP 2001-38202 A JP 2005-103403 A

The object of the present invention is to exhibit sufficient gas adsorption for harmful gas components in tobacco when brought into contact with a gas flow having a high flow rate as seen when passing through a tobacco filter. Another object of the present invention is to provide a gas adsorbent for cigarette filters, which is capable of producing less harmful odorous components such as amine impurities derived from the gas adsorbent itself and less harmful harmful components such as aromatic compounds. .

The inventors of the present invention have intensively studied to achieve the above object, and in order for the gas adsorbent to efficiently adsorb harmful components contained in a gas flow having a high flow rate, the average pore radius is particularly relatively small. In addition to this, we obtained the knowledge that the amount of malodorous components such as amine impurities and the amount of released free harmful components such as aromatic compounds and the neutral salt decomposition capacity must be less than the prescribed amount. . Further, in addition to the concept of the average pore radius, it has been found that the adsorption effect of harmful components is enhanced when the acid adsorption capacity is required to be a predetermined amount or more.
That is, the gas adsorbent provided by the present invention has the following conditions (I), (II), (IV) and (V), or the following (I), (III), (IV) and (V Gas adsorbent for a tobacco filter that satisfies the condition (2), the gas adsorbent comprising a weakly basic anion exchange resin having a styrene-divinylbenzene crosslinked structure skeleton and containing an amino group, weakly basic anion exchange resin temperature 40 to 100 ° C., which was obtained by washing with strong acid at a concentration 0.1～5N, or at least a portion of the line physician 110 ° C. or higher 160 ° C. or less of the polymerization reaction A gas adsorbent obtained by introducing an amino group into a polymer obtained by setting the time at 110 ° C. or higher to 1 hour or longer .
(I) The average pore radius of the gas adsorbent in mercury porosimeter measurement is 330 to 3000 mm.
(II) The amine elution amount from the gas adsorbent per unit mass is 10 μeq / g or less.
(III) The content of the monocyclic aromatic compound represented by the following formula 1 in the gas adsorbent per unit mass is 4 mg / g or less.

(In the above formula 1, R represents a substituent selected from a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, and an alkenyl group having 1 to 3 carbon atoms. N is a number from 1 to 6, and the number of substituents R. When there are a plurality of R, each R may be the same or different.)
(IV) The neutral salt decomposition capacity of the gas adsorbent per unit mass is 0.43 meq / g or less.
(V) The acid adsorption capacity of the gas adsorbent per unit mass is 1.5 meq / g or more.

The gas adsorbent of the present invention comprises a weakly basic anion exchange resin having a styrene-divinylbenzene crosslinked structure skeleton and containing an amino group, and at least a part of the polymerization reaction is performed at 110 ° C. or higher and 160 ° C. are performed by the following washing obtained by introducing an amino group to the resulting polymer by the in which time 110 ° C. or higher and 1 hour or more, a temperature 40 to 100 ° C., the strong acid concentration 0.1~5N It is preferable that it is obtained .
Also, the weakly basic anion exchange resin, after washing with a strong acid, it is preferable that the further washed with methanol.
The weakly basic anion exchange resin is preferably in the OH form.

The gas adsorbent of the present invention efficiently removes harmful substances present in cigarette smoke from a gas flow having a high flow rate, and further, malodor components such as amine impurities derived from the gas adsorbent itself and monocyclic aromatics. Low release of free harmful components such as compounds.
Therefore, the gas adsorbent of the present invention can remove harmful gases in tobacco smoke and is suitably used as a tobacco filter.

The constituent requirements and the like of the present invention will be described in detail below, but these are examples of embodiments of the present invention and are not limited to these contents.
The gas adsorbent provided by the present invention comprises the following conditions (I), (II), (IV) and (V), or the following (I), (III), (IV) and (V) It satisfies the conditions.
(I) The average pore radius of the gas adsorbent in mercury porosimeter measurement is 330 to 3000 mm.
(II) The amine elution amount from the gas adsorbent per unit mass is 10 μeq / g or less.
(III) The content of the monocyclic aromatic compound represented by the following formula 1 in the gas adsorbent per unit mass is 4 mg / g or less.

(In the above formula 1, R represents a substituent selected from a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, and an alkenyl group having 1 to 3 carbon atoms. N is a number from 1 to 6, and the number of substituents R. When there are a plurality of R, each R may be the same or different.)
(IV) The neutral salt decomposition capacity of the gas adsorbent per unit mass is 0.43 meq / g or less.
(V) The acid adsorption capacity of the gas adsorbent per unit mass is 1.5 meq / g or more.
Hereinafter, the gas adsorbent of the present invention will be described in detail.

First, among the above conditions, the condition (I) will be described.
In general, when the gas adsorbent is porous having a large number of pores, the contact area between the gas adsorbent and the gas to be treated is large, so that the gas adsorbability such as the gas adsorption amount and the adsorption efficiency is excellent. However, the gas adsorption efficiency varies depending on the pore radius of the gas adsorbent.
Among conventional gas adsorbents, for example, the porous material of activated carbon is about 10 to 30 mm, the porous material such as silica gel and alumina is about 20 to 100 mm, and Duolite A7 which is an ion exchange resin is 150 to 200 mm. It has an average pore radius of about. However, since the average pore radius is small so that the gas component can be sufficiently diffused into the pores, the efficiency of gas adsorption is poor, particularly when passing through a tobacco filter during smoking (suction). Under such a fast gas flow condition of about 10 to 30 m / sec, the gas adsorbability was low.
Therefore, in the present invention, a gas adsorbent is used as a gas adsorbent index in order to efficiently take in and adsorb a target substance from a gas flow having a relatively high flow rate as seen when passing through a tobacco filter during smoking. The average pore radius is defined.
That is, as defined in the above condition (I), the gas adsorbent of the present invention has an average pore radius of 330 Å or more, preferably 350 Å or more, 3000 Å or less, preferably 2500 Å or less. By making the average pore radius of the gas adsorbent within the above range, not only the surface area is simply increased, but also the gas adsorbent can enter the pores even under fast gas flow conditions of about 10 to 30 m / sec. It is excellent in uptake and gas diffusibility in the pores, and can exhibit high performance as a gas adsorbent.

The average pore radius is a parameter relating to the pore structure on the resin surface, and represents the radius of the pores on the resin surface as an average value.
In general, molecular sieve diffusion and surface diffusion, in which a pore structure having a size several times the size of the molecule to be trapped is optimal for gas adsorption, have been considered. It has been found that the pore radius of the agent requires a larger structure (Knudsen diffusion region). The reason for this is not clear, but the following mechanism is presumed.
In general, the harmful component molecules in the gas move within the mean free path. It is known that this mean free path is about 300 で は for acetaldehyde, which is a kind of carbonyl compound, about 200 で は for acetone, and about 500 で は for hydrogen cyanide under the conditions of 25 ° C and atmospheric pressure, for example. Therefore, if the gas adsorbent has a pore diameter equal to or greater than the mean free path, harmful component molecules can be introduced into the pores of the gas adsorbent (see FIG. 1).

  Here, the mean free path refers to the average distance that each atom or molecule flies from one collision to the next. It plays an important role in transport properties such as diffusion coefficient because it shows how far a gas molecule carries a certain physical property by colliding with other molecules or atoms, and how far a certain physical property is carried before the next collision. (Source: Chemical Dictionary, Tokyo Chemical Doujin, p. 1289)

Therefore, in addition to the above average pore radius, a pore structure having many pores having a pore radius of usually 300 mm or more, particularly 400 mm or more, particularly 500 mm or more is preferable. Specifically, those having the above pores in terms of pore volume are usually 0.05 ml / g or more, preferably 0.1 ml / g or more, more preferably 0.3 ml / g or more, and particularly preferably 0.5 ml / g or more.
If the pore radius is too large, the surface area per weight of the resin (gas adsorbent) becomes small, and there is a possibility that the amount of harmful components adsorbed is not sufficient.

The average pore radius can be measured by using a mercury porosimeter. In a mercury porosimeter, pressure is applied to mercury that has a large surface tension and does not react with most substances, and is pressed into the pores of a vacuum-dried sample (in the present invention, a gas adsorbent). Measure the volume of mercury intruded into the water.
In general, the relationship between the pressure when pressure is applied to enter the pores of the gas adsorbent and the pore diameter at which mercury can enter at that pressure is expressed by the Washburn formula as shown in the following calculation formula 1.
Formula 1:
Pr = -2σ cos θ
In the above calculation formula 1, P is pressure, r is pore radius, σ is surface tension of mercury, usually about 480 dyne / cm, and θ is contact angle between mercury and pore wall surface, usually about 140 °.
From the pressure and the amount of mercury that has entered the sample pores, the average pore radius can be calculated based on the above calculation formula 1, assuming that the pores are cylindrical.
Specific examples of measurement methods are shown below.
<Method of measuring pore properties>
A vacuum-dried resin (gas adsorbent) is placed in a glass cell, and the pore radius and pore volume of the resin are measured with a mercury porosimeter. Based on the histogram showing the distribution of the pores with the pore volume and pore radius as the vertical axis and the horizontal axis, respectively, the pore radius of the portion with the largest total pore volume is defined as the average pore radius.

In order to keep the average pore radius of the gas adsorbent within the above range, the base material of the gas adsorbent includes aromatic polymer resin, (meth) acrylic polymer resin, and phenolic polymer resin. It is preferable to use a polymer resin having a three-dimensional crosslinked structure selected from:
Here, the aromatic polymer resin is a polymer resin containing an aromatic ring in the main chain or side chain of the polymer, for example, a copolymer of a monovinyl aromatic monomer and a crosslinkable aromatic monomer. Is mentioned.
(Meth) acrylic polymer resin is a polymer resin containing a repeating unit derived from a (meth) acrylic monomer in the main chain or side chain of the polymer, for example, one type or two or more types A polymer of a (meth) acrylic monomer, or a copolymer of one or more (meth) acrylic monomers and one or two or more vinylic monomers other than a (meth) acrylic monomer. The phenolic polymer resin to be used is a polycondensate of one or more phenolic compounds.

When silica is used as the base material for the gas adsorbent, the pores can be controlled by the following method, for example.
In general, silica is produced by adding silicon alkoxide such as tetraethoxysilane, solvent and water to gel, and aging and drying, but by changing precipitation conditions, thermal decomposition conditions, etc. when gelling, The pore structure can be controlled. Silica can also be gelled by adding a surfactant (long chain alkyl chain amine and / or long chain alkyl chain ammonium salt) to silicon alkoxide such as tetraethoxysilane, solvent and water. , The pore structure can be controlled. By controlling the alkyl chain, water, solvent and gel point of this surfactant, the desired pores can be obtained.

Next, among the above conditions, the condition (II) will be described.
Among conventional gas adsorbents, those having relatively good adsorptivity to harmful components such as carbonyl compounds include ion exchange resins having amino groups as described in Patent Document 3 and Patent Document 4, Patents A substance in which an amino group is fixed to the base of a matrix structure, such as a reactant in which a 3-aminopropylsilyl group is bonded to silica gel as described in Document 1, is known.
However, a part of the amino compound used in the synthesis stage remains unreacted without being fixed to the base of the matrix structure, and is contained as an impurity in the gas adsorbent. This unreacted amino compound causes amine odor and amine compound leakage.
In general, the greater the amount of amino groups immobilized in the gas adsorbent, the better the adsorptivity to the carbonyl compound, but the greater the amount of unreacted amino compound remaining. Therefore, the conventional gas adsorbent having good carbonyl compound adsorptivity contains an amine odor component derived from the gas adsorbent itself, and this is a bad odor, thus preventing its use as a gas adsorbent.

With respect to such a problem, in the gas adsorbent of the present invention, the intensity of an amine odor which is a bad odor is defined using the amine elution amount per unit mass of the gas adsorbent as an index.
That is, the gas adsorbent of the present invention has not only the definition of the average pore radius of the condition (I) but also the amine elution amount from the gas adsorbent per unit mass as defined in the condition (II). 10 μequivalent / g or less, preferably 5 μequivalent / g or less, more preferably 1 μequivalent / g or less, particularly preferably 0.1 μequivalent or less, and very little malodor derived from the gas adsorbent itself, especially amine odor. .

The amine elution amount is measured, for example, by the following procedure using an organic or inorganic strong acid aqueous solution.
<Amine dissolution test method>
The column is filled with a gas adsorbent as an analyte, and 0.5 to 5N hydrochloric acid aqueous solution is passed as an eluent to elute the amine. The obtained eluent is measured by an analytical method capable of quantifying amines, such as a gas chromatographic method, a liquid chromatographic method, an ion chromatographic method, a mass spectrometry method, or a nuclear magnetic resonance spectrum method.

In order to keep the amine elution amount from the gas adsorbent within the above range, the gas adsorbent after amino group introduction is unreacted by washing with an organic solvent such as methanol, acetone, propanol or THF (tetrahydrofuran). The amino compound may be removed. In addition, you may heat the said washing | cleaning as needed. Further, the cleaning method may be batch cleaning or column passing. In addition to the above washing, or alone, it may be washed with the above organic solvent at the final product stage.
In addition, the amino compound remaining in the resin can also be removed by applying a treatment for bringing the gas adsorbent before or after introduction of the amino group into contact with water vapor (hereinafter sometimes referred to as “water vapor purification treatment”). Can do. In addition, the steam purification treatment is preferable because it also has the effect of thermally decomposing ammonium groups contained in the resin, reducing the neutral salt decomposition capacity, and reducing odor.

Next, among the above conditions, the condition (III) will be described.
Among conventional gas adsorbents, those having relatively good adsorptivity to carbonyl compounds, which are the main harmful gas components in tobacco, have amino groups as described in Patent Document 3 and Patent Document 4. Ion exchange resins are known. The ion exchange resin having an amino group is obtained by immobilizing an amino group on the base of a matrix structure formed by polymerizing a polymerizable monomer and further crosslinking as necessary. In the synthesis stage, a polymerizable monocyclic aromatic compound is used as a polymerizable monomer and / or a crosslinking agent.
However, some of the polymerizable monocyclic aromatic compounds used in the synthesis stage remain unreacted or remain as oligomers that could not be grown to a matrix structure and become impurities in the ion exchange resin. Remain. Therefore, conventional gas adsorbents with good carbonyl compound adsorptivity release monocyclic aromatic compounds having a benzene ring such as toluene, styrene, divinylbenzene, ethylvinylbenzene, diethylbenzene, and phenol. Aromatic compounds are free harmful gas components derived from the gas adsorbent itself, and are known to cause, for example, health effects as well as a decrease in gas adsorption rate, gas adsorption rate, and odor. ing.

For such a problem, the gas adsorbent of the present invention generally uses the aromatic compound of the gas adsorbent as an index with the content of the monocyclic aromatic compound represented by the following formula 1 per unit mass of the gas adsorbent as an index. In particular, the release of monocyclic aromatic compounds having a benzene ring.
That is, in the gas adsorbent of the present invention, the content of the monocyclic aromatic compound represented by the following formula 1 in the gas adsorbent per unit mass is 4 mg / g or less, more preferably 1 mg / g or less, Preferably it is 0.1 mg / g or less, more preferably 0.01 mg / g or less, more preferably 0.001 mg / g or less, and has a harmful aromatic compound derived from the gas adsorbent itself, particularly a benzene ring. The amount of monocyclic aromatic compounds released is very small.

(In the above formula 1, R represents a substituent selected from a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, and an alkenyl group having 1 to 3 carbon atoms. N is a number from 1 to 6, and the number of substituents R. When there are a plurality of R, each R may be the same or different.)

The content of the monocyclic aromatic compound represented by the above formula 1 is measured, for example, by the following procedure.
<Aromatic compound dissolution test method>
The column is filled with a gas adsorbent as an analyte, and a polar organic solvent such as isopropanol, acetone or THF (tetrahydrofuran) is passed as an eluent to elute the aromatic compound. The obtained eluent is measured by an analytical method capable of quantifying aromatic compounds such as gas chromatography, liquid chromatography, mass spectrometry, and nuclear magnetic resonance spectroscopy.

In order to keep the content of the monocyclic aromatic compound in the gas adsorbent within the above range, the gas adsorbent is released in a free state by a method such as washing with an organic solvent such as methanol, acetone, propanol, or THF (tetrahydrofuran). The monocyclic aromatic compound may be removed. In addition, you may heat the said washing | cleaning as needed. Further, the cleaning method may be batch cleaning or column passing. In addition to the above washing, or alone, it may be washed with the above organic solvent at the final product stage.
In addition, the above monocyclic ring can also be obtained by subjecting it to steam purification treatment at the polymerization polymer stage and / or the chloromethylated polymer stage at the time of preparing the base resin before introducing the ion exchange group and / or the product stage after introducing the ion exchange group. Aromatic compounds can be removed. Prior to the introduction of the exchange group, since it is excellent in thermal stability, it is possible to ventilate high-temperature superheated steam. On the other hand, since the thermal stability of the resin is inferior after amination, it is preferable to pass low-temperature water vapor.

Next, among the above conditions, the condition (IV) will be described.
As described above under condition (II), the amine odor component derived from the unreacted amino compound in the gas adsorbent has a bad odor, which hinders its use as a gas adsorbent.
On the other hand, the amine odor component of the gas adsorbent is also generated by the decomposition of a nitrogen-containing substituent (for example, a quaternary ammonium group) incorporated into the gas adsorbent by a chemical bond. That is, this invention prescribes | regulates the amount of amine odor components of a gas adsorbent more appropriately by making condition (IV) into the requirement.

The neutral salt decomposition capacity represents the amount of a functional group derived from a quaternary ammonium group in the alkali adsorption capacity or the acid adsorption capacity. Specifically, the neutral salt decomposition capacity means an amount capable of decomposing nitrogen-containing substituents (for example, quaternary ammonium groups) incorporated into the gas adsorbent by chemical bonds. As a factor for promoting the decomposition of the functional group derived from the quaternary ammonium group, when the counter ion of the ion exchange group is in the OH form, it is heated and dried (the quaternary ammonium group is stabilized by hydration). , When it loses moisture, it is easily decomposed).
As a result of decomposition of the nitrogen-containing substituent of the gas adsorbent, an amine odor is generated, which impairs the function as a gas adsorbent. Therefore, the neutral salt decomposition capacity can appropriately express the amount of amine odor components resulting from the decomposition of the nitrogen-containing substituent of the gas adsorbent.
That is, the gas adsorbent of the present invention has a neutral salt decomposition capacity per unit mass of 0.43 meq / g or less, preferably 0.2, as defined in the above condition (IV). It is milliequivalent / g or less, more preferably 0.15 milliequivalent / g or less, more preferably 0.10 milliequivalent / g or less, and very little malodor derived from the gas adsorbent itself, especially amine odor. . The lower limit of the neutral salt decomposition capacity is most preferably 0, and is usually 0.01 to 0.05 meq / g.

The neutral salt decomposition capacity is measured by the following procedure, for example.
<Neutral salt decomposition capacity measurement method>
The neutral salt decomposition capacity of the anion exchange resin of the present invention is analyzed and measured by the following method.
First, an anion exchange resin is packed in a column, and a 5% NaCl aqueous solution having a volume 25 times the resin volume is passed through the column to convert the counter ion to Cl form. 10.0 ml of this resin is taken, and 75-fold volume of 2N-NaOH aqueous solution is passed through to regenerate Cl form to OH form. Wash thoroughly with demineralized water until the washing filtrate becomes neutral, and then collect 25% of 5% NaCl aqueous solution to collect all the effluent. The effluent is titrated with 1N hydrochloric acid or 0.1N hydrochloric acid to measure the neutral salt decomposition capacity. This is converted per 1 ml of resin, and the neutral salt decomposition capacity per volume is calculated. On the other hand, 10.0 ml of resin is taken with a graduated cylinder, this is drained with a centrifuge, and the weight of the resin after draining is measured. This resin is dried in a vacuum dryer at 50 ° C. for 8 hours, and the weight of the resin after drying is measured. The neutral salt decomposition capacity per dry weight is calculated from the weight in the drained state and the weight after drying.

In order to bring the neutral salt decomposition capacity of the gas adsorbent into the above range, a known method for suppressing the neutral salt decomposition capacity of the gas adsorbent can be employed.
For example, as a method for synthesizing a silica-based support, an amine species having an amino group (—NH ₂ ) in advance, for example, aminopropyltrialkoxysilane, 3 (2 (2-Aminoethylamino) ethylamino) propyl-trimethoxysilane, or the like is reacted. Is mentioned. If such a reaction is used, the neutral salt decomposition capacity can be suppressed.
For example, in an ion exchange resin, when an amine species is reacted with a chloromethyl group of an ion exchange resin precursor, the chloromethyl group is completely converted to amino by using a large excess of an amine species such as dimethylamine. Therefore, the by-product of the quaternary ammonium salt can be suppressed, and the neutral salt decomposition capacity can be suppressed low. Further, in the case of amine species such as polyethylene polyamine represented by diethylenetriamine, neutral salt decomposition capacity can be kept low by reducing the amount of amine species used (amine amount). Moreover, since the by-product quaternary ammonium salt is easily thermally decomposed, the neutral salt decomposition capacity can be suppressed by heating in advance to decompose the quaternary ammonium group.

Next, among the above conditions, the condition (V) will be described.
As described above in condition (I), it is presumed that a gas adsorbent having a larger pore radius than the conventional gas adsorbent can induce harmful components into the pores of the gas adsorbent. The agent can be taken into the pores and has excellent gas diffusibility in the pores, and can exhibit high performance as a gas adsorbent. However, the gas adsorption efficiency varies depending on how the harmful components taken into the pores can be retained, that is, the amount of adsorption of the harmful gas components of the gas adsorbent.
For example, even when the average pore radius is as large as 350 mm or more, if the adsorption amount of harmful gas components is small, the gas components are not retained even if they are sufficiently diffused in the pores. It was found that gas adsorbability may be low.

Therefore, in the present invention, the acid adsorption capacity of the gas adsorbent per unit mass is defined as a gas adsorbability index in order to more efficiently adsorb the target substance taken in efficiently.
Tobacco smoke contains organic acids such as formic acid, acetic acid, propionic acid, sulfur dioxide, nitrogen dioxide, hydrochloric acid, nicotinic acid, hydrogen cyanide, hydrogen sulfide, etc. as harmful gases other than low molecular weight aliphatic aldehydes . Therefore, these other harmful gases contained in tobacco smoke are also harmful gas components that are likely to be encountered in the living environment.
Therefore, in the present invention, it is preferable to prescribe the adsorptivity of the gas adsorbent to harmful gases in general, particularly hydrogen cyanide and hydrogen sulfide contained in tobacco smoke, using the acid adsorption capacity per unit mass of the gas adsorbent as an index. .
In the present invention, when the acid adsorption capacity of the gas adsorbent per unit mass is specified, the adsorption amount of the acidic component is 1.5 meq / g or more, preferably 2.0 meq / g or more, More preferably, it is 2.5 meq / g or more, particularly preferably 3.0 meq / g or more.

The acid adsorption capacity measurement test is performed, for example, using a 0.5 to 5N aqueous hydrochloric acid solution as a test solution in the following procedure.
<Acid adsorption capacity measurement test method>
A sodium hydroxide aqueous solution is brought into contact with a gas adsorbent as an analyte to regenerate the acidic component adsorption ability, and then mixed with a predetermined amount of 0.5 to 5N hydrochloric acid aqueous solution and sufficiently brought into contact therewith. Next, the solution portion in the mixture is sampled, neutralized with a basic solution of a predetermined concentration, for example, 0.5 to 5N sodium hydroxide aqueous solution, and the amount of hydrochloric acid aqueous solution used for acid adsorption and titration. The acid adsorption capacity is calculated from the amount of basic solution consumed.

More specifically, for example, the following procedures can be mentioned.
Collect 10.0 ml of the gas adsorbent with a graduated cylinder, fill it in a glass column, pass through 200 ml of 2N-hydrochloric acid aqueous solution, and wash with demineralized water. Next, 250 ml of 2N-sodium hydroxide aqueous solution is passed through. Further, the desalted water is passed until the effluent is neutral. The obtained adsorbent is put into a 500 ml Erlenmeyer flask, 300 ml of 0.2N hydrochloric acid aqueous solution is added, and shaken for 8 hours. After shaking, 20.0 ml of the supernatant is sampled with a whole pipette, titrated with a 0.1N aqueous sodium hydroxide solution, the amount of adsorbed hydrochloric acid is converted per volume, and the acid adsorption capacity is determined.

  In order to set the acid adsorption capacity of the gas adsorbent within the above range, the amount of acid adsorbing groups introduced into the gas adsorbent may be adjusted by a known method. For example, in an acrylic ion exchange resin, a functional group is introduced by a reaction between a glycidyl group and an amine species, so that the glycidyl group is contained to some extent. In addition, in the case of a phenol type or a styrene type, an amine is introduced by introducing a chloromethyl group, so that the chloromethyl group is introduced more than the introduced amount of the acid adsorption group. In the case of activated carbon, (i) an amine having a low molecular weight is used and diffused to the pore structure of the activated carbon when using the amine deposition method. (Ii) In order to increase the attachment efficiency, for example, a method of using an amine compound having a partially hydrophobic group such as a long-chain aliphatic amine or benzylamine can be employed.

In addition, the gas adsorbent of the present invention preferably has the following characteristics (VI) and (VII). Moreover, when using the gas adsorbent of this invention as a gas adsorbent for tobacco filters, what has the following characteristics (VIII) and (IX) is preferable.
(VI) The amount of propionaldehyde adsorbed on the gas adsorbent per unit mass is 240 mg / g or more when measured using a 2 wt% propionaldehyde aqueous solvent solution.
(VII) The concentration of the aqueous propionaldehyde solution after contact of 50.0 g of the gas adsorbent with 100.0 ml of a 100 ppm aqueous propionaldehyde solution at 25 ° C. for 3 minutes is 80 ppm or less.
(VIII) The amount of nicotinamide adsorbed on the gas adsorbent per unit mass is 10 mg / g or less when measured using a 1 wt% nicotinamide aqueous solution.
(IX) The amount of l-menthol adsorbed on the gas adsorbent per unit mass is 50 mg / g or less when measured using a 2 wt% 1-menthol aqueous solution based on a 50 wt% methanol aqueous solution.

  As described above, the carbonyl compound is one of harmful gas components that are likely to be encountered in the living environment. In the present invention, using the amount of propionaldehyde adsorbed per unit mass of the gas adsorbent as an index, the adsorbability of the gas adsorbent to all carbonyl compounds, particularly low molecular aliphatic aldehydes, satisfies the above (VI). preferable.

  That is, in the gas adsorbent of the present invention, as defined in the above condition (VI), the propionaldehyde adsorption amount measured using a 2 wt% propionaldehyde aqueous solvent solution is 240 mg / g or more, preferably 300 mg / g. g or more, more preferably 340 mg / g or more. The gas adsorbent of the present invention is excellent in adsorptivity to carbonyl compounds among harmful gas components, and in particular, low molecular weight having about 1 to 5 carbon atoms such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, crotonaldehyde, acrolein and the like. Excellent adsorptivity to aliphatic aldehydes. The “adsorptive” and “adsorption amount” include not only the mode in which the carbonyl compound is actually adsorbed on the gas adsorbent, but also functional groups (for example, anion exchange groups) contained in the gas adsorbent. A mode in which volatile carbonyl compounds are reduced as a result of the formation of a quanta by the aldol condensation of a carbonyl compound as a catalyst is also included.

In the propionaldehyde adsorption test, an aqueous solvent solution in which the propionaldehyde concentration is adjusted to 2% by weight is used as a test solution. The aqueous solvent used for the preparation of the test solution is, for example, mere water such as demineralized water or pure water or a mixed solution of water-soluble organic solvent and water, preferably mere water or 50% by weight or less of water-soluble organic. It is a mixture of solvent and water. As a specific example of the test solution, a 2 wt% aqueous propionaldehyde solution based on a 10 wt% aqueous methanol solution can be used.
The propionaldehyde adsorption test is performed by the following procedure, for example.

<Propionaldehyde adsorption test method>
The gas adsorbent as the analyte is mixed with the propionaldehyde aqueous solvent solution adjusted to the above predetermined concentration, shaken sufficiently at room temperature, and then the supernatant is sampled. For example, gas chromatography or liquid chromatography The concentration of propionaldehyde is measured by an analysis method capable of quantifying propionaldehyde such as, and the amount of adsorption is calculated.

  In order to make the amount of propionaldehyde adsorbed on the gas adsorbent within the above range, the gas adsorbent may be appropriately prepared by increasing the pore radius as described above and increasing the acid adsorption capacity. .

In view of the fact that the present invention aims at “gas” adsorption, in order to more appropriately express the gas adsorbent of the present invention from the viewpoint of adsorption speed, it is more preferable that the above (VII) is satisfied.
That is, in the gas adsorbent of the present invention, as specified in the above condition (VII), 50.0 g of the gas adsorbent was brought into contact with 100.0 ml of a 100 ppm aqueous propionaldehyde solution at 25 ° C., and the propionaldehyde after 3 minutes had passed. The concentration of the aqueous solution is 80 ppm or less. The propionaldehyde concentration after 3 minutes is preferably 70 ppm or less. Further, the propionaldehyde concentration after 10 minutes is usually 60 ppm or less, preferably 50 ppm or less, and more preferably 45 ppm or less.
The propionaldehyde adsorption rate test is performed by the following procedure, for example.

<Propionaldehyde adsorption rate test method>
To a 300 ml Erlenmeyer flask, 5.0 g of a gas adsorbent (drained) is added, and 100.0 ml of a propionaldehyde aqueous solution with a concentration of 100 ppm adjusted to a temperature of 25 ° C. in advance is instantaneously injected therein. Shake on a shaker set at 25 ° C. under conditions that maintain the resin suspension, sample the supernatant 3 minutes later, 10 minutes after adding propionaldehyde aqueous solution, gas chromatography (GC) and high-speed liquid The concentration of propionaldehyde is measured by chromatography (HPLC).

  In order to make the concentration of the aqueous propionaldehyde solution within the above range, the gas adsorbent may be appropriately prepared by increasing the pore radius and increasing the acid adsorption capacity as described above.

  Here, there is a view that the conditions (VI) and (VII) do not appropriately express the phenomenon of trapping harmful gas in the gas phase system in terms of bringing the aqueous solution into contact with the gas adsorbent. However, as shown in the examples described later, the amount of adsorption under the conditions (VI) and (VII) is substantially proportional to the amount of gas adsorbed in the results of the gas phase gas capture test described below. Therefore, it can be said that the conditions (VI) and (VII) represent the gas trapping ability in the gas phase system almost appropriately.

Nicotinic acid amide is one of the flavor components originally contained in tobacco smoke, and gives a tobacco-like flavor. Therefore, when the present invention is used for a tobacco filter, the nicotinic acid amide contained in the cigarette smoke in general, particularly the gas components that give a tobacco-like flavor, with the nicotinic acid adsorption amount per unit mass of the gas adsorbent as an index. It is preferable to define the adsorptivity of the gas adsorbent with respect to.
That is, when the gas adsorbent of the present invention is used for a tobacco filter, as specified in the above condition (VIII), when the amount of adsorbed nicotinamide of the gas adsorbent is specified, 1% by weight of nicotinic acid is used. The adsorbed amount of nicotinamide of the gas adsorbent per unit mass measured using an amide aqueous solution is 10 mg / g or less, preferably 1 mg / g or less, more preferably 0.1 mg / g or less. Does not damage the ingredients.

  The adsorption amount of nicotinamide represented by the following formula 2 is measured by the following procedure using, for example, a 1% by weight nicotinamide aqueous solution as a test solution.

<Nicotinamide adsorption test method>
First, an aqueous nicotinamide solution adjusted to the predetermined concentration is prepared as a test solution. Next, after mixing the gas adsorbent, which is the analyte, with the test solution and shaking well at room temperature, the supernatant is sampled. For example, gas chromatography, liquid chromatography, mass spectrometry, nuclear magnetic The concentration of nicotinamide is measured by an analysis method that can quantify nicotinamide, such as resonance spectroscopy, and the amount of adsorption is calculated.

  In order to make the adsorption amount of nicotinamide on the gas adsorbent within the above range, a large amount of hydrophilic groups (ion exchange groups) of the gas adsorbent may be introduced. That is, as described above, the acid adsorption amount may be increased to prepare appropriately.

l-menthol is one of the flavor components mainly added to tobacco and gives a refreshing feeling. Therefore, when the present invention is used for a tobacco filter, the gas component for l-menthol added to tobacco, in general, gives a refreshing feeling with the amount of l-menthol adsorbed per unit mass of the gas adsorbent as an index. It is preferable to define the adsorptivity of the adsorbent.
That is, the l-menthol adsorption amount of the gas adsorbent per unit mass is 50 mg / g or less, preferably 40 mg / g or less, more preferably 30 mg / g or less, and does not impair the flavor components added to the tobacco.

In the l-menthol adsorption test, l-menthol represented by the following formula 3 is used as a 2 wt% 1-menthol aqueous solution based on a 50 wt% methanol aqueous solution.
The l-menthol adsorption test is performed, for example, by the following procedure.

<1-Menthol adsorption test method>
The gas adsorbent that is the analyte is mixed with a 2 wt% 1-menthol aqueous solution based on a 50 wt% methanol aqueous solution adjusted to the above predetermined concentration, shaken sufficiently at room temperature, and then the supernatant is sampled, for example, The concentration of l-menthol is measured by an analytical method that can quantify l-menthol, such as gas chromatography, liquid chromatography, mass spectrometry, and nuclear magnetic resonance spectroscopy, and the amount of adsorption is calculated.

  In order to make the amount of 1-menthol adsorbed to the gas adsorbent within the above range, a large number of hydrophilic groups (ion exchange groups) of the gas adsorbent may be introduced. That is, as described above, the acid adsorption amount may be increased to prepare appropriately.

When the gas adsorbent of the present invention satisfies the above (VIII) and / or (IX), it effectively removes harmful substances such as carbonyl compounds and hydrogen cyanide, while nicotinic acid amide originally contained in tobacco. In addition, there is little adsorption of flavor components useful for tobacco such as l-menthol added to tobacco, and there is little emission of malodorous components derived from the gas adsorbent itself such as amine impurities.
Therefore, the gas adsorbent satisfying the above (VIII) and / or (IX) can selectively remove harmful gas components in tobacco smoke without impairing the flavor of tobacco.
In addition, the gas adsorbent of the present invention may have the following characteristics.

  In applications that remove harmful gases such as cigarette filters, air purifiers, and car air conditioners, the passing speed of harmful gases in gas adsorbents is extremely high. Considering this point, the weight average particle size of the gas adsorbent of the present invention is usually 50 μm or more, more preferably 100 μm or more, particularly preferably 300 μm or more, usually 1500 μm or less, further 800 μm or less, particularly 750 μm or less, especially 600 μm or less. It is preferable that If the weight average particle diameter of the gas adsorbent is too large, there are problems of a decrease in adsorption rate, pulverization due to resin crushing, and generation of fine powder. On the other hand, if the weight average particle diameter is too small, there are problems such as generation of ventilation resistance, deterioration of workability when filling the filter, powder scattering, manufacturing cost, and deterioration of workability due to generation of static electricity. The weight average particle diameter of the gas adsorbent of the present invention refers to the weight average particle diameter at 25 ° C. and 50% relative humidity. For example, in the case of an ion exchange resin, the moisture retention varies depending on the type of ion exchange group, the exchange capacity, etc., but the relative humidity at 25 ° C. In the state of 50%, it is usually 5 to 30% by weight.

The weight average particle diameter is measured, for example, by the following procedure.
<Weight average particle size measurement method>
The sieves having a sieve mesh diameter of 1180 μm, 850 μm, 710 μm, 600 μm, 425 μm, and 300 μm are stacked so that the sieve mesh diameter decreases as it goes downward. The stacked sieve is placed on a bat, and about 100 mL of a gas adsorbent is placed in a 1180 μm sieve stacked on the top.
Gently pour water onto the resin from a rubber tube connected to tap water and screen the small particles downward. The gas adsorbent remaining in the 1180 μm sieve is further screened for small particles by the following method. That is, water is filled up to a depth of about 1/2 of another bat, and a 1180 μm sieve is repeatedly shaken by giving up and down and rotational motion in the bat, and small particles are sieved.
The small particles in the vat are returned onto the next 850 μm sieve, and the gas adsorbent remaining on the 1180 μm sieve is collected in another vat. If the gas adsorbent is clogged in the sieve, place the sieve in the vat reversely, closely contact the rubber tube connected to the tap water, and take out the gas adsorbent clogged with the water by strongly flowing water. The taken-out gas adsorbent is transferred to a bat that collects the gas adsorbent remaining on the 1180 μm sieve, and the volume is measured with a graduated cylinder. Let this volume be a (mL). The gas adsorbent that passed through the 1180 μm sieve was subjected to the same operation for each of the 850 μm, 710 μm, 600 μm, 425 μm, and 300 μm sieves. e (mL) and f (mL) are obtained, and finally, the volume of the resin that has passed through the 300 μm sieve is measured with a graduated cylinder to be g (mL).
V = a + b + c + d + e + f + g, a / V × 100 = a ′ (%), b / V × 100 = b ′ (%), c / V × 100 = c ′ (%), d / V × 100 = d ′ ( %), E / V × 100 = e ′ (%), f / V × 100 = f ′ (%), g / V × 100 = g ′ (%).
From the above a ′ to g ′, the residual amount cumulative (%) of each sieve is taken on one axis, and the diameter (mm) of the sieve mesh is taken on the other axis, and this is plotted on the logarithmic probability paper. Take 3 points in the order of the remaining amount, draw a line that satisfies these 3 points as much as possible, obtain the diameter (mm) of the sieve mesh corresponding to 50% of the accumulated residue from this line, and calculate the weight average The particle size.
In addition, the calculation method of the said weight average particle diameter is described, for example in Mitsubishi Chemical Corporation ion exchange resin division "Diaion I basics edition" 14th edition (September 1, 1999) pp.139-141. This is a known calculation method.
The gas adsorbent of the present invention having the above weight average particle diameter can be obtained by, for example, a known classification method. As the classification method, classification using a sieve, a water sieve using a water stream, a wind sieve using an air stream, and the like can be used.

As described above, in the gas adsorbent of the present invention, the pore structure and the accompanying characteristics are important elements in the mechanism of gas adsorption. Therefore, any material that satisfies the above various conditions can be used as the gas adsorbent of the present invention regardless of the type of the material. Specifically, for example, an organic or inorganic base having an average pore radius of the condition (I) specified in the present invention, a neutral salt decomposition capacity of the condition (IV), and an acid adsorption capacity of the condition (V) After synthesizing the material and introducing a functional group that adsorbs harmful components to the base material, an appropriate washing treatment and / or the above-described steam purification treatment are performed, so that the amine elution amount of the condition (II) and the condition (III The gas adsorbent of the present invention can be obtained by adjusting the content of the monocyclic aromatic compound. Further, as exemplified below, by adjusting the amine elution amount under the condition (II) specified in the present invention and the content of the monocyclic aromatic compound under the condition (III) by a specific synthesis method, The gas adsorbent of the present invention can also be synthesized by synthesizing an organic or inorganic base material having an average pore radius of I), a neutral salt decomposition capacity of condition (IV), and an acid adsorption capacity of condition (V). can get. In this case, the washing treatment after the functional group introduction and / or the above-described steam purification treatment may not be required, but it is preferable to perform the washing treatment and / or the above-described steam purification treatment.
Alternatively, by adjusting the properties of existing ion exchange resins made of anion exchange resin and cation exchange resin, and existing adsorbents based on inorganic materials such as silica, alumina, or activated carbon by washing treatment etc., the present invention Gas adsorbent.
The base material may have different physical properties from the final product due to shrinkage and swelling under the conditions of washing and post-treatment. Therefore, when synthesizing an organic or inorganic base material, or when using an existing adsorbent as a base material, the “final product” has an average pore radius, a condition (condition (I) specified in the present invention ( It is necessary to design the base material to have a neutral salt decomposition capacity of IV) and an acid adsorption capacity of condition (V). Specifically, for example, the following adjustment is required.
(I) The base polymer is designed so that the average pore radius is larger than the condition (I).
(Ii) The acid adsorption capacity of the base polymer is designed to be larger than the condition (V).

  The synthetic adsorbent is a synthetic resin in which a functional group having ion exchange ability is chemically, physically or physicochemically fixed to a matrix having a three-dimensional crosslinked polymer structure, for example, an aromatic synthetic adsorbent, Examples of (meth) acrylic synthetic adsorbents (in the present invention, “(meth) acrylic” means “acrylic” or / and “methacrylic”) and phenolic synthetic adsorbents. it can.

Examples of the aromatic synthetic adsorbent include a synthetic adsorbent having a crosslinked structure skeleton obtained by copolymerization of a monovinyl aromatic monomer and a crosslinkable aromatic monomer. Examples of the monovinyl aromatic monomer include alkyl-substituted styrenes such as styrene, methylstyrene, and ethylstyrene, and halogen-substituted styrenes such as bromostyrene. Among these, styrene or a monomer mainly composed of styrene is preferable. Moreover, as a crosslinkable aromatic monomer, divinylbenzene, trivinylbenzene, divinyltoluene, divinylnaphthalene, divinylxylene, etc. are mentioned. Of these, divinylbenzene is preferred. Industrially produced divinylbenzene usually contains a large amount of by-product ethyl vinylbenzene (ethyl styrene), but such divinylbenzene can also be used in the present invention.
Specific examples include styrene-divinylbenzene synthetic adsorbents.

As the (meth) acrylic synthetic adsorbent, (A) a cross-linking agent part containing a poly (meth) acrylic acid ester of a polyhydric alcohol, and (B) an ester having a polymerizable unsaturated group and a functional group and / or Examples thereof include a matrix having a basic skeleton portion containing ether.
Poly (meth) acrylic acid esters of polyhydric alcohols include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, glycerol poly (meth) acrylate, polyethylene glycol (meth) acrylate , Trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, and the like. Of these, ethylene glycol di (meth) acrylate is preferred. In addition, as the ester and / or ether having a polymerizable unsaturated group and a functional group, a glycidyl ester of a carboxylic acid (preferably having 3 to 12 carbon atoms) having one polymerizable vinyl group or isopropenyl group, Examples thereof include hydroxyalkyl esters of carboxylic acids, alkenyl (preferably having 3 to 12 carbon atoms) glycidyl ethers having one polymerizable vinyl group or isopropenyl group. Among these, glycidyl (meth) acrylate, allyl glycidyl ether, and 2-hydroxyethyl (meth) acrylate are preferable.
Specific examples include a matrix having a resin skeleton of a methacrylic crosslinked polymer obtained by polymerizing ethylene glycol dimethacrylate, glycidyl methacrylate, and divinylbenzene.

Examples of the phenol-based synthetic adsorbent include synthetic adsorbents obtained by polycondensation of phenol-based compounds. Examples of phenolic compounds include phenol, phenol derivatives, paraphenylenediamine, and the like.
Specific examples include phenol-formaldehyde resins. The phenol-based synthetic adsorbent can be produced, for example, by mixing catechol, phenol, paraformaldehyde and a diluting solvent in an aqueous hydrochloric acid solution and performing polycondensation by suspension polymerization in a reverse phase.

The synthetic adsorbent is preferably an ion exchange resin having a functional group, more preferably a weakly basic to strongly basic anion exchange resin, and particularly preferably a weakly basic anion exchange resin.
Here, the “weakly basic anion exchange resin” is a resin having a weakly basic anion exchange group such as a primary to tertiary amino group. In general, weakly basic anion exchange resins can exchange anions only in acidic or neutral solutions, and salts of strong bases such as HCl and H ₂ SO ₄ and weak bases such as NH ₄ Cl can be easily anion exchanged. Yes, but weak acids are difficult to exchange anions.
On the other hand, the “strongly basic anion exchange resin” is a resin having a strongly basic anion exchange group such as a quaternary ammonium group. In general, a strong base anion exchange resin can perform anion exchange in a solution in the entire pH range from acidic to alkaline, and can exchange not only strong acids and neutral salts but also weak acids.

In the present invention, a weakly basic anion exchange resin is particularly preferable among the anion exchange resins.
Preferred weak basic anion exchange resins include those obtained by washing a known weak basic anion exchange resin with an acid, those subjected to a steam purification treatment, and cross-linked polystyrene obtained by a high temperature polymerization reaction. And the like. In addition, you may manufacture the gas adsorbent (anion exchange resin) of this invention combining 2 or more among the acid washing | cleaning mentioned later, water vapor | steam purification process, and high temperature polymerization reaction process.

<Weakly basic anion exchange resin obtained by washing with acid>
Known weakly basic anion exchange resins for washing include, for example, Diaion CR20 (trade name, manufactured by Mitsubishi Chemical Corporation), WA21 (trade name, manufactured by Mitsubishi Chemical Corporation), WA30 (trade name, manufactured by Mitsubishi Chemical Corporation). HPA25 (trade name, manufactured by Mitsubishi Chemical Corporation), Duolite A361 (trade name, manufactured by Rohm and Haas), Purolite A103 (trade name, manufactured by Purolite), Amberlite IRA93 (trade name, manufactured by Rohm and Haas), Duolite A378 (trade name, manufactured by Rohm and Haas), Lewatit MP64 (trade name, manufactured by LANXESS), Dowex MWA1 (trade name, manufactured by Dow Chemical), Amberlite IRA904 (trade name, manufactured by Rohm and Haas) It is done.

The acid used for washing is preferably a strong acid, and examples thereof include 0.1 to 5N hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, and nitric acid. The strong acid may be mixed with a water-soluble organic solvent. Specific examples of the water-soluble organic solvent include alcohols such as methanol, ethanol, isopropyl alcohol, THF (tetrahydrofuran), dioxane, dimethylformamide. Etc.
Washing is performed by stirring the ion exchange resin in a strong acid. The higher the acid temperature, the higher the cleaning effect, and it is room temperature to 120 ° C, preferably 40 to 100 ° C, more preferably 40 to 80 ° C. The cleaning method may be batch cleaning or column cleaning.

A specific method for washing a weakly basic anion exchange resin will be described below.
That is, a known weakly basic anion exchange resin is washed using a strong acid such as hydrochloric acid or sulfuric acid having a temperature of 40 to 80 ° C. and a concentration of 0.1 to 5 N with sufficient stirring. After washing, the column is filled with the resin, the strong acid having a temperature of 40 to 80 ° C. and a concentration of 0.1 to 5 N is passed through the column, and then demineralized water is passed to remove excess strong acid.
Next, methanol is passed through the resin in the column at 2 BV to 4 BV (“BV” represents a volume (L) with respect to 1 L of the resin (gas adsorbent)), and further, room temperature to 50 ° C., concentration of 0. A 1 to 3 N aqueous sodium hydroxide solution is passed through to convert the ion exchange groups of the resin in the column to the OH form. Finally, by passing demineralized water, a weakly basic anion exchange resin that satisfies the conditions required for the present invention can be obtained.

<Weakly basic anion exchange resin obtained by steam purification treatment>
The steam purification treatment is a polymerization polymer and / or chloromethylated polymer before the introduction of ion exchange groups, or a product after introduction of ion exchange groups, which is brought into contact with water vapor to leave unreacted remaining during base resin synthesis. This is a treatment method for removing a monocyclic aromatic compound, an aromatic compound containing an unreacted amino compound or a polymerizable monomer remaining at the time of introducing an ion exchange group.
The temperature atmosphere temperature of water vapor when contacting water vapor varies depending on the type of resin. In the case of a weakly basic anion exchange resin, it is usually 150 ° C. or lower, preferably 120 ° C. or lower. On the other hand, for polymerized polymers and chloromethylated polymers, the temperature is usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 140 ° C. or higher. Moreover, it is 250 degrees C or less normally, Preferably it is 220 degrees C or less.
The amount of water vapor is usually 0.01 kg / h or more, preferably 0.05 kg / h or more, more preferably 0.1 kg / h or more, particularly preferably 0.3 kg / h or more in terms of water relative to 1 L of resin. It is. Moreover, it is 10 kg / h or less normally, Preferably it is 5 kg / h or less, More preferably, it is 2 kg / h or less.
If the amount of water vapor contacted is too small, there is a problem that the residue cannot be removed and / or the high-boiling residue is difficult to remove. On the other hand, when there is too much water vapor | steam, it not only leads to the loss of a thermal energy, but in the case of an aminated product, a product may decompose | disassemble.
Specifically, for example, the following method is used as a method of bringing the water vapor into contact.
Water vapor is passed through the jacketed SUS column or a SUS column kept warm with a heat insulating material in an upward flow or a downward flow. When acids and halogens are discharged due to the flow of water vapor, a column with a Teflon (registered trademark) coating on the wall surface in the column is used. Water vapor discharged from the column is cooled by a heat exchanger and recovered as water.

<Weak Basic Anion Exchange Resin Obtained by Introducing Ion Exchange Groups into Crosslinked Polystyrene Obtained by High Temperature Polymerization Reaction>
As a weakly basic anion exchange resin obtained by introducing ion exchange groups into a crosslinked polystyrene obtained by a high temperature polymerization reaction, a crosslinked polystyrene obtained by polymerizing the crosslinked polystyrene at a temperature higher than the normal reaction temperature is used. Examples include weakly basic anion exchange resins used for the base. By performing a polymerization reaction at a temperature higher than usual, it is possible to suppress the remaining of impurities such as the low polymer component derived from the base resin and the free polymer component and the generation of decomposition products, so that the conditions necessary for the present invention are satisfied. A weakly basic anion exchange resin is obtained.
Examples of the high temperature polymerization include a polymerization reaction in which at least a part of the polymerization reaction is usually performed at a high temperature of 100 ° C. or higher. The preferable high temperature polymerization conditions will be described below.

(Conditions for high temperature polymerization reaction)
The high temperature polymerization reaction has the following technical significance. That is, due to high temperature conditions, impurities such as the low polymer component and the free polymer component are easily incorporated into the polymerization reaction in a glass transition state or a state close thereto, and the remaining low polymer component or free polymer component It is thought that the amount of In addition, the structure of the polymer chain generated by polymerization becomes more robust and dense, so that the remaining low polymer components and free polymer components can be trapped in the structure of the polymer chain and then eluted. It is thought that the nature decreases. Therefore, from this viewpoint, the polymerization temperature is usually 100 ° C. or higher, preferably 110 ° C. or higher. As a specific example, the glass transition point of crosslinked polystyrene is usually about 105 ° C. when the degree of crosslinking is 5%, and about 108 ° C. when the degree of crosslinking is usually 10%. By conducting a polymerization reaction of the crosslinked polystyrene near this temperature, Residues of impurities such as low polymer components derived from the base resin and free polymer components and generation of decomposition products can be suppressed.
However, if the temperature is too high, it takes time to increase the temperature of the polymerization solution, the range of selection of the polymerization initiator is reduced, the production equipment becomes expensive, or the polymerization temperature is increased. However, the upper limit of the temperature is usually 160 ° C. or lower, preferably 150 ° C. or lower, more preferably 140, because the effect of reducing elution may not be improved any more, or the produced polymer may be modified or decomposed. It is below ℃.

  The time for the high temperature polymerization reaction (the time at which the temperature is 100 ° C. or higher) is usually 1 hour or longer, preferably 2 hours or longer, and usually 20 hours or shorter, preferably 10 hours or shorter, more preferably 6 hours or shorter. is there. If the time of the high-temperature polymerization reaction is too short, the above-described effects cannot be obtained sufficiently. On the other hand, if the time is too long, the above-described effects are not sufficiently exhibited because the amount of the remaining polymerization initiator is smaller than the amount necessary for the reaction. The produced polymer may be modified or decomposed.

  The high temperature polymerization reaction may be carried out continuously, or may be carried out intermittently in several steps with a period of 100 ° C. or less in the middle. In that case, the time which is 100 degreeC or more should just be in said range in total. However, from the viewpoint of sufficiently obtaining the above effects, it is preferable to continuously perform the high temperature polymerization reaction.

(Method of polymerization reaction)
The method of the polymerization reaction is not particularly limited, and any of various known methods such as emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization and the like can be used alone or in combination of two or more. . These may be appropriately selected according to the type and application of the target polymer.
In particular, when the obtained polymer is used as an ion exchange resin or a synthetic adsorbent as described later, the shape of the polymer is preferably granular, particularly spherical or substantially spherical. In order to produce a (or substantially spherical) polymer, it is effective to perform water-in-oil type or oil-in-water type suspension polymerization.

  When water-in-oil type or oil-in-water type suspension polymerization is performed, the water phase and the oil phase are placed in a reactor, and the polymerization reaction is performed while the suspension is put into a suspended state by means such as stirring. The dispersed phase and the continuous phase have a ratio value of (volume of the dispersed phase) :( volume of the continuous phase), usually 1: 1 or more, preferably 1: 1.5 or more, and usually 1:10 or less, preferably Is preferably in the range of 1: 6 or less, more preferably 1: 4 or less.

  As the water phase component, water is usually used. On the other hand, the oil phase is mainly composed of raw material monomers and an organic solvent used as necessary. Further, the polymerization initiator is present in the oil phase in the case of a water-insoluble polymerization initiator such as a peroxide such as benzoyl peroxide or an azo compound such as azobisisobutyronitrile, On the other hand, in the case of a water-soluble polymerization initiator such as persulfate, hydrogen peroxide, or hydroperoxide, it is present in the aqueous phase.

  Various physical properties (viscosity, specific gravity, interfacial tension, etc.) of the oil phase vary greatly depending on the configuration and composition. For this reason, it is preferable to adjust the specific gravity of the oil phase to usually 0.8 or more and 1.4 or less, and it is preferable to adjust the viscosity of the oil phase to usually 0.1 cps (centipoise) or more and 200 cps or less. When suspending oil phase droplets in the aqueous phase, the difference between the specific gravity of the aqueous phase and the specific gravity of the oil phase {(specific gravity of the aqueous phase)-(specific gravity of the oil phase)} is usually 0 or more, Preferably it is 0.5 or less, More preferably, it is 0.2 or less.

  When the aqueous phase is a continuous phase, the aqueous phase is immiscible with the oil phase composed of the raw material monomers and the like and needs to be an inert liquid suitable for allowing the oil phase to be dispersed therein as droplets. There is. Usually the aqueous phase contains a suspending agent. The suspension that can be used routinely depends on the type, composition and amount of the aqueous phase component used. The suspending agent used here is not particularly limited, and a suspending agent used for normal suspension polymerization can be appropriately selected and used. Representative examples include gelatin, polyvinyl alcohol, starch, polyacrylamide, poly (dimethyldiallyl) ammonium chloride, water-inert inorganic compounds such as magnesium silicate, and carboxymethyl-methylcellulose, ethylcellulose, hydroxypropylcellulose and the like. Of cellulose ethers. One of these suspending agents may be used alone, or two or more thereof may be used in any combination. However, in order to maintain uniformity in particle size without coalescence and crushing of the generated oil phase droplets, the type of water phase component and the concentration of the suspending agent are determined by correlation with the physical properties of the oil phase. To do. When maintaining the uniformity of the particle size of the oil phase droplets, the suspending agent is usually 0.01% by weight or more, preferably 0.05% by weight or more, and usually 5% by weight with respect to the total weight of the aqueous phase. % Or less, preferably 1.5% by weight or less.

(Polymerization atmosphere)
In the present invention, the amount of oxygen in the polymerization reaction system is preferably as low as possible, usually 5 ppm or less, particularly 3 ppm or less, and more preferably 1 ppm or less, as a ratio to the total raw material monomers. In addition, U.S. Pat. No. 4,192,921, JP-A-53-124184, etc. also propose a polymerization method while circulating nitrogen containing oxygen gas. However, in the polymerization reaction (especially radical polymerization reaction), if oxygen is present in the reaction system, the terminal radical is easily copolymerized with oxygen, so oxygen is incorporated into the polymerization reaction of the raw material monomer, and a polymer containing a peroxide bond. Produces. As a result, this peroxide bond can be chemically and thermally cleaved during the resin production process, washing process, or during resin use, causing oligomer generation and elution, and this peroxide bond. Is decomposed to form decomposed products such as formaldehyde and benzaldehyde, which may cause elution. Therefore, in order to suppress the elution of such oligomers and decomposition products, it is important to keep the oxygen amount in the polymerization reaction system extremely low and maintain this state.

  In order to reduce the amount of oxygen in the reaction system, it is preferable to carry out the reaction after sufficiently replacing the gas phase in the reactor with an inert gas. Degassing methods include a method of bubbling an inert gas, a method of repeating degassing under reduced pressure, a method of replacing dissolved oxygen in a liquid phase or gas phase with an inert gas by pressurization and / or heating, etc. Can be replaced by methods known in the art. Examples of the inert gas include nitrogen gas and argon gas, and nitrogen gas is preferable.

(Number of stages of polymerization)
As described above, at least a part of the polymerization reaction needs to be performed at a high temperature of 100 ° C. or higher, but this high temperature polymerization reaction may be combined with a polymerization reaction at a lower temperature and performed in multiple stages.
For example, as described above, when an organic solvent is not present in the reaction system (for example, in the case of producing a gel-type polymer, etc.), the conversion rate of the raw material monomer (conversion rate) is still low at 100 ° C. When the temperature is higher than the above, the raw material monomer is vaporized together with water to fill the reactor, and a part of the monomer is polymerized at the lid portion of the reactor, which causes a problem of adhering as an aggregate. Therefore, the polymerization reaction is first carried out at a relatively low temperature of less than 100 ° C. (this is referred to as “preliminary polymerization” as appropriate), and the monomer conversion rate is increased to some extent, and then the high temperature polymerization reaction of 100 ° C. or more is carried out. (This is appropriately referred to as “post-stage polymerization”).
In this case, the temperature of the pre-polymerization is usually 50 ° C. or higher, preferably 60 ° C. or higher, more preferably 70 ° C. or higher, and usually 100 ° C. or lower, preferably 90 ° C. or lower, more preferably 85 ° C. or lower. . If the temperature of the former stage polymerization is too low, the conversion rate of the polymerizable monomer is low, which is not preferable because the amount of deposits in the latter stage polymerization increases. On the other hand, if the temperature of the pre-polymerization is too high, the amount of deposits increases, and a dimer structure or a trimer structure due to thermal polymerization peculiar to styrene is not preferable.

  The time for the pre-polymerization varies depending on the half-life temperature and amount of the polymerization initiator, the polymerizability of the monomer, the degree of crosslinking of the resin, etc., but usually 2 hours or more, preferably 3 hours or more, more preferably 4 hours or more, The range is usually 24 hours or less, preferably 12 hours or less, more preferably 8 hours or less. If the prepolymerization time is too short, it is not preferable because the polymerization cannot be completed and the amount of the remaining low polymer component, free polymer component and the like cannot be reduced. In addition, if the pre-polymerization time is too long, it is not preferable because the productivity is lowered.

(Introduction of ion exchange groups)
The weakly basic anion exchange resin can be obtained by introducing an ion exchange group into the polymer (crosslinked polystyrene) obtained by the above polymerization.
Examples of the ion exchange group (anion exchange group) include a quaternary ammonium group, a primary to tertiary amino group (—N ⁺ H _n R _3-n ), and the like (R represents an arbitrary substituent, n Represents an integer of 1 to 3. Specific examples of the quaternary ammonium group and primary to tertiary amino group include ammonia group, methylamino group, dimethylamino group, diethylamino group, ethylenediamino group, diethylenetriamino group, triethylenetetramino group, polyethyleneimine group, butylene. Examples include a diamino group, a hexanediamino group, and an ethanolamino group.
In addition, any one of the above ion exchange groups may be introduced alone, or two or more may be introduced into the same polymer in any combination.

The ion exchange group can be introduced according to a known method. What is necessary is just to select and implement an appropriate method according to the base | substrate (polymer of this invention) used as introduction | transduction object, or the kind of ion exchange group to introduce | transduce.
For example, when a primary to tertiary amino group is introduced as a weakly basic anion exchange group, a technique described in JP-A No. 2001-106725 is used.

In addition to the above, as a method for introducing a weakly basic anion exchange group, a substrate to be introduced is chloromethylated according to a known method, and then diethylenetriamine, ethylenediamine, dimethylamine, diethylamine, monomethylamine, dibutylamine, piperazine And an amination method by adding amines such as ammonia and ammonia. By introducing such a substituent, the removal efficiency of harmful substances such as carbonyl compounds is further increased.
Initially, it was assumed that the removal mechanism of the carbonyl compound was only capture by formation of a primary amino group and a Schiff base of the carbonyl compound. However, as a result of examining the reaction mechanism, carbonyl compounds can be captured not only by primary amines but also by weakly basic anion exchange resins having secondary amines and tertiary amines, and strong basic anion exchange resins having trimethylammonium groups. Even if it exists, it discovered that a carbonyl compound could be capture | acquired with high efficiency. This is presumably because aldol condensation or aldehyde polymerization reaction is performed on the resin surface of the anion exchange resin in addition to the Schiff base formation reaction. In other words, it is presumed that oligomerization of the carbonyl compound by a so-called basic catalyst proceeds.
Considering that the aldehyde capture reaction relates to the generation of a Schiff base and the aldol condensation reaction, the weakly basic anion exchange group is preferably highly basic.
Accordingly, medium basic amine species such as ethylenediamine, diethylenetriamine, polyethylene polyamine, and polyalkylamine are preferred to the aminomethyl group that is a primary amine. From the viewpoint of the aldol condensation reaction, it is desirable that the neutral salt decomposition ability, which is a strongly basic functional group, is high, but the neutral salt decomposition ability is 0.43 meq / g or less in terms of odor and elution. Is preferable as described above.

In general, in an ion exchange resin, micropores exist in a state containing water, and gas components are diffused therein to perform gas adsorption. When the degree of cross-linking of the ion exchange resin is high, the micropores are small and the target molecules are difficult to diffuse. As a result, the capture efficiency decreases. On the contrary, if the degree of cross-linking is low, the pore structure is difficult to develop, so that it is difficult to diffuse into the pores.
In the present invention, the moisture content of the gas adsorbent is preferably 3 to 20%, 5 to 20%, and particularly preferably 5 to 15%. When the moisture content is within the above range, the gas diffusibility is appropriately maintained in the micropore, and the performance as a gas adsorbent can be maintained.

The moisture content of the gas adsorbent can be measured, for example, by the following procedure.
<Measurement of moisture content>
An aqueous NaOH solution is brought into contact with the gas adsorbent that is the subject to regenerate the anion exchange group, and then dehydrated by an appropriate device such as a centrifuge, and an appropriate amount of the dehydrated gas adsorbent is weighed. The weighed gas adsorbent is further vacuum dried, and the mass of the vacuum adsorbed gas adsorbent is measured. The moisture content of the gas adsorbent can be calculated from the mass after dehydration and the mass after vacuum drying. In addition, the moisture in the resin can be directly measured with a Karl Fischer moisture meter.

Further, as an adsorbent based on an inorganic material such as silica, alumina or activated carbon, those in which a primary to tertiary amino group or a quaternary ammonium group is fixed to these base structures are preferable.
As what fixed the primary thru | or tertiary amino group or the quaternary ammonium group based on the silica, the reactant which introduce | transduced 3-aminopropylsilyl group into the silica gel particle can be illustrated, for example.

  Examples of the adsorbent in which primary to tertiary amino groups or quaternary ammonium groups are added to alumina include, for example, silica, an alumina carrier impregnated with a solution containing a polymerizable monomer, polymerized, and ions as necessary. Examples thereof include a carrier into which an exchange group has been introduced. A polymerizable monomer having an ion exchange group may be used as necessary. For example, aminomethylstyrene or aminoethyl (meth) acrylate monomer can be used. In order to minimize elution, a polyfunctional polymerizable monomer may be added to the polymerizable monomer.

Examples of adsorbents in which primary to tertiary amino groups or quaternary ammonium groups are attached to activated carbon include, for example, tetravalent metals (Group 4A elements such as titanium, zirconium, hafnium, and thorium, Group 4B such as germanium, tin, and lead) Phosphoric acid salts and divalent metals (periodic table group 1B elements such as copper, periodic table group 2A elements such as magnesium, calcium, strontium and barium), and periodic table group 2B elements such as zinc and cadmium A periodic table group 6A element such as chromium and molybdenum; a periodic table group 7A element such as manganese; and a periodic table group 8 element such as iron, ruthenium, cobalt, rhodium, nickel, and palladium. Examples thereof include adsorbents in which sulfamic acid or sulfamate is supported on the adsorbing composition to be contained.
Further, an adsorbent formed by supporting activated carbon on a cyclic saturated secondary amine and at least one selected from a non-volatile acid, urea, and thiourea can be exemplified.
In addition, as in the case of the silica and alumina carriers, there may be mentioned a carrier into which an ion exchange group is introduced as necessary after impregnating a solution containing a polymerizable monomer and polymerizing. A polymerizable monomer having an ion exchange group may be used as necessary. For example, aminomethylstyrene or aminoethyl (meth) acrylate monomer can be used. In order to minimize elution, a polyfunctional polymerizable monomer may be added to the polymerizable monomer.

Moreover, aminobenzene sulfonic acid and hydrogen phosphate and / or phosphoric acid are attached to a porous body such as activated carbon, and the addition ratio of the hydrogen phosphate and / or phosphoric acid is 1 mol of aminobenzene sulfonic acid. The adsorbent which is 0.2-6 mol with respect to it can be illustrated.
Further, phosphoric acid and ethylenediamine and / or triethanolamine are attached to activated carbon, ethylenediamine phosphate and / or triethanolamine phosphate are attached to activated carbon, or phosphoric acid is added to activated carbon. An adsorbent obtained by adding an acid and then adding ethylenediamine and / or triethanolamine as an amine phosphate can be exemplified.

  Furthermore, an adsorbent in which an aliphatic group primary or secondary amine having a vapor pressure at 20 ° C. of 5 mmHg or less is attached to an activated carbon material, or a polyalkyleneimine having a number average molecular weight of 250 to 3000 on an activated carbon material. For example, an adsorbent in which polyethyleneimine is added in an amount of 1 to 50% by weight, preferably 5 to 30% by weight can be exemplified.

As described above, the gas adsorbent of the present invention efficiently removes harmful substances such as hydrogen cyanide and hydrogen sulfide present in cigarette smoke from a gas flow having a high flow velocity, and allows the gas adsorbent to pass through the gas adsorbent. There is little release of malodorous components such as amine impurities and free harmful components such as monocyclic aromatic compounds derived from the gas adsorbent itself in the gas.
Therefore, the gas adsorbent of the present invention is used in gas filters or devices in general for removing harmful gases, and in particular, removes harmful gases in tobacco smoke such as cigarette filters, air purifiers and car air conditioners. It is suitably used for a gas filter of equipment that is required to do.

When the gas adsorbent of the present invention is used in a cigarette filter, not only harmful substances are efficiently removed from smoke passing through the cigarette filter during smoking, but also malodorous and harmful components derived from the gas adsorbent itself. This reduces the risk of losing tobacco flavor or harming health.
In addition, when the gas adsorbent of the present invention is used in a gas filter of a device that is required to remove harmful gases in cigarette smoke such as an air cleaner or a car air conditioner, it is harmful from the air sucked at high speed. Not only is the material removed efficiently, but the air exhausted from the device does not contain malodorous or harmful components derived from the gas adsorbent itself, which makes the device user uncomfortable. Or the risk of harming the health of the device user.

The gas adsorbent of the present invention is typically used in the form of a gas filter by being supported on a support having a large surface area such as porous particles or highly breathable fiber aggregates, but it contains a non-toxic gas. As long as the processing gas can contact the gas adsorbent of the present invention, it may be used in a form other than the gas filter. When the gas adsorbent of the present invention is used as a tobacco filter, it is usually sufficient to add fine particles of the gas adsorbent of the present invention or fine particles carrying the gas adsorbent of the present invention to tobacco filter fibers.
The adsorbent of the present invention can be used alone, but can also be used in combination with other gas adsorbents.
In addition, it is preferable to use the gas adsorbent itself after processing it into the form of particles having a very small particle size or porous particles so that the contact area between the gas adsorbent of the present invention and the non-treatment gas can be increased.

  The invention will be described in more detail with reference to the following examples. The test methods performed in this example are as follows.

(1) Measurement of pore properties (pore radius, pore volume, surface area) Vacuum dried resin (gas adsorbent) is placed in a glass cell, and the pores of the resin with a mercury porosimeter (Autopore 9220, manufactured by Shimadzu Corporation) Radius and pore volume were measured. From the histogram showing the distribution of pores with the measured pore volume and pore radius as the vertical axis and the horizontal axis, respectively, the pore radius of the portion with the largest total pore volume was determined as the average pore radius.
The surface area of the resin (gas adsorbent) was measured by a nitrogen adsorption method (Flowsorb 2300 type, manufactured by Micrometrics).
In the table, a surface area of 0 indicates a case where no or almost no pores are observed.

(2) Amine elution test A column with an inner diameter of 15 mmΦ is filled with 50 g of resin (gas adsorbent) drained with a centrifugal separator using demineralized water, and 2N aqueous hydrochloric acid solution is used as an eluent with SV1 (What is “SV1”?) 5BV ("5BV" means that 5L was passed through 1L of resin (gas adsorbent) in 1 hour) by volume flow rate (L / h) per hour for 1L of resin (gas adsorbent). And the eluent was recovered. The absorbance (wavelength 254 nm) of the recovered eluent was measured, and analyzed by ion chromatography or further high performance liquid chromatography (HPLC) under the following conditions.
Note that “BV” represents that 1 L of liquid (gas adsorbent) was passed through in 1 hour.

  HPLC analysis: column ODS column Elution from a 50% aqueous acetonitrile solution to a 100% acetonitrile solution with a gradient of 5% / min. UV detector, measurement wavelength 254 nm.

(3) Aromatic compound elution test A column with an inner diameter of 15 mmΦ was filled with 50 g of resin (gas adsorbent) drained with a centrifuge using demineralized water, and isopropyl alcohol was passed as 5 BV at SV1 at room temperature as the eluent. And the eluent was collected. The recovered eluent was analyzed by gas chromatography (GC) and HPLC, and the contents of toluene, styrene, ethylvinylbenzene, divinylbenzene, diethylbenzene and phenol were measured. GC analysis conditions and HPLC analysis conditions are as follows.

GC analysis conditions: Column HP-5 (HP) Heated from 50 ° C to 250 ° C at a rate of 10 ° C / min. The carrier gas uses He. FID detector HPLC analysis: Column ODS column Elution with a gradient of 50% acetonitrile to 100% acetonitrile with a gradient of 5% / min. After reaching 10 minutes, hold for 5 minutes with 100% acetonitrile solution for 5 minutes. UV detector, measurement wavelength 254 nm.

(4) Measurement of neutral salt decomposition capacity Anion exchange resin was packed in a column, and a 5% NaCl aqueous solution having a volume 25 times the resin capacity was passed through the column to convert the counter ion to Cl form. 10.0 ml of this resin was taken, and 75 volumes of 2N-NaOH aqueous solution was passed through to regenerate the Cl form to the OH form. The washed filtrate was sufficiently washed with demineralized water until neutral, and then 25% of a 5% NaCl aqueous solution was passed through to collect all the effluent. The neutral salt decomposition capacity was calculated by titrating the effluent with hydrochloric acid.

(5) Acid adsorption capacity measurement test 10.0 ml of the adsorbent is collected with a graduated cylinder, filled in a glass column, passed through 200 ml of 2N-hydrochloric acid aqueous solution, and washed with demineralized water. Next, 250 ml of 2N-sodium hydroxide aqueous solution is passed through. Further, desalted water was passed through until the effluent was neutral. Put this resin in a 500 ml Erlenmeyer flask, add 300 ml of 0.2N HCl aqueous solution, and shake for 8 hours. After shaking, 20.0 ml of the supernatant was sampled with a whole pipette, titrated with a 0.1N-NaOH aqueous solution, and the amount of adsorbed hydrochloric acid was converted per weight and per volume to determine the acid adsorption capacity.

(6) Propionaldehyde adsorption test 10.0 g of resin (gas adsorbent) is added to a 200 ml Erlenmeyer flask, and 50.0 g of a 2 wt% propionaldehyde aqueous solution based on a 10 wt% methanol aqueous solution is added to the flask. Shake for 1 day. After completion of shaking, the supernatant was sampled, and the concentration of propionaldehyde was measured by gas chromatography (GC) under the following conditions to calculate the amount of adsorption.

  GC analysis conditions: Column HP-5 (HP) Analyzed at a constant temperature of 50 ° C. Retention time is 2.512 minutes. FID detector

(7) Adsorption rate test of propionaldehyde Add 5.00 g of drained resin (gas adsorbent) to a 300 ml Erlenmeyer flask, and 100.0 ml of propion with a concentration of 100 ppm adjusted to 25.0 ° C. in advance. An aqueous aldehyde solution was instantaneously injected, and the mixture was shaken on a shaker set at 25.0 ° C. under conditions that maintain the suspended state of the resin. Supernatant liquids after 3 minutes and 10 minutes from the introduction of the aqueous propionaldehyde solution were sampled, the concentration of propionaldehyde was measured by gas chromatography (GC), and the amount of adsorption was calculated.
The analysis conditions are the same as in (6) above.

(8) Nicotinamide Adsorption Test 10.0 g of resin (gas adsorbent) was added to a 200 ml Erlenmeyer flask, and 50.0 g of a 1% weight nicotinamide aqueous solution was added thereto, followed by shaking at room temperature for 1 day. . After the shaking, the supernatant was sampled, and the concentration of nicotinamide was measured by HPLC under the following conditions.

  HPLC analysis conditions: Liquid A (10% acetonitrile aqueous solution), Liquid B (70% acetonitrile aqueous solution). Elution from solution A to solution B with a gradient of 10% / min. Hold for 3 minutes in 70% aqueous acetonitrile. The retention time of nicotinamide is 4.4 minutes. This peak was detected at UV254 nm, the concentration of nicotinamide was measured from the calibration curve, and the adsorption amount was calculated.

(9) l-Menthol adsorption test To 200 ml Erlenmeyer flask, 10.0 g of resin (gas adsorbent) was added, and 50.0 g of 2 wt% 1-menthol aqueous solution based on 50 wt% methanol aqueous solution was added thereto, Shake at room temperature for 1 day. After completion, the supernatant was sampled and the concentration of l-menthol was measured by gas chromatography (GC) under the following conditions.

  GC analysis conditions: Column HP-5 (HP) The temperature was raised from 50 ° C. to 250 ° C. at 10 ° C./min. The retention time of l-menthol was 10.8 minutes. This peak was detected by an FID detector, the concentration of l-menthol was measured from the calibration curve, and the adsorption amount was calculated.

(10) Reference test: gas phase gas capture test (6) Propionaldehyde adsorption test and (7) Propionaldehyde adsorption rate test confirm that gas capture ability in gas phase system is properly expressed. In order to do this, the following gas phase gas capture test was performed for some of the examples and comparative examples described below. The gas adsorption rate preferable as a gas adsorbent is usually 40% or more, preferably 45% or more.
A quartz tube having an inner diameter of 8.0 mmΦ (outer diameter 10.0 mmΦ) was filled with 40 mg of vacuum-dried adsorbent and 100 mg of glass beads (ASONE BZ-06), and both ends were fixed with glass wool. (The packed bed of resin is 8.0 mmΦ × 4.0 mm) 1000 ppm of acetaldehyde gas (1.0% acetaldehyde standard gas diluted with nitrogen gas at the inlet of the adsorbent filling tube. The internal standard method is used for the quantitative method. Acetaldehyde 100 ppm of methane gas was added to the gas, and a quantitative analysis of acetaldehyde was performed based on the methane gas.) A tetrabag was attached, and a 100 ml gas syringe and a GC device were connected to the outlet via a three-way valve. A gas tight syringe was sucked at 35 ml / 2 seconds with a low-speed cylinder unit, and gas was sucked into a quartz glass tube. The adsorption temperature was 24 ° C to 26 ° C. After inhalation, the valve was switched to feed inhaled gas to the GC, and acetaldehyde that was not adsorbed was quantified by GC. This operation was repeated every 5 minutes and repeated 10 times, and the adsorption rate (%) and the adsorption behavior were evaluated.
Shimadzu GC-14A was used for gas chromatography. The column was a DB-WAX column (0.53 mmΦ × 30 mm), the analysis temperature was 60 ° C., the column inlet temperature was 50 ° C., the detector temperature was 50 ° C., and the detector was an FID detector.

(11) Measurement of weight average particle diameter Sieves having a sieve mesh diameter of 1180 μm, 850 μm, 710 μm, 600 μm, 425 μm, and 300 μm were stacked so that the sieve mesh diameter became smaller as it went downward. The stacked sieve was placed on a bat, and about 100 mL of a gas adsorbent was placed in a 1180 μm sieve stacked on the uppermost stage.
Water was gently poured onto the resin from a rubber tube connected to tap water, and the small particles were sieved downward. The gas adsorbent remaining in the 1180 μm sieve was further screened for small particles by the following method. That is, water was filled to a depth of about 1/2 of another bat, and a 1180 μm sieve was repeatedly shaken by applying up and down and rotating motions in the bat to screen out small particles.
The small particles in the vat were returned to the next 850 μm sieve, and the gas adsorbent remaining on the 1180 μm sieve was collected in another vat. If the gas adsorbent was clogged in the sieve, the sieve was placed on the vat in reverse and brought into close contact with a rubber tube connected to tap water, and the gas adsorbent clogged with the sieve was taken out by strongly flowing water. The taken out gas adsorbent was transferred to a vat from which the gas adsorbent remaining on the 1180 μm sieve was collected, and the total volume was measured with a graduated cylinder. This volume was defined as a (mL). The gas adsorbent that passed through the 1180 μm sieve was subjected to the same operation for each of the 850 μm, 710 μm, 600 μm, 425 μm, and 300 μm sieves, and the volume b (mL), c (mL), d (mL), e (mL) and f (mL) were obtained, and finally the volume of the resin that passed through the 300 μm sieve was measured with a graduated cylinder to obtain g (mL).
V = a + b + c + d + e + f + g, a / V × 100 = a ′ (%), b / V × 100 = b ′ (%), c / V × 100 = c ′ (%), d / V × 100 = d ′ ( %), E / V × 100 = e ′ (%), f / V × 100 = f ′ (%), g / V × 100 = g ′ (%).
From the above a ′ to g ′, the residual amount cumulative (%) of each sieve is taken on one axis, and the diameter (mm) of the sieve mesh is taken on the other axis, and this is plotted on the logarithmic probability paper. Take 3 points in the order of the remaining amount, draw a line that satisfies these 3 points as much as possible, obtain the diameter (mm) of the sieve mesh corresponding to 50% of the accumulated residue from this line, and calculate the weight average The particle diameter was taken.

Example 1
Diaion (registered trademark) CR20 (trade name, an amino group-containing weakly basic anion exchange resin manufactured by Mitsubishi Chemical Corporation) was drained with a centle, 100 ml was taken, and a 1 L four-necked flask equipped with a condenser and a stirring blade was attached. Put in. 400 ml of 2N-HCl was added thereto, and the mixture was stirred at 80 ° C. for 5 hours. The solution was extracted, 400 ml of a new 2N-HCl solution was added, and the mixture was further stirred for 5 hours and washed.
After the flask was cooled to room temperature, the resin was filled in a glass column, and a 1N-HCl aqueous solution was passed through 5 BV at SV1 at room temperature. Further, after washing with a 1N HCl aqueous solution, 10 BV was passed through with demineralized water, and the excess hydrochloric acid solution was removed.
Next, while the ion exchange group of the resin in the column after washing was in the Cl form, methanol was passed through 5 BV at SV1 at room temperature. Further, methanol was removed by passing 5 BV through demineralized water.
This resin was passed through 1N-NaOH aqueous solution at 5 BV, the ion exchange group of the resin in the column was ion-exchanged into OH form (free form), and finally, desalted water 5 BV was passed through as in Example 1. It was used for the test as a gas adsorbent (amino group-containing weakly basic anion exchange resin).

(Example 2)
A chloromethylated polymer having a main skeleton having a structure represented by the following formula 4 which is a precursor of Diaion (registered trademark) CR20 (trade name, an amino group-containing weakly basic anion exchange resin manufactured by Mitsubishi Chemical Corporation) 1 (after washing with 1N-HCl aqueous solution and then passing 10 BV with demineralized water to remove excess hydrochloric acid solution) (hereinafter referred to as “washing precursor”). ) Was aminated as follows.
50 g of the above washing precursor was taken in a 500 ml four-necked flask equipped with a condenser and stirring blades, 250 ml of demineralized water was added, and the mixture was stirred at room temperature for 1 hour. To this, 30 g of 45% aqueous sodium hydroxide solution and 70 g of 50% dimethylamine aqueous solution were added and stirred at 50 ° C. for 5 hours.
After the reaction, the resin was taken out, filled into a glass column, washed with 20 BV water with demineralized water, and the amine used in the reaction was removed as the gas adsorbent (amino group-containing weakly basic anion exchange resin) of Example 2. It used for the test.

  (In the above formula 4, m and n each represent an integer of 1 or more.)

(Example 3)
The same cleaning precursor used in Example 2 was aminated as follows.
50 g of the above washing precursor is taken into a 500 ml four-necked flask equipped with a cooling tube and a stirring blade, 150 ml of demineralized water, 30 g of 45% sodium hydroxide aqueous solution and 200 g of diethylenetriamine (DETA, Tokyo Chemical) are added at 120 ° C. Stir for 5 hours.
After the reaction, the resin was taken out, filled into a glass column, washed with 20 BV water with demineralized water, and the amine used in the reaction was removed as the gas adsorbent of Example 3 (amino group-containing weakly basic anion exchange resin). It used for the test.

Example 4
The same cleaning precursor used in Example 2 was aminated as follows.
Into a 500 ml four-necked flask equipped with a condenser and a stirring blade, 50 g of the washing precursor is taken, and 100 ml of demineralized water, 44 g of 45% sodium hydroxide aqueous solution and 49 g of diethylenetriamine (DETA, Tokyo Chemicals) are added, and 120 to 120 The temperature was raised to ° C and stirred at 120 ° C for 5 hours.
After the reaction, the resin was taken out and washed with demineralized water until the solution became neutral. Thereafter, the resin purified by the method shown in Example 1 was subjected to the test as the gas adsorbent of Example 4 (amino group-containing weakly basic anion exchange resin).

(Example 5)
In Example 4, except that the charged weight of diethylenetriamine (DETA, Tokyo Chemicals) was changed from 49 g to 12.25 g, the gas adsorbent of Example 5 (amino group-containing weakly weakened) was treated in the same manner as in Example 4. Basic anion exchange resin).

(Example 6)
In Example 4, except that the charged weight of diethylenetriamine (DETA, Tokyo Chemicals) was changed from 49 g to 6.12 g, the gas adsorbent of Example 6 (amino group-containing weak weakness) was treated in the same manner as in Example 4. Basic anion exchange resin).

(Examples 7, 8, and 9)
0.5 L of the gas adsorbent obtained in Example 1 was taken out and classified into three stages using a wire mesh sieve. The weight average particle diameter of the resin at each stage was 550 μm, 760 μm, and 380 μm, respectively.
These resins were dried with a vacuum dryer until the water content was about 10%. Then, it was placed in a constant temperature and humidity chamber at 25 ° C. and a relative humidity of 75% for 3 days. Meanwhile, the resin was periodically flowed and mixed. The moisture of the resin after conditioning was about 12.5%, and the weight average particle diameters of the resin after conditioning were 510 μm, 700 μm, and 350 μm, respectively.
The gas adsorbent having a weight average particle diameter of 510 μm was used as the gas adsorbent of Example 7 (amino group-containing weakly basic anion exchange resin), the gas adsorbent having a weight average particle diameter of 700 μm was the gas of Example 8. An adsorbent (amino group-containing weakly basic anion exchange resin) and a gas adsorbent having a weight average particle diameter of 350 μm were used as the gas adsorbent of Example 9 (amino group-containing weakly basic anion exchange resin). Provided.

(Example 10)
The following organic phase and aqueous phase were added to a 3 L SUS pressure reactor equipped with a stirring blade, a nitrogen introduction tube, a pressure gauge, a pressure sensor, and a thermometer protection tube.
Organic phase: 63% divinylbenzene 83.9 g, styrene 129.5 g, isooctane 254.7 g, purity 75% benzoyl peroxide 1.28 g, PBZ (t-butyl perbenzoate, manufactured by NOF Corporation) 1.185 g prepared did.
Aqueous phase: 985 ml of demineralized water, 53.3 ml of 3% polyvinyl alcohol solution and 21 ml of 0.1% NaNO ₂ aqueous solution were prepared.
Next, the reaction vessel was depressurized to 5 kPa while stirring the reaction blade, and then 0.3 MPa of nitrogen gas was injected. This operation was repeated five times, and nitrogen gas was bubbled while stirring at 200 ml / min for 15 minutes to remove dissolved oxygen in the reactor to 0.1 ppm or less.
The temperature of the reactor was adjusted to 25 ° C., and the mixture was stirred at 120 rpm for 1 hour. Then, after stirring at 80 degreeC for 4 hours, it heated up at 115 degreeC further and stirred for 4 hours. The pressure at 80 ° C. was 0.09 MPa, and the pressure at 115 ° C. was 0.25 MPa. After cooling the reactor, the resin was taken out, washed with demineralized water, and then a white resin having a slight isooctane odor was obtained.
200 g of this resin was put into a 2 L four-necked flask equipped with a stirring blade and a cooling tube, and isooctane remaining in the resin was removed by steam distillation.
At this stage, a resin having a moisture content of 59.5%, a specific surface area of 34 m ² / g, an average pore radius of 1101 mm, and a pore volume of 1.67 ml / g was obtained. The polymerization yield was 99.5% or more. Further, styrene remaining in the resin was 1.2 ppm, EVB (ethylvinylbenzene) was 0.4 ppm, and DVB (divinylbenzene) was 0.1 ppm.
To 50 g of the resin obtained by the above procedure, 300 g of chloromethyl methyl ether was added and stirred at 50 ° C. for 1 hour. Chloromethylation was carried out by adding 15 g of zinc chloride, and then amination treatment was carried out in the same manner as in Example 2 as the gas adsorbent of Example 10 (amino group-containing weakly basic anion exchange resin). .

(Example 11)
The following organic phase and aqueous phase were added to a 3 L SUS pressure reactor equipped with a stirring blade, a nitrogen introduction tube, a pressure gauge, a pressure sensor, and a thermometer protection tube.
Organic phase: A solution of 138.5 g of 63% divinylbenzene, 210.6 g of styrene, 419 g of toluene, 1.16 g of 75% purity benzoyl peroxide and 0.87 g of PBZ (t-butyl perbenzoate, manufactured by NOF Corporation) was prepared.
Aqueous phase: 1624 ml of demineralized water, 51.3 ml of 3% polyvinyl alcohol solution, and 34 ml of 0.1% NaNO ₂ aqueous solution were prepared.
Next, the reaction vessel was depressurized to 5 kPa while stirring the reaction blade, and then 0.3 MPa of nitrogen gas was injected. This operation was repeated five times, and nitrogen gas was bubbled while stirring at 200 ml / min for 15 minutes to remove dissolved oxygen in the reactor to 0.2 ppm or less.
The temperature of the reactor was adjusted to 25 ° C., and the mixture was stirred at 115 rpm for 1 hour. Thereafter, the temperature was raised from room temperature to 80 ° C. and stirred for 4 hours, and then further heated to 120 ° C. and polymerized for 4 hours. After cooling the reactor, the resin was taken out and washed with toluene. This operation was repeated 4 times.
200 g of this resin was put into a 2 L four-necked flask equipped with a stirring blade and a cooling tube, and toluene remaining in the resin was removed by steam distillation, and then aminated in the same manner as in Example 2. The gas adsorbent of Example 11 (amino group-containing weakly basic anion exchange resin) was subjected to the test.

The same cleaning precursor used in Example 2 was aminated as follows.
50 g of the above washing precursor is taken in a 500 ml four-necked flask equipped with a condenser and a stirring blade, 80 ml of demineralized water, 44 g of 45% sodium hydroxide aqueous solution, 19.6 g of diethylenetriamine (DETA, Tokyo Chemicals), and 75 g of toluene. In addition, the temperature was raised to 80 ° C. and stirred for 5 hours.
After the reaction, the resin was taken out and washed with demineralized water until the solution became neutral. The obtained resin was transferred to a 1 L flask equipped with a stirrer and a distillation apparatus, 0.5 L of demineralized water was added, and steam distillation was performed at a bath temperature of 110 ° C. (internal temperature 108 ° C.). With the distilling of water, demineralized water was added dropwise to keep the liquid level constant. A product obtained by removing toluene remaining in the resin by steam distillation was used as a gas adsorbent of Example 12 (amino group-containing weakly basic anion exchange resin).

(Example 13)
The following organic phase and aqueous phase were added to a 3 L SUS pressure reactor equipped with a stirring blade, a nitrogen introduction tube, a pressure gauge, a pressure sensor, and a thermometer protection tube.
Organic phase: 63% divinylbenzene 143.7 g, styrene 221.9 g, toluene 438.9 g, polystyrene (molecular weight 48,000) 95.1 g, purity 75% benzoyl peroxide 2.44 g, PBZ (t-butyl perbenzoate) (Manufactured by NOF Corporation) 1.87 g of solution was prepared.
Aqueous phase: 1678 ml of demineralized water, 91.4 ml of 3% polyvinyl alcohol solution, and 36 ml of 0.1% NaNO ₂ aqueous solution were prepared.
Next, the reaction vessel was depressurized to 5 kPa while stirring the reaction blade, and then 0.3 MPa of nitrogen gas was injected. This operation was repeated five times, and nitrogen gas was bubbled while stirring at 200 ml / min for 15 minutes to remove dissolved oxygen in the reactor to 0.1 ppm or less.
The temperature of the reactor was adjusted to 25 ° C., and the mixture was stirred at 120 rpm for 1 hour. Then, it heated up to 80 degreeC and hold | maintained for 4 hours. The temperature was further raised to 120 ° C., and the mixture was stirred for 4 hours. The pressure at 80 ° C. was 0.072 MPa, and the pressure at 120 ° C. was 0.29 MPa. After cooling the reactor, the resin was taken out and washed with demineralized water to obtain a white resin.
200 g of this resin was filled in a glass column, 5 times the amount of toluene was passed through, and the added polystyrene was removed.
Thereafter, the obtained resin was put into a 2 L four-necked flask equipped with a stirring blade and a cooling tube, and toluene remaining in the resin was removed by steam distillation.
At this stage, a resin having a specific surface area of 50 m ² / g, an average pore radius of 753 mm, and a pore volume of 0.99 ml / g was obtained. The polymerization yield was 97.8% or more.
To 50 g of the dry resin obtained by the above procedure, 300 g of chloromethyl methyl ether was added and stirred at 25 ° C. for 1 hour. Zinc chloride 60g was added here, and it heated up at 50 degreeC, and stirred for 5 hours, and chloromethylated. Centrifugal (5 minutes) water-wet polymer is placed in a 1 L four-necked flask, 325 ml of demineralized water is added, and 438 g of 48% NaOH is added with stirring. Next, 49.7 g of diethylenetriamine (DETA, Tokyo Chemicals) was added. The bath temperature was raised from room temperature to 115 ° C. (internal temperature 110 ° C.) in 2 hours and stirred for 5 hours. After completion, the resin was taken out, the reaction solution was taken out, and washed with demineralized water in batch. After repeating this operation three times, the resin was transferred to a glass column and passed through until it became neutral with demineralized water. Provided.

(Example 14)
In Example 13, except that the charged weight of diethylenetriamine (DETA, Tokyo Chemicals) was changed from 49.7 g to 31.1 g, the gas adsorbent (amino group) of Example 14 was treated in the same manner as in Example 13. Containing weakly basic anion exchange resin).

Example 15
In Example 13, except that the charged weight of diethylenetriamine (DETA, Tokyo Chemical) was changed from 49.7 g to 15.5 g, the gas adsorbent (amino group) of Example 15 was treated in the same manner as in Example 13. Containing weakly basic anion exchange resin).

(Example 16)
In Example 13, except that the charged weight of diethylenetriamine (DETA, Tokyo Chemicals) was changed from 49.7 g to 10.4 g, the gas adsorbent (amino group) of Example 16 was treated in the same manner as in Example 13. Containing weakly basic anion exchange resin).

(Example 17)
The following organic phase and aqueous phase were added to a 2 L SUS pressure reactor equipped with a stirring blade, a nitrogen introduction tube, a pressure gauge, a pressure sensor, and a thermometer protection tube.
Organic phase: 63% divinylbenzene 83.9 g, styrene 129.5 g, isooctane 202.7 g, purity 75% benzoyl peroxide 1.28 g, PBZ (t-butyl perbenzoate, manufactured by NOF Corporation) 1.185 g prepared did.
Aqueous phase: 985 ml of demineralized water, 53.3 ml of 3% polyvinyl alcohol solution and 21 ml of 0.1% NaNO ₂ aqueous solution were prepared.
Next, the reaction vessel was depressurized to 5 kPa while stirring the reaction blade, and then 0.3 MPa of nitrogen gas was injected. This operation was repeated five times, and nitrogen gas was bubbled while stirring at 200 ml / min for 15 minutes to remove dissolved oxygen in the reactor to 0.1 ppm or less.
The temperature of the reactor was adjusted to 25 ° C., and the mixture was stirred at 120 rpm for 1 hour. Then, after stirring at 80 degreeC for 4 hours, it heated up at 115 degreeC further and stirred for 4 hours. The pressure at 80 ° C. was 0.088 MPa, and the pressure at 115 ° C. was 0.28 MPa. After cooling the reactor, the resin was taken out, washed with demineralized water, and then a white resin having a slight isooctane odor was obtained.
200 g of this resin was put into a 2 L four-necked flask equipped with a stirring blade and a cooling tube, and isooctane remaining in the resin was removed by steam distillation.
At this stage, a resin having a specific surface area of 53 m ² / g, an average pore radius of 472 mm, and a pore volume of 1.42 ml / g was obtained.
Chloromethylation was performed in the same manner as in Example 13 using 50 g of the resin obtained by the above procedure, and amination was performed with diethylenetriamine (DETA, Tokyo Chemicals) as in Example 13, but diethylenetriamine (DETA, Tokyo Chemicals). A gas adsorbent (amino group-containing weakly basic anion exchange resin) of Example 17 was subjected to the test as a gas adsorbent of Example 17 except that the charged weight was changed from 49.7 g to 124.2 g. .

(Example 18)
In Example 17, a white resin having a slight isooctane odor was obtained in the same manner as in Example 17 except that the charged weight of isooctane was changed from 202.7 g to 211.3 g.
Thereafter, a resin having a specific surface area of 44 m ² / g, an average pore radius of 603 mm, and a pore volume of 1.48 ml / g was obtained after the removal of isooctane remaining in the resin.
Using 50 g of the resin obtained by the above procedure, the same chloromethylation or amination treatment as in Example 17 was used as the gas adsorbent of Example 18 (amino group-containing weakly basic anion exchange resin) for the test. did.

Example 19
In Example 17, a white resin having a slight isooctane odor was obtained in the same manner as in Example 17 except that the charged weight of isooctane was changed from 202.7 g to 224.1 g.
Thereafter, a resin having a specific surface area of 34 m ² / g, an average pore radius of 1101 kg, and a pore volume of 1.67 ml / g was obtained after the removal of isooctane remaining in the resin.
Using 50 g of the resin obtained by the above procedure, the same chloromethylation or amination treatment as in Example 17 was used as the gas adsorbent of Example 19 (amino group-containing weakly basic anion exchange resin) for the test. did.

(Example 20)
The following organic phase and aqueous phase were added to a 3 L SUS pressure reactor equipped with a stirring blade, a nitrogen introduction tube, a pressure gauge, a pressure sensor, and a thermometer protection tube.
Organic phase: 63% divinylbenzene 50.8 g, styrene 353.4 g, isooctane 303.2 g, purity 75% benzoyl peroxide 1.90 g, PBZ (t-butyl perbenzoate, manufactured by NOF Corporation) 1.60 g solution was prepared. did.
Aqueous phase: 1492 ml of demineralized water, 67.1 ml of 3% polyvinyl alcohol solution, and 31.8 ml of 0.1% NaNO ₂ aqueous solution were prepared.
Next, the reaction vessel was depressurized to 5 kPa while stirring the reaction blade, and then 0.3 MPa of nitrogen gas was injected. This operation was repeated five times, and nitrogen gas was bubbled while stirring at 200 ml / min for 15 minutes to remove dissolved oxygen in the reactor to 0.1 ppm or less.
The temperature of the reactor was adjusted to 25 ° C., and the mixture was stirred at 120 rpm for 1 hour. Then, after stirring at 80 degreeC for 4 hours, it heated up at 115 degreeC further and stirred for 4 hours. The pressure at 80 ° C. was 0.088 MPa, and the pressure at 115 ° C. was 0.27 MPa. After cooling the reactor, the resin was taken out, washed with demineralized water, and then a white resin having a slight isooctane odor was obtained.
200 g of this resin was put into a 2 L four-necked flask equipped with a stirring blade and a cooling tube, and isooctane remaining in the resin was removed by steam distillation. To 50 g of the obtained dry resin, 150 g of chloromethyl methyl ether and 150 g of 1,2-dichloroethane were added and stirred at 25 ° C. for 1 hour. To this was added 35 g of iron chloride, the temperature was raised to 50 ° C., and the mixture was stirred for 8 hours for chloromethylation. Centrifugation (5 minutes) of water-wet polymer is put into a 1 L four-necked flask, 325 ml of demineralized water and 225 ml of toluene are added, and 438 g of 48% NaOH is added with stirring. Next, 21.6 g of ethylenediamine was added. The bath temperature (internal temperature 80 ° C.) was raised to 82 ° C. in 2 hours from room temperature and stirred for 6 hours. After completion, the resin was taken out, transferred to another flask, and toluene was removed by steam distillation. The resin was transferred to a glass column and passed through until it became neutral with demineralized water and subjected to the test as the gas adsorbent of Example 20 (amino group-containing weakly basic anion exchange resin).

(Example 21)
In Example 20, chloromethylation and amino acid were changed in the same manner as in Example 20 except that the charged weight of 68% divinylbenzene was changed from 50.8 g to 38.1 g and the charged weight of styrene was changed from 353.4 g to 366.1 g. The treated product was subjected to the test as the gas adsorbent of Example 21 (amino group-containing weakly basic anion exchange resin).

(Example 22)
The following organic phase and aqueous phase were added to a 3 L SUS pressure reactor equipped with a stirring blade, a nitrogen introduction tube, a pressure gauge, a pressure sensor, and a thermometer protection tube.
Organic phase: A solution containing 95.3 g of 63% divinylbenzene, 308.9 g of styrene, 364 g of n-heptane, 1.70 g of 75% purity benzoyl peroxide, and 1.53 g of PHD (Perhexyl D, manufactured by NOF Corporation) was prepared.
Aqueous phase: 1664 ml of demineralized water, 67.4 ml of 3% polyvinyl alcohol solution, and 35.3 ml of 0.1% NaNO ₂ aqueous solution were prepared.
Next, the reaction vessel was depressurized to 5 kPa while stirring the reaction blade, and then 0.3 MPa of nitrogen gas was injected. This operation was repeated five times, and nitrogen gas was bubbled while stirring at 200 ml / min for 15 minutes to remove dissolved oxygen in the reactor to 0.1 ppm or less.
The temperature of the reactor was adjusted to 25 ° C., and the mixture was stirred at 120 rpm for 1 hour. Then, after stirring at 80 degreeC for 4 hours, it heated up at 130 degreeC and stirred for 6 hours. The pressure at 80 ° C. was 0.093 MPa, and the pressure at 130 ° C. was 0.46 MPa. After cooling the reactor, the resin was taken out, washed with demineralized water, and then a white resin having a slight n-heptane odor was obtained.
200 g of this resin was put into a 2 L four-necked flask equipped with a stirring blade and a cooling tube, and n-heptane remaining in the resin was removed by steam distillation. To 50 g of the obtained dry resin, 150 g of chloromethyl methyl ether and 150 g of 1,2-dichloroethane were added and stirred at 25 ° C. for 1 hour. To this was added 35 g of iron chloride, the temperature was raised to 50 ° C., and the mixture was stirred for 8 hours for chloromethylation. Centrifugation (5 minutes) of water-wet polymer is put into a 1 L four-necked flask, 325 ml of demineralized water and 225 ml of toluene are added, and 438 g of 48% NaOH is added with stirring. Next, 32.7 g of diethylenetriamine (DETA, Tokyo Chemicals) was added. The bath temperature (internal temperature 80 ° C.) was raised to 82 ° C. in 2 hours from room temperature and stirred for 6 hours. After completion, the resin was taken out, transferred to another flask, and toluene was removed by steam distillation. The resin was transferred to a glass column and allowed to pass through demineralized water until neutral, and the test was conducted as the gas adsorbent of Example 22 (amino group-containing weakly basic anion exchange resin).

(Example 23)
In Example 16, except that the amination conditions were changed as follows, the same treatment as in Example 16 was used as a gas adsorbent (amino group-containing weakly basic anion exchange resin) in Example 23 for testing. Provided.
Into a 1 L four-necked flask, 140 g of water-wet polymer cut into a centle (5 minutes) was placed in a flask, 200 ml of dimethoxymethane was added, and 438 g of 48% NaOH was added with stirring. Next, 10.4 g of diethylenetriamine (DETA, Tokyo Chemicals) was added. The bath temperature was raised from room temperature to 45 ° C. (internal temperature 43 ° C.) in 30 minutes, and the mixture was stirred for 5 hours. After completion, the resin was taken out, the reaction solution was taken out, and washed with demineralized water in batch. After this operation was repeated three times, the resin was filled in a glass column and passed through until it became neutral with demineralized water.

(Example 24)
In Example 22, except that the amination conditions were changed as follows, the same treatment as in Example 22 was used as a gas adsorbent (amino group-containing weakly basic anion exchange resin) in Example 24 for testing. Provided.
Into a 1 L four-necked flask, 140 g of water-wet polymer cut into a centle (5 minutes) was placed in a flask, 200 ml of dimethoxymethane was added, and 438 g of 48% NaOH was added with stirring. Next, 32.7 g of diethylenetriamine (DETA, Tokyo Chemicals) was added. In 30 minutes from room temperature, the bath temperature was raised to 48 ° C. (internal temperature 43 ° C.) and stirred for 5 hours. After completion, the resin was taken out, the reaction solution was taken out, and washed with demineralized water in batch. After this operation was repeated three times, the resin was filled in a glass column and passed through until it became neutral with demineralized water.

(Example 25)
In Example 17, except that the conditions for amination were changed as follows, the same treatment as in Example 17 was used as the gas adsorbent of Example 25 (amino group-containing weakly basic anion exchange resin) for testing. Provided.
Into a 1 L 4-necked flask, 100 g of water-wet polymer cut into a centle (5 minutes) is placed in a flask. Next, 25.5 g of diethylenetriamine (DETA, Tokyo Chemicals) was added. The bath temperature (internal temperature 43 ° C.) was raised to 50 ° C. in 30 minutes from room temperature and stirred for 5 hours. After completion, the resin was taken out, the reaction solution was taken out, and washed with demineralized water in batch. After this operation was repeated three times, the resin was filled in a glass column and passed through until it became neutral with demineralized water.

(Example 26)
Wet "Sebeads (registered trademark) EC-EP / S" (trade name, a methacrylic polymer having an epoxy group manufactured by Mitsubishi Chemical Corporation) in a 1 L four-necked flask equipped with a stirring blade and a cooling tube. In a wet state, 50 g was added. To this, 350 ml of demineralized water and 50 g of diethylenetriamine (DETA, Tokyo Kasei) were added, the temperature was raised to 70 ° C., and the mixture was stirred at 70 ° C. for 6 hours.
After the reaction, the resin was taken out and washed with demineralized water. The resin washed with water was returned again to the 1 L four-necked flask, 500 ml of 2N sulfuric acid aqueous solution was added, and the mixture was stirred at 50 ° C. for 5 hours. After completion, the resin was washed with demineralized water on Nutsche. Further, the resin was filled in a glass column, and 10 BV of demineralized water was passed therethrough. Further, a 10-fold volume of 2N-sodium hydroxide aqueous solution was passed through, followed by further passing through desalted water and treating the OH-type ion form with the gas adsorbent of Example 26 (methacrylic weakly basic anion exchange). Resin).

(Example 27)
Wet “Sebeads (registered trademark) FP-EP200” (trade name, methacrylic polymer having an epoxy group manufactured by Mitsubishi Chemical Corporation) in a 1-L four-necked flask equipped with a stirring blade and a cooling tube. 50 g was added in the state. To this, 350 ml of demineralized water and 50 g of diethylenetriamine (DETA, Tokyo Kasei) were added, the temperature was raised to 100 ° C., and the mixture was stirred at 100 ° C. for 10 hours.
After the reaction, the resin was taken out and washed with demineralized water. The resin washed with water was returned again to the 1 L four-necked flask, 500 ml of 2N sulfuric acid aqueous solution was added, and the mixture was stirred at 50 ° C. for 5 hours. After completion, the resin was washed with demineralized water on Nutsche. Further, the resin was filled in a glass column, and 10 BV of demineralized water was passed therethrough. Further, a 10-fold volume of 2N-sodium hydroxide aqueous solution was passed through, followed by further passing through demineralized water and treating the OH-type ion form with the gas adsorbent of Example 27 (methacrylic weakly basic anion). It was used for the test as an exchange resin.

(Example 28)
In Example 27, instead of “Sebeads (registered trademark) EC-EP200”, “Sebeads (registered trademark) FP-EP300” (trade name, a methacrylic polymer having an epoxy group manufactured by Mitsubishi Chemical Corporation) was used. What was processed like Example 27 was used for the test as the gas adsorbent of Example 28 (methacrylic weakly basic anion exchange resin).

(Example 29)
In Example 27, instead of “Sebeads (registered trademark) EC-EP200”, “Sebeads (registered trademark) FP-EC-EP / S” (trade name, a methacrylic polymer having an epoxy group manufactured by Mitsubishi Chemical Corporation) A sample treated in the same manner as in Example 27 except that was used as a gas adsorbent (methacrylic weakly basic anion exchange resin) in Example 29 was subjected to the test.

(Example 30)
“Sebeads (registered trademark) FP-HA13” (trade name, methacrylic weakly basic anion exchange resin manufactured by Mitsubishi Chemical Corporation) itself was tested as the gas adsorbent (methacrylic weakly basic anion exchange resin) of Example 30. It was used for.

(Comparative Example 1)
Diaion (registered trademark) CR20 (trade name, an amino group-containing weakly basic anion exchange resin manufactured by Mitsubishi Chemical Corporation) itself was used as a gas adsorbent (amino group-containing weakly basic anion exchange resin) of Comparative Example 1 for the test. did.

(Comparative Example 2)
Duolite A7 (trade name, a phenolic weakly basic anion exchange resin manufactured by Rohm and Haas) itself was used as a gas adsorbent (phenolic weakly basic anion resin) of Comparative Example 2 for the test.

(Comparative Example 3)
A 1 L four-necked flask was charged with 400 ml of cyclohexane and 800 mg of ethylcellulose to prepare a polymerization bath solution. On the other hand, vinylformamide (CH ₂ ═CH—NHCHO) (purity 94%, main impurity is formic acid) 180 g, divinylbenzene (purity 80%) 20.0 g, demineralized water 4.5 g, V-50 ( A monomer solution of 400 mg of an azo polymerization initiator, trade name, manufactured by Wako Pure Chemical Industries, Ltd. was prepared. Both solutions were previously bubbled with nitrogen.
The monomer solution prepared above was gradually added dropwise while stirring the cyclohexane solution at 100 rpm in a nitrogen atmosphere. After stirring for 30 minutes to achieve distribution equilibrium, the temperature was raised and polymerization was carried out at 65 ° C. for 8 hours. After completion of the temperature increase, the monomer phase gelled in about 15 minutes. After completion of the polymerization, the reaction solution was put on a Buchner funnel, and the resulting cross-linked copolymer was washed with methanol to remove residual divinylbenzene, cyclohexane and the like, and then washed with water. The polymerization yield was 81%. The obtained cross-linked copolymer was white in appearance, but was slightly opaque by microscopic observation. The obtained polymer was a gel-type crosslinked copolymer having a swelling degree of 4.63 ml / g and a water content of 68.9%, and the specific surface area was 0 m ² / g.
100 ml of the above-mentioned crosslinked copolymer drained and 100 ml of demineralized water were placed in a 500 ml flask, and 25 g of sodium hydroxide was added thereto. Hydrolyzed at 90 ° C. for 4 hours. After completion of the reaction, the crosslinked copolymer washed with water was subjected to the test as a gas adsorbent of Comparative Example 3 (gel-type weakly basic anion exchange resin having an amino group).
The obtained crosslinked copolymer had an average particle shape of about 330 μm, a degree of swelling of 7.33 ml / g, and a water content of 78.9%.

(Comparative Example 4)
Granular activated carbon (manufactured by Kishida Chemical) was washed 10 times with 50 times the volume of demineralized water until the supernatant became colorless and transparent, and subjected to the test as a gas adsorbent (activated carbon) of Comparative Example 4.

(Comparative Example 5)
An aminated silica gel was prepared by the following method.
Add 20.0 g of “Wakogel C-200” (trade name, silica gel manufactured by Wako Pure Chemical Industries, Ltd.), 100 g of toluene, and 20.0 g of γ-aminopropyltriethoxysilane to a 1.5 L pressurized reaction can at 130 ° C. The reaction was stirred for 10 hours. Next, the silica carrier produced by the above reaction was washed with methanol three times, finally washed with water, and vacuum-dried. The obtained aminated silica gel was used for the test as a gas adsorbent (amino group-containing silica gel) of Comparative Example 5.

(Comparative Example 6)
Diaion (registered trademark) SA12A (trade name, styrene gel-type strongly basic anion exchange resin manufactured by Mitsubishi Chemical Corporation) itself was tested as a gas adsorbent of Comparative Example 6 (styrene-based gel type strongly basic anion exchange resin). It was used for.
In addition, since the gas adsorbent of Comparative Example 6 was a gel-type anion exchange resin, pores were not confirmed (surface area was 0).

(Comparative Example 7)
Diaion (registered trademark) DCA11 (trade name, styrene-based porous weak anion exchange resin manufactured by Mitsubishi Chemical Corporation) itself was tested as the gas adsorbent of Comparative Example 7 (styrene-based porous weak anion exchange resin). It was used for.

(Comparative Example 8)
Diaion (registered trademark) WA30 (trade name, a styrene-based high-basic anion exchange resin manufactured by Mitsubishi Chemical Corporation) itself was used as a gas adsorbent of Comparative Example 8 (styrene-based high-basic anion-exchange resin). As a test.

(Comparative Example 9)
Diaion (registered trademark) PA 312 (trade name, styrene-based porous weak anion exchange resin manufactured by Mitsubishi Chemical Corporation) itself was tested as a gas adsorbent of Comparative Example 8 (styrene-based porous weak anion exchange resin). It was used for.

(Comparative Example 10)
In Example 26, instead of “Sebeads (registered trademark) EC-EP / S”, “Sepabaeds (registered trademark) FP-EP200” (trade name, a methacrylic polymer having an epoxy group manufactured by Mitsubishi Chemical Corporation) was used. A sample treated in the same manner as in Example 26 except that it was used was subjected to the test as the gas adsorbent of Comparative Example 10 (methacrylic porous weak anion exchange resin).

(Comparative Example 11)
In Example 26, instead of “Sebeads (registered trademark) EC-EP / S”, “Sebeads (registered trademark) FP-EP300” (trade name, a methacrylic polymer having an epoxy group manufactured by Mitsubishi Chemical Corporation) was used. A sample treated in the same manner as in Example 26 except that it was used was subjected to the test as the gas adsorbent of Comparative Example 11 (acrylic porous weak anion exchange resin).

(Comparative Example 12)
"Sebeads (registered trademark) FP-EP200" in a wet state as a resin in a 1 L four-necked flask equipped with a stirring blade and a condenser tube (trade name, methacrylic polymer having an epoxy group manufactured by Mitsubishi Chemical Corporation) Was added in a wet state. To this, 350 ml of demineralized water and 50 g of diethylenetriamine (DETA, Tokyo Kasei) were added, and the temperature was raised to 30 ° C. Stir at 30 ° C. for 5 hours. After the reaction, the resin was taken out and washed with demineralized water. The resin washed with water was returned again to the 1 L four-necked flask, 500 ml of 2N sulfuric acid aqueous solution was added, and the mixture was stirred at 50 ° C. for 5 hours. After completion, the resin was washed with demineralized water on Nutsche. Further, the resin was filled in a glass column, and 10 BV of demineralized water was passed therethrough. Further, a 10-fold volume of 2N-sodium hydroxide aqueous solution was passed through, followed by further passing through demineralized water to obtain an OH-form ion form of the gas adsorbent of Comparative Example 12 (amino group-containing methacrylic acid weak base). Anion exchange resin).

(Comparative Example 13)
In Comparative Example 12, “Sebeads (registered trademark) FP-EP300” (trade name, a methacrylic polymer having an epoxy group manufactured by Mitsubishi Chemical Corporation) was used instead of “Sebeads (registered trademark) EC-EP200”. Except for the above, the same treatment as in Comparative Example 12 was used for the test as the gas adsorbent of Comparative Example 13 (methacrylic porous weak anion exchange resin).

(Comparative Example 14)
“Sepabeads (registered trademark) FP-HA20” (trade name, methacrylic weakly basic anion exchange resin having hexamethylenediamino group manufactured by Mitsubishi Chemical Corporation) itself was used as the gas adsorbent of Comparative Example 14 (having hexamethylenediamino group). Methacrylic weakly basic anion exchange resin).

(Comparative Example 15)
“Sepabeads (registered trademark) FP-DA05” (trade name, methacrylic weakly basic anion exchange resin having a dimethylamino group manufactured by Mitsubishi Chemical Corporation) itself was used as the gas adsorbent of Comparative Example 15 (methacrylic group having a dimethylamino group). Weakly basic anion exchange resin).

(Comparative Example 16)
"Sebeads (registered trademark) FP-DA20" (trade name, methacrylic weakly basic anion exchange resin having a dimethylamino group manufactured by Mitsubishi Chemical Corporation) itself was used as the gas adsorbent of Comparative Example 16 (methacrylic group having a dimethylamino group). Weakly basic anion exchange resin).

(Comparative Example 17)
“Sepabeads (registered trademark) FP-HA05” (trade name, a methacrylic weakly basic anion exchange resin having a hexamethylenediamino group manufactured by Mitsubishi Chemical Corporation) itself was used as the gas adsorbent of Comparative Example 17 (having a hexamethylenediamino group). Methacrylic weakly basic anion exchange resin).

(Comparative Example 18)
“Hokuetsu HS” (trade name, phenolic porous weak anion exchange resin manufactured by Ajinomoto Fine Techno Co.) itself was used as a gas adsorbent (phenolic porous weak anion exchange resin) of Comparative Example 18 for the test. did.

(Comparative Example 19)
“Hokuetsu KS” (trade name, phenolic porous weak anion exchange resin manufactured by Ajinomoto Fine Techno Co.) itself was used as a gas adsorbent of Comparative Example 19 (phenolic porous weak anion exchange resin) for testing. did.

(Comparative Example 20)
“Hokuetsu HS” (trade name, phenolic porous weak anion exchange resin manufactured by Ajinomoto Fine Techno Co., Ltd.) was vacuum-dried as a resin at 50 ° C. until the previous day in a 2 L four-necked flask equipped with a stirring blade and a condenser. ) 57.6 g (containing 0.14 mol as amine) was charged. To this, 200 ml (2.59 mol) of CME (chloromethyl methyl ether, manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred at 25 ° C. for 0.5 hour. Further, FeCl ₃ (15 g (31 mmol) of 0.09 g / g resin was added. The mixture was heated to 45 ° C. and stirred for 8 hours. The reaction was continued under gentle reflux. After completion, the mixture was cooled to 25 ° C. Then, 100 g of demineralized water was added and chloromethylated by hydrolysis.
The chloromethylated polymer (resin) obtained above is charged with 50 g of drained resin in a 500 ml four-necked flask, 50 ml of diethylenetriamine (DETA, Tokyo Kasei) is added and stirred at 110 ° C. The solution gradually turns from a clear solution to a brown solution. The resin is originally black like activated carbon, but the black state remains the same. Stir at 110 ° C. for 6 hours. After completion, the resin washed with water was subjected to the test as the gas adsorbent of Comparative Example 20 (amino group-containing phenolic porous weak anion exchange resin).

(Comparative Example 21)
“Hokuetsu KS” (trade name, phenolic porous weak anion exchange resin manufactured by Ajinomoto Fine Techno Co., Ltd.), which was vacuum-dried as a resin at 50 ° C. until the previous day in a 2 L four-necked flask equipped with a stirring blade and a condenser. 59.0 g (containing 0.14 mol as amine) was added. To this, 200 ml (2.59 mol) of CME (chloromethyl methyl ether, manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred at 25 ° C. for 0.5 hour. Further, FeCl ₃ (15 g (62 mmol) of 0.17 g / g resin was added. The mixture was heated to 45 ° C. and stirred for 8 hours. The reaction was continued under gentle reflux. After cooling, 100 g of demineralized water was added and chloromethylated by hydrolysis.
The chloromethylated polymer obtained as described above was subjected to an amination treatment in the same manner as in Comparative Example 20 and subjected to the test as a gas adsorbent of Comparative Example 21 (amino group-containing phenolic porous weak anion exchange resin).

(Comparative Example 22)
“Hokuetsu HS” (phenolic weak base anion exchange resin manufactured by Ajinomoto Fine Techno Co.) as a resin was chloromethylated in the same manner as in Comparative Example 20.
The chloromethylated polymer (resin) obtained above is charged with 50 g of drained resin in a 500 ml four-necked flask, added with 60 ml of EDA (ethylenediamine), and stirred at 100 ° C. The solution gradually turns from a clear solution to a brown solution. The resin is originally black like activated carbon, but the black state remains the same. Stir at 100 ° C. for 6 hours. After completion, the resin was washed with water. When 2N-hydrochloric acid is further passed, a reddish brown solution flows out. Gradually yellow, pale yellow and colorless. Further, after washing with 10 BV of water with demineralized water and passing 10 BV with 2N-NaOH, 20 BV of water with demineralized water was used as a gas adsorbent of Comparative Example 20 (amino group-containing phenolic porous weak anion exchange resin). Provided.

(Comparative Example 23)
“Hokuetsu KS” (phenolic weakly basic anion exchange resin manufactured by Ajinomoto Fine Techno Co.) as a resin was chloromethylated by the same method as in Comparative Example 21.
The chloromethylated polymer obtained above was aminated in the same manner as in Comparative Example 22 and subjected to the test as a gas adsorbent of Comparative Example 23 (amino group-containing phenolic porous weak anion exchange resin).

(Comparative Example 24)
150ml of toluene (genuine chemical) 150ml, 3-aminopropyltriethoxy dried with molecular sieve 4A (Kishida Chemical) on 50.0g of silica gel (Micro Bead Silica Gel Grade 500-75 / 200 Lot No 4012796 manufactured by Fuji Silysia Chemical) 50.0 g (0.226 mol) of silane (manufactured by Tokyo Chemical Industry) was added, and the bath temperature was set to 110 ° C. (internal temperature 108 ° C.) and stirred for 8 hours.
When the solution was mixed, it was a clear suspension, but gradually became a milky white suspension after 1 hour.
After the reaction, the silica gel carrier was washed with toluene, further washed with methanol, and further washed with demineralized water.
The obtained silica gel was vacuum-dried at 50 ° C. for 10 hours and used for the test as the gas adsorbent of Comparative Example 24 (silica gel-based weakly basic anion exchange resin).
In addition, N content was measured for the dried silica gel by elemental analysis, and acid adsorption capacity was measured.

(Comparative Example 25)
150 ml of toluene (genuine chemical) 150 ml, 3-aminopropyltriethoxy dried with molecular sieve 4A (genuine chemical special grade) on 50.0 g of silica gel (Micro Bead Silica Gel Grade 1000-75 / 200 Lot No 2080990 manufactured by Fuji Silysia Chemical) 50.0 g (0.226 mol) of silane (manufactured by Tokyo Chemical Industry) was added, and the bath temperature was set to 110 ° C. (internal temperature 108 ° C.) and stirred for 8 hours.
When the solution was mixed, it was a clear suspension, but gradually became a milky white suspension after 1 hour.
After the reaction, the silica gel carrier was washed with toluene, further washed with ethanol, and further washed with demineralized water.
The silica gel obtained was vacuum-dried at 50 ° C. for 10 hours and used for the test as the gas adsorbent of Comparative Example 25 (silica gel weakly basic anion exchange resin).
In addition, N content was measured for the dried silica gel by elemental analysis, and acid adsorption capacity was measured.

(Comparative Example 26)
150 ml of toluene, 3-aminopropyltriethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) dried on 50.0 g of silica gel (Micro Bead Silica Gel Grade 2000-75 / 200 Lot No 3121290 manufactured by Fuji Silysia Chemical) with molecular sieve 4A (genuine chemical product special grade) ) 50.0 g (0.226 mol) was added, the bath temperature was set to 110 ° C. (internal temperature 108 ° C.), and the mixture was stirred for 8 hours.
The solution was slightly refluxed.
When the solution was mixed, it was a clear suspension, but gradually became a milky white suspension after 1 hour.
After the reaction, the silica gel carrier was washed with toluene, further washed with ethanol, and further washed with demineralized water.
The obtained silica gel was vacuum-dried at 50 ° C. for 10 hours and used for the test as a gas adsorbent of Comparative Example 26 (silica gel-based weakly basic anion exchange resin).
In addition, N content was measured for the dried silica gel by elemental analysis, and acid adsorption capacity was measured.

(Comparative Example 27)
Silica gel (Micro Bead Silica Gel Grade 500-75 / 200 Lot No 4012796 manufactured by Fuji Silysia Chemical) 30.0 g, ethanol (genuine chemical special grade) 50 ml, demineralized water 50 ml, 3-aminopropyltriethoxysilane (manufactured by Tokyo Chemical Industry) 30 0.0 g (0.226 mol) was added, the bath temperature was set to 80 ° C. (internal temperature 108 ° C.), and the mixture was stirred for 8 hours.
When the solution was mixed, it was a clear suspension, but gradually became a milky white suspension after 1 hour.
After the reaction, the silica gel carrier was washed with ethanol, further washed with methanol, and further washed with demineralized water.
The obtained silica gel, which was vacuum-dried at 50 ° C. for 10 hours, was subjected to the test as the gas adsorbent of Comparative Example 27 (silica gel-based weakly basic anion exchange resin).
In addition, N content was measured for the dried silica gel by elemental analysis, and acid adsorption capacity was measured.

(Comparative Example 28)
Silica gel (Micro Bead Silica Gel Grade 2000-75 / 200 Lot No 3121290 manufactured by Fuji Silysia Chemical) 30.0 g, ethanol 50 ml, demineralized water 50 ml, 3-aminopropyltriethoxysilane (manufactured by Tokyo Chemical Industry) 30.0 g (0.226 mol) ), The bath temperature was set to 80 ° C. (inner temperature 78 ° C.), and the mixture was stirred for 8 hours.
The solution was slightly refluxed.
When the solution was mixed, it was a clear suspension, but gradually became a milky white suspension after 1 hour.
After the reaction, the silica gel carrier was washed with ethanol, further washed with methanol, and further washed with demineralized water.
The obtained silica gel was vacuum-dried at 50 ° C. for 10 hours and used as a gas adsorbent of Comparative Example 28 (silica gel-based weakly basic anion exchange resin).
In addition, N content was measured for the dried silica gel by elemental analysis, and acid adsorption capacity was measured.

(Comparative Example 29)
Silica gel (Micro Bead Silica Gel Grade 500-75 / 200 Lot No 4012796 manufactured by Fuji Silysia Chemical) 35.0 g, THF (tetrahydrofuran) (genuine chemical special grade) 100 ml, 3-aminopropyltriethoxysilane (manufactured by Tokyo Chemical Industry) 35. 0 g (0.226 mol) was added, the bath temperature was set to 70 ° C. (internal temperature 67 ° C.), and the mixture was stirred for 8 hours.
From the beginning it was a clear suspension.
After the reaction, the silica gel carrier was washed with THF (tetrahydrofuran), further washed with methanol, and further washed with demineralized water.
The obtained silica gel was vacuum-dried at 50 ° C. for 10 hours and used as a gas adsorbent of Comparative Example 29 (silica gel-based weakly basic anion exchange resin).
In addition, N content was measured for the dried silica gel by elemental analysis, and acid adsorption capacity was measured.

(Comparative Example 30)
Silica gel (Micro Bead Silica Gel Grade 2000-75 / 200 Lot No 3121290 manufactured by Fuji Silysia Chemical) 35.0 g, THF (tetrahydrofuran) (genuine chemical special grade) 100 ml, 3-aminopropyltriethoxysilane 35.0 g (0.226 mol) ), The bath temperature was set to 70 ° C. (internal temperature 67 ° C.), and the mixture was stirred for 8 hours.
From the beginning it was a white suspension.
After the reaction, the silica gel carrier was washed with THF (tetrahydrofuran), further washed with methanol, and further washed with demineralized water.
The obtained silica gel, which was vacuum-dried at 50 ° C. for 10 hours, was subjected to the test as the gas adsorbent of Comparative Example 30 (silica gel weakly basic anion exchange resin).
In addition, N content was measured for the dried silica gel by elemental analysis, and acid adsorption capacity was measured.

(Comparative Example 31)
Add 35.0 g of silica gel (Merck Silica Gel 60 1,07734,1000 Merck), 100 ml of THF (tetrahydrofuran) (special grade chemical), 35.0 g (0.226 mol) of 3-aminopropyltriethoxysilane, bath temperature Was set to 70 ° C. (internal temperature 67 ° C.) and stirred for 8 hours.
From the beginning it was a clear suspension.
After the reaction, the silica gel carrier was washed with THF (tetrahydrofuran), further washed with methanol, and further washed with demineralized water.
The obtained silica gel was vacuum-dried at 50 ° C. for 5 hours and used for the test as the gas adsorbent of Comparative Example 31 (silica gel-based weakly basic anion exchange resin).
In addition, N content was measured for the dried silica gel by elemental analysis, and acid adsorption capacity was measured.

(Comparative Example 32)
50.0 g of silica gel (Micro Bead Silica Gel Grade 500-75 / 200 Lot No 4012796 manufactured by Fuji Silysia Chemical), 50 ml of toluene dried with molecular sieve 4A (pure chemical product special grade), 3 (2 (2-Aminoethylamino) ethylamino) propyl 35.0 g (0.132 mol) of -trimethoxysilane (manufactured by Sigma-Aldrich) was added, and the bath temperature was set to 110 ° C. (internal temperature 108 ° C.) and stirred for 8 hours.
From the beginning it was a clear suspension.
After the reaction, the silica gel carrier was washed with toluene, further washed with methanol, and further washed with demineralized water.
The silica gel obtained was vacuum-dried at 50 ° C. for 10 hours and used for the test as the gas adsorbent of Comparative Example 32 (silica gel weakly basic anion exchange resin).
In addition, N content was measured for the dried silica gel by elemental analysis, and acid adsorption capacity was measured.

(Comparative Example 33)
50.0 g of silica gel (Micro Bead Silica Gel Grade 2000-75 / 200 Lot No 3121290 manufactured by Fuji Silysia Chemical), 50 ml of toluene dried with molecular sieve 4A (pure chemical product special grade), 3 (2 (2-Aminoethylamino) ethylamino) propyl 35.0 g (0.132 mol) of -trimethoxysilane (manufactured by Sigma-Aldrich) was added, the bath temperature was set to 70 ° C. (internal temperature 68 ° C.), and the mixture was stirred for 8 hours.
Although it was slightly opaque, it was a suspension solution with a transparent feeling despite being porous.
After the reaction, the silica gel carrier was washed with toluene, further washed with methanol, and further washed with demineralized water.
The silica gel obtained was vacuum-dried at 50 ° C. for 10 hours and used for the test as the gas adsorbent of Comparative Example 33 (silica gel weakly basic anion exchange resin).
In addition, N content was measured for the dried silica gel by elemental analysis, and acid adsorption capacity was measured.

(Comparative Example 34)
35.0 g of silica gel (Wako-gel C-300, manufactured by Wako Pure Chemical Industries), 50 ml of toluene dried with molecular sieve 4A (genuine chemical special grade), 3 (2 (2-Aminoethylamino) ethylamino) propyl-trimethoxysilane (manufactured by Sigma-Aldrich) ) 50.0 g was added, the bath temperature was set to 70 ° C. (internal temperature 68 ° C.), and the mixture was stirred for 8 hours.
From the beginning it was a clear suspension.
After the reaction, the silica gel carrier was washed with toluene, further washed with methanol, and further washed with demineralized water.
The obtained silica gel was vacuum-dried at 50 ° C. for 5 hours and subjected to the test as a gas adsorbent of Comparative Example 34 (silica gel weakly basic anion exchange resin).
In addition, N content was measured for the dried silica gel by elemental analysis, and acid adsorption capacity was measured.

  The gas adsorbents obtained in each Example and Comparative Example were evaluated by the above tests. The results are shown in Tables 1-4.

The schematic diagram of the mechanism (presumption) which capture | acquires the harmful substance in the gas flow of the gas adsorbent of this invention is shown.

Explanation of symbols

1 Toxic Component Molecule 2 Mean Free Path of Toxic Component Molecule 3 Gas Adsorbent 4 Pore Diameter 5 Ion Exchange Group

Claims (4)

Gas adsorption for a tobacco filter that satisfies the following conditions (I), (II), (IV), and (V), or the following conditions (I), (III), (IV), and (V): The gas adsorbent has a styrene-divinylbenzene crosslinked structure skeleton and is composed of a weakly basic anion exchange resin containing an amino group, and the weakly basic anion exchange resin has a temperature of 40 to 100 ° C., which was obtained by washing with strong acid at a concentration 0.1～5N, or are performed by the 110 ° C. or higher 160 ° C. or less at least a portion of the polymerization reaction, 1 hour or more at a time 110 ° C. or higher gas adsorbent, characterized in that the obtained polymer is therefore also introduced amino groups by the.
(I) The average pore radius of the gas adsorbent in mercury porosimeter measurement is 330 to 3000 mm.
(II) The amine elution amount from the gas adsorbent per unit mass is 10 μeq / g or less.
(III) The content of the monocyclic aromatic compound represented by the following formula 1 in the gas adsorbent per unit mass is 4 mg / g or less.

(In the above formula 1, R represents a substituent selected from a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, and an alkenyl group having 1 to 3 carbon atoms. N is a number from 1 to 6, and the number of substituents R. When there are a plurality of R, each R may be the same or different.)
(IV) The neutral salt decomposition capacity of the gas adsorbent per unit mass is 0.43 meq / g or less.
(V) The acid adsorption capacity of the gas adsorbent per unit mass is 1.5 meq / g or more. Gas adsorbent is a styrene - has a divinyl benzene cross-linked scaffold, be those made of weakly basic anion exchange resin containing amino groups, at least some rows physician 110 ° C. or higher 160 ° C. or less of the polymerization reaction , a material obtained by introducing an amino group into the polymer obtained by 1 hour or more 110 ° C. or higher at which time, the temperature 40 to 100 ° C., is obtained by washing with strong acid at a concentration 0.1~5N The gas adsorbent according to claim 1, wherein The gas adsorbent according to claim 1 or 2 , wherein the weakly basic anion exchange resin is further washed with methanol after washing with a strong acid. The gas adsorbent according to any one of claims 1 to 3 , wherein the weakly basic anion exchange resin is in an OH form.

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