JP2001038202A - Gas adsorbent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain excellent thermal stability and to reduce emission of contaminants by including a polymers having structural units expressed by a specific formula. SOLUTION: The gas adsorbent comprises a polymer having structural units expressed by the formula (wherein A is a 3-8C alkylene or a 4-8C alkoxymethylene; R1, R2 and R3 are each independently hydrogen, a 1-6C alkyl or an alkanol; and X is a counter ion of ammonium salt, and a ring (a) may be further substituted). The gas adsorbent is used as proper shapes such as a granular, a powder, a fiber shape or the like. The gas adsorbent is such a structure that a granular, a powder shaped, or a fiber shaped gas adsorbent may be carried by a fiber shaped synthetic resin foam having continuous vapor cells, membrane substrates or the like. Also, it may be such a structure that another polymer substrates formed into various kinds of shapes such as the fiber, the membrane or the like are, by using graft polymerization, graft- polymerized with the polymer expressed by the formula.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel gas adsorbent, and more particularly to a gas adsorbent comprising an anion exchanger having excellent gas phase heat stability.

[0002]

2. Description of the Related Art Clean rooms are used not only in the cutting-edge industries such as the semiconductor industry, precision machine industry, and photography industry, but also in biological manufacturing such as pharmaceutical manufacturing and hospitals. The field of application has expanded to. As environmental conditions in such an industrial field, air purification as well as temperature, humidity, and air flow are extremely important. Particularly in the semiconductor industry, efforts are being made to remove as much as possible gas ions in the air that cause contamination of the wafer surface as the degree of integration of the LIS increases year by year. Chemical filters that remove gas and ion components in the air are used,
Chemical filters using ion exchangers not only have a high removal rate of gas and ion components at the ppb level, but also do not release non-adsorbed substances unlike filters made of activated carbon. . As the ion exchange group, a cation exchange group such as a sulfonic acid group and a carboxyl group, and an anion exchange group such as a quaternary ammonium group and a tertiary amino group are used.

Among these, strongly basic anion exchange fibers having a quaternary ammonium group have a high basicity and an excellent ability to remove acidic gas, but are more unstable than other tertiary and secondary amino groups. And the release of the amines used for the quaternary ammonium conversion tends to occur. This phenomenon is called Hofma
This is called nn decomposition and is well known in the field of ion exchange resins. In general, the ion-exchange resin is more unstable in a dry state, and among them, there are various problems when a strongly basic anion-exchange resin is used in the air in a regeneration type. In particular, in the precision industry such as the semiconductor industry, there is a concern that the surface of a wafer may be contaminated. Therefore, conventionally, the fourth
In many cases, a weakly basic anion exchanger having a lower amine such as a tertiary amine as an ion exchange group is used instead of the strongly basic anion exchanger having a tertiary ammonium group.

On the other hand, as a method for producing a gas adsorbent utilizing an ion exchange reaction, as disclosed in Japanese Patent Publication No. 6-20554, a fiber is produced by using a polymerizable monomer having an ion exchange group. And the like, and a method of forming a polymerizable monomer having a group capable of introducing an ion exchange group and then introducing an ion exchange group.
When the ion-exchange group is introduced after molding, the difficulty of the introduction reaction and purification after the reaction affect the performance of the gas adsorbent. In other words, if the raw materials, solvents, catalysts and by-products of the reaction involved in the reaction remain, they are released into the air during use of the gas adsorbent and cause contamination, so it is necessary to remove as much as possible. However, the use of an excessive amount of raw materials is disadvantageous due to the low synthesis rate and the low conversion. When ion-exchange groups are introduced into styrene, which is used as a raw material for various functional materials, the introduction of sulfonic acid groups requires a long-term, severe reaction with excess sulfuric acid or chlorosulfonic acid, and an anion. In order to introduce the exchange group, the reaction is performed in two steps because it is reacted with chloromethyl methyl ether as a specific chemical substance and then with trimethylamine or the like. Purification of an excessively used reagent and purification in the case of multi-step reactions involve difficulties and are economically disadvantageous. Also, Japanese Patent Application Laid-Open
Japanese Patent No. 24334 discloses a gas adsorbent comprising an anion exchanger in which a branched alkyl group having 1 to 8 carbon atoms is introduced between a benzene ring and an ammonium group of a styrenic polymer. Speed was not yet satisfactory.

[0005]

DISCLOSURE OF THE INVENTION The present invention comprises a strongly basic anion exchanger having a quaternary ammonium group which is excellent in the performance of removing acidic gases, and the amount of amine released therefrom is extremely small. It is an object to provide a gas adsorbent. Further, the present invention can be produced using a polymerizable monomer into which an ion-exchange group has been introduced in advance, or using a polymerizable monomer which is easy to introduce an ion-exchange group after molding. Therefore, the present invention provides a gas adsorbent that emits less polluting substances.

[0006]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a specific polymer, namely, an amino group or an ammonium group, has 3 carbon atoms.
By using a styrene-based polymer into which a spacer group consisting of an alkylene group having from 8 to 8 or an alkyleneoxymethylene group having from 4 to 8 carbon atoms has been introduced, the above-mentioned problems can be solved and a styrene skeleton conventionally used in general The present inventors have further found that the gas adsorption rate can be improved as compared with an ammonium group obtained by quaternizing an aminomethyl group, and arrived at the present invention. That is, the present invention resides in a gas adsorbent comprising a polymer having a structural unit represented by the following general formula (1).

[0007]

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(In the formula (1), A represents an alkylene group having 3 to 8 carbon atoms or an alkoxymethylene group having 4 to 8 carbon atoms, and R ₁ , R ₂ , and R ₃ each independently represent a hydrogen atom, a carbon atom, X represents an alkyl group or an alkanol group represented by Formulas 1 to 6, and X
Represents a counter ion of an ammonium salt. Ring a may be further substituted. )

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The gas adsorbent of the present invention is a strongly basic gas adsorbent having a polymer having at least the structural unit represented by the general formula (1). In the general formula (1),
A represents an alkylene group having 3 to 8 carbon atoms or an alkoxymethylene group having 4 to 8 carbon atoms. As the alkylene group, a linear, cyclic propylene group, butylene group, pentylene group,
A hexylene group, a heptylene group and the like can be mentioned, and as the alkoxymethylene group, an alkyleneoxymethylene group corresponding thereto can be mentioned, but a linear alkylene group is preferable. Particularly, a linear alkylene group having 3 to 4 carbon atoms is preferable. When A is an ethylene chain, the ammonium group is easily decomposed and desorbed by Hoffman decomposition, so that it is chemically unstable. When A has more than 8 carbon atoms, the molecular weight per structural unit increases, and the gas adsorbent becomes Is not preferred because the ion exchange capacity per unit weight of

A in the general formula (1) may be located at any of the o-, m- and p-positions of the styrene residue, but is preferably at the m- or p-position. R ₁ , R ₂ , and R ₃ of the anion exchange group in the general formula (1) represent a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, or the like. Carbon number 1
6, preferably 1 to 4 alkyl groups, or 1 to 6 carbon atoms such as a hydroxyethyl group and a hydroxypropyl group;
Preferably it is 1-4 alkanol groups. R ₁ ,
R ₂ and R ₃ may be the same. When the ion exchange capacity per unit weight is increased and the heat resistance is taken into consideration, R ₁ , R ₂ , and R ₃ are preferably a methyl group, particularly preferably a trimethylammonium group.

[0011] The X ^over a counterion of the ammonium salt, as with counterions conventional ion exchangers for example,
OH ^-, HCO _{3 ^{over, CO 3 2-, Cl -,}} Br -, SO
₄ ^2-, CH ₃ COO ^{chromatography,} and the like. As the gas adsorbent, OH ⁻ , HCO ₃ ^— , and CO ₃ ²⁻ are particularly preferable.
Ring a may be further substituted with an alkyl group, a halogen atom, or the like. Here, examples of the alkyl group include lower alkyl groups such as a methyl group and an ethyl group, and examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom. The gas adsorbent having the above structural unit can be used in an appropriate shape. Specific examples include particles, powders, fibers, aggregates of single fibers or short fibers, woven or nonwoven fabrics, nets, hollow fibers, membranes, and felts. In order to obtain these shapes, a composite material combined with another material may be used. Further, when forming into a fibrous form, a composite fiber with another polymer or a short fiber may be mixed with a short fiber of another material, followed by papermaking. Alternatively, a structure in which the above-mentioned particulate, powdery or fibrous gas adsorbent is carried on a net-like base made of another material, a synthetic resin foam having open cells, a film-like base, or the like may be used. As a supporting method at this time, a known method can be used, but it is preferable to use an impregnating agent so that the supported particles or powder do not become a source of fine particles.

Also, a structure in which the polymer represented by the above general formula (1) of the present invention is graft-polymerized on other polymer base materials formed into various shapes such as fibers and membranes by utilizing graft polymerization. But it doesn't matter. However, these materials to be combined need to be combined within a range that does not reduce the function of gas adsorption. Although the compounding ratio varies depending on the concentration of the gas to be removed, it is preferable that the structure of the general formula (1) is usually at least 5% by weight or more based on the total weight of the adsorbent.

The gas adsorbent of the present invention preferably has a large surface area in order to keep the gas removal efficiency high. Although the numerical value differs depending on the shape, when it is made into a fibrous form, the fiber diameter is usually 1 to 1000 μm, more preferably 5 to 200 μm.
μm. When in the form of particles, the particle size is usually 1 to
It is 1000 μm, more preferably 3 to 800 μm.
When the nonwoven fabric is used, the basis weight is 10 to 100 g /
m ² and a porosity of 50 to 98% are preferred. Further, the gas adsorbent of the present invention is used for gas purification in a clean room, in a known form, for example, by contacting with a gas to be removed,
Alternatively, it can be suitably used by a method such as passing. At this time, in order to increase the efficiency of ion exchange, it is preferable that the gas adsorbent of the present invention has a shape in which the structure represented by the general formula (1) is uniformly distributed. Further, the thickness, density, and the like of the gas adsorbent of the present invention can be determined in consideration of the concentration of the gas to be removed and the allowable pressure loss.

The gas removed by the gas adsorbent of the present invention is an acidic substance or an acidic gas. Specifically, N
Ox, SOx, HCl, HF, PH ₃ , H ₃ PO ₄ , boric acid, BF3, hydrogen bromide, sulfuric acid, nitric acid, organic phosphoric acid, etc.
For example, it is an acidic substance emitted in a semiconductor manufacturing process or the like. These concentrations are usually 10 pp in a clean room.
b or more. For example, NOx is usually 10
５０50 ppb and SOx are usually present in an amount of about 10 to 50 ppb, which is usually reduced to 5 ppb or less, preferably 1 ppb or less.
It is effective to reduce it to b or less. However, since the acid gas concentration in the clean room and how much the acid gas is reduced depend on the type and application of the clean room, considering the required performance and economics, the shape and gas of the gas adsorbent of the present invention are determined by preliminary experiments. Adsorption capacity can be determined.

The flow rate of the gas flowing through the gas adsorbent of the present invention is as follows.
Preliminary tests can be carried out to determine the values as appropriate, but usually SVs of about 1000 to 100000 h ^-1 can be used. Humidity when the gas adsorbent of the present invention is used,
About 20 to 80% is preferable. Further, in order to keep the gas removal efficiency by the ion exchange reaction high, 40 to 70% is more preferable. In the gas adsorbent according to the present invention, the method for synthesizing the polymer having the structural unit represented by the general formula (1) is not particularly limited, but can be produced by, for example, the following method. . The following general formula (2)

[0016]

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(In the formula (2), A represents an alkylene group having 3 to 8 carbon atoms or an alkoxymethylene group having 4 to 8 carbon atoms, Z represents a halogen atom or a hydroxyl group, and ring b is further substituted. And then introducing an anion exchange group into the polymer. The following general formula (3)

[0018]

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(In the formula (3), A represents an alkylene group having 3 to 8 carbon atoms or an alkoxymethylene group having 4 to 8 carbon atoms;
₁ , R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkanol group, and X represents a counter ion of an ammonium salt. Ring c may be further substituted. A) a method of polymerizing the polymerizable monomer represented by The following general formula (4)

[0020]

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(In the formula (4), A represents an alkylene group having 3 to 8 carbon atoms or an alkoxymethylene group having 4 to 8 carbon atoms;
₁ and R ₂ each independently represent a hydrogen atom, a carbon number of 1 to 6;
And the ring d may be further substituted. ), And then quaternizing the ion exchange group. In the general formulas (2), (3) and (4),
Specific examples of A, R ₁ , R ₂ , R _3, X and the substituents on the rings b to d include the same as those shown in the general formula (1). When Z is a halogen atom, a chlorine atom, a bromine atom,
An iodine atom is used, and a bromine atom is particularly preferred. The polymerizable monomer to be a precursor represented by the general formula (2) can be synthesized by several methods. For example, it can be synthesized by reacting a Grignard reagent of chlorostyrene with 1, ω-dihalogenoalkane. Alternatively, Japanese Unexamined Patent Application Publication No.
The method described in Japanese Patent Application Laid-Open No. 9921 may be used. When the polymerizable monomer of the general formula (2) is used as a polymerizable monomer, a precursor of a gas adsorbent having a structural unit of the following general formula (5) is formed on a polymer substrate. .

[0022]

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(Wherein A represents an alkylene group having 3 to 8 carbon atoms or an alkoxymethylene group having 4 to 8 carbon atoms, Z represents a halogen atom or a hydroxyl group, and ring e may be further substituted. The gas adsorbent of the present invention can be obtained by reacting the polymer with ammonia or an amine according to a known method, and further converting the terminal functional group Z to an ammonium group with an alkylating agent, if necessary. The polymerizable monomers of the general formulas (3) and (4) can be obtained by reacting the monomer of the general formula (1) with ammonia or an amine to convert Z to an amino group or an ammonium group. Further, the monomer of the general formula (3) can be obtained by treating the monomer of the general formula (4) with an alkylating agent such as an alkyl halide.

In the general formula (2) or (5), the method of converting the functional group Z into an amino group or an ammonium group can be performed according to a known method. That is, when Z is a halogen atom, it may be reacted with an alkylamine such as ammonia, methylamine, dimethylamine, trimethylamine, and dimethylethanolamine. When Z is a hydroxyl group, it may be once converted into a halogen atom and then reacted with the above-mentioned ammonia or alkylamines.
When introducing the amino group and the ammonium group, a solvent is generally used. Specifically, water, methanol, acetone, 1,2-dichloroethane, dioxane,
Toluene and the like. The reaction temperature varies depending on the reaction mode, the type of the functional group, and the type of the solvent.
Is common.

As a method for polymerizing the polymerizable monomers represented by the general formulas (2) to (4), various known methods can be used. Specifically, a method of mixing and polymerizing the polymerizable monomers represented by the general formulas (2) to (4) with a polymerization initiator, a chemical graft polymerization, or a graft polymerization by ionizing radiation is preferable. As the polymerization initiator, benzoyl peroxide, lauroyl peroxide, t-butyl hydroperoxide, azobisisobutyronitrile, or the like is used, and is usually 0.1 to 5 wt. %, But the amount of the initiator can be adjusted depending on the shape to be formed. The polymerization temperature varies depending on the type and concentration of the polymerization initiator, but is usually selected in the range of 40 to 150 ° C, more preferably 50 to 100 ° C. The polymerization time is usually in the range of 1 to 30 hours, preferably in the range of 1 to 15 hours.

In the case of graft polymerization, a method using ionizing radiation regardless of the type and shape of the polymer substrate is suitably used. As ionizing radiation, α-ray, β-ray, γ
Any of an electron beam, an accelerated electron beam, and an ultraviolet ray can be used, but an accelerated electron beam and a γ-ray are particularly preferable. The irradiation dose is particularly preferably from 20 to 300 kGy. If the amount is too small, sufficient active sites for the reaction will not be generated, and if the irradiation dose is excessive, the polymer substrate will be greatly damaged and deteriorated, resulting in an increase in cost and a problem. When performing grafting by the radiation method, a simultaneous radiation method in which a polymer base material and a polymerizable monomer to be grafted are coexistent and irradiated and grafted together, and only the polymer base material is previously irradiated with radiation, And a pre-irradiation method of contacting with a polymerizable monomer. In the present invention, any of the irradiation methods can be used, but a pre-irradiation method in which there is little possibility that a homopolymer of a polymerizable monomer is generated is more preferable.

The polymer substrate which has been irradiated is grafted by contacting or impregnating the polymerizable monomer solution in a liquid phase under oxygen-free conditions. If necessary, the polymerizable monomer solution can be heated. In the liquid phase graft polymerization in which the irradiated substrate is graft-polymerized while immersed in the monomer solution, the reaction temperature is usually 10 to 90.
° C, preferably 20 to 60 ° C, and the reaction time is usually 1 to 12
A time, preferably 2 to 10 hours, is suitable. The reaction temperature of the impregnated graft polymerization in which a predetermined amount of monomer is applied to the irradiated substrate and reacted in a vacuum or an inert gas is usually 10 to 90 ° C., preferably 20 to 60 ° C. But usually 0.1 to 10 hours, preferably 0.2 to
8 hours is suitable. In this case, since the substrate after the graft polymerization is in a dry state, there are advantages such as easy handling of the substrate and a small amount of waste liquid generated.

Gas-phase graft polymerization in which an irradiated substrate is brought into contact with a monomer vapor can be applied only to a monomer having a relatively high vapor pressure and tends to cause uneven grafting. There is an advantage that the substrate is in a dry state. In this case, the reaction temperature is usually 10
-90 ° C, preferably 20-80 ° C, and the reaction time is generally 1-12 hours, preferably 2-10 hours. In the present invention, when polymerizing the polymerizable monomers represented by the general formulas (2) to (4) by a known method, a solvent for dissolving or suspending the polymerizable monomer may coexist. . Specifically, water and various solvents such as alcohols, ethers, aromatics, aliphatics, esters, and halogens can be used as organic solvents, and these can be used alone or as a mixture. Can be either. Specifically, methanol,
Examples include ethanol, isopropyl alcohol, toluene, benzene, xylene, hexane, cyclohexane, ethyl acetate, butyl acetate, and methylene chloride.

In the present invention, when polymerizing the polymerizable monomers represented by the general formulas (2) to (4),
A polymerizable monomer other than the monomer represented by (4) may coexist. As the second polymerizable monomer,
It is selected from a crosslinkable monomer having two or more unsaturated hydrocarbons and a polymerizable monomer having one. Specifically, divinylbenzene, polyvinylbenzene, alkyldivinylbenzene, dialkyldivinylbenzene, bis (alkylstyrene), ethylene glycol di (meth) acrylate,
(Poly) ethylene glycol di (meth) acrylate,
Polyethylene bis (meth) acrylamide, styrene,
Examples thereof include alkylstyrene, (meth) acrylate, (meth) acrylic acid, acrylonitrile, hydroxyethyl (meth) acrylate, vinylpyrrolidone, and dimethylacrylamide.

These second polymerizable monomers can be added as long as the function of the gas adsorbent is not reduced. The content is usually from 0 to the polymerizable monomer.
It is used at 50% by weight, preferably at 0-20% by weight.
In the present invention, when polymerizing the polymerizable monomers represented by the general formulas (2) to (4), known polymerization techniques can be used according to the shape to be molded. Specifically, techniques such as suspension polymerization, solution weight, and bulk polymerization can be used. In the gas adsorbent of the present invention thus obtained, since a spacer having 3 or more carbon atoms exists between the benzene ring and the amino group or the ammonium group, the desorption of the ion-exchange group can be performed at room temperature or at a high temperature. Few. Further, since the polymerizable monomer is highly reactive, an ion-exchange group can be introduced under mild conditions, or an amine or the like used in the production for polymerizing a monomer having an ion-exchange group already introduced. Is easy to remove. Therefore, the gas adsorbent according to the present invention is much cleaner than a conventional ion exchange type gas adsorbent having a quaternary ammonium group.

The gas adsorbent of the present invention can be used not only in the advanced industrial fields such as the semiconductor industry, precision machine industry and photographic industry, but also in biological clean rooms such as the pharmaceutical manufacturing industry and hospitals, but also recently in the food industry and agricultural fields. In addition, it can be used for air purification in clean rooms in peripheral industries. In particular, in the field of semiconductor industry, as the degree of integration of the LIS has been increasing year by year, efforts have been made to remove gas ions in the air which cause contamination of the wafer surface as much as possible. The material is useful. It is also useful when highly purified air is required, regardless of the industrial field.

[0032]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the invention. In the following Examples and Comparative Examples, meq / g indicates a milliequivalent per dry ion exchanger weight. The exchange capacity of the anion exchanger was measured according to Diaion Manual (issued by Mitsubishi Chemical Corporation). In addition, the manufacturing method of the monomer was shown as a reference example. Reference Example 1 (Synthesis of 4-bromobutylstyrene) The synthesis of 4-bromobutylstyrene was described in JP-A-4-349.
The method described in Example 941 was used.

Production Example 1 9-bromobutylstyrene 92.7 obtained in Reference Example 1
An ion-exchange resin having the following performance was obtained by the method described in JP-A-4-34991 using parts by weight and 7.3 parts by weight of industrial grade divinylbenzene. Neutral salt decomposition capacity 3.65 meq / g Neutral salt decomposition capacity 1.10 meq / ml Water content 54.1% Comparative Production Example 1 The performance of Diaion SA10A used as a comparison is as follows. Neutral salt decomposition capacity 1.37 meq / ml Water content 45.9%

Example 1 and Comparative Example 1 As Examples 1 and Comparative Example 1, the counter ion of the resin of Production Example 1 and Comparative Production Example 1 was OH ⁻ , and the temperature was 25 ° C.
It was allowed to stand for 24 hours in a humidity chamber at a relative humidity of 45%, and it was confirmed that the resin moisture had become constant. 1 g of each of these resins was sealed in a Tedlar bag, and the inside was replaced with N ₂ . After leaving at 25 ° C. for 1 hour, the gas was collected and the ammonia concentration was measured. Example 1 (resin of Production Example 1): 1.8 ppb Comparative Example 1 (resin of Comparative Production Example 1): 85 ppb Was.

Example 2 and Comparative Example 2 The resins of Production Example 1 and Comparative Production Example 1 were prepared in the same manner as in Example 2 and packed in a glass column having an inner diameter of 5 cm at a layer height of 1 cm.
A glass fiber filter was installed at the column inlet and column outlet. A gas containing HCl was passed through this column, and the removal rate before and after the column was measured. HCl containing gas (C
l ^- concentration of 100 to 120 ppb) is a standard gas (10
0 ppm) with high-purity air. Measurements after passing through a gas in ultrapure water, is absorbed into water the Cl ^- it was quantified by ion chromatography. The ion removal rate was Example 2 (resin of Production Example 1): 94% Comparative Example 2 (resin of Comparative Production Example 1): 88%.

Example 3 An electron beam was applied to a polyethylene-coated polypropylene non-woven fabric (average diameter: 50 g / m 2) having an average diameter of 20 μm in a nitrogen atmosphere for 200 hours.
After irradiation with kGy, the substrate was immersed in a 50% dimethyl sulfoxide solution of 4-bromobutylstyrene obtained in Reference Example 1 and reacted at 40 ° C. for 5 hours to obtain a graft ratio of 58%. The grafted non-woven fabric was reacted in a 30% aqueous solution of trimethylamine at 50 ° C. for 5 hours to obtain a grafted nonwoven fabric.
-Introducing an ammonium group into bromobutylstyrene,
Thus, a quaternary ammonium ion exchanger was obtained. The obtained ion exchanger was treated with an aqueous solution of sodium hydroxide and subsequently with an aqueous solution of sodium chloride to convert it to Cl form, and the ion exchange capacity was measured, which was 1.50 meq / g.
The nonwoven fabric overlaid five cutouts in 5cm diameter set in a funnel-shaped holder, as well as Cl Example 2 ^- was measured removal rate. As a result, the removal rate was 95%.

[0037]

According to the gas adsorbent of the present invention, the quaternary ammonium group has excellent thermal stability. Low release of pollutants from the gas adsorbent due to by-products due to the introduction of ion exchange groups and residual reagents used in the reaction. Therefore, it is an extremely clean gas adsorbent, and has the advantage of minimizing contamination of air and the like when used. The gas adsorbent of the present invention can purify air required to clean a clean room or the like, and has a remarkable industrial value.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08J 9/36 CEZ C08J 9/36 CEZ // C08L 101: 00 F-term (Reference) 4D012 BA01 CK10 4F074 CE16 CE24 CE48 CE85 4G066 AB13D AC13C AC14B AC14C AD06B AD10B AD13B AD20B AE10B AE19C BA09 BA16 CA02 CA29 CA31 DA03 FA07 FA11 FA31 4J100 AB07P AB08P AB09P AB10P BA03P BA04P BA29P BA32H BA32P BA33H BA61P CA01 HA04

Claims (12)

[Claims] 1. A gas adsorbent comprising a polymer having a structural unit represented by the following general formula (1). Embedded image (In the formula (1), A represents an alkylene group having 3 to 8 carbon atoms or an alkoxymethylene group having 4 to 8 carbon atoms, and R ₁ ,
R ₂ and R ₃ each independently represent a hydrogen atom, a carbon number of 1 to 6;
X represents a counter ion of an ammonium salt. Ring a may be further substituted. ) 2. In the general formula (1), A has 3 to 3 carbon atoms.
The gas adsorbent according to claim 1, wherein the gas adsorbent is a straight-chain alkylene group. 3. The gas adsorbent according to claim ₁ , wherein in formula (1), R ₁ , R ₂ and R ₃ are all methyl groups. 4. The polymer according to claim 1, wherein the polymer is a trimethylvinylphenylbutylammonium bromide polymer.
The gas adsorbent according to 1. 5. The gas adsorbent according to claim 1, wherein the shape of the polymer is particulate, powdery or fibrous. 6. The gas adsorbent according to claim 1, wherein the polymer is supported on a synthetic resin foam. 7. The polymer is represented by the following general formula (2): (In the formula, A is an alkylene group having 3 to 8 carbon atoms or 4 carbon atoms.
And Z represents an alkoxymethylene group, and Z represents a halogen atom or a hydroxyl group. Ring b may be further substituted. The gas adsorbent according to any one of claims 1 to 6, wherein an anion exchange group is introduced after polymerizing the polymerizable monomer represented by (1). 8. The polymer represented by the following general formula (3): (In the formula (3), A represents an alkylene group having 3 to 8 carbon atoms or an alkoxymethylene group having 4 to 8 carbon atoms, and R ₁ ,
R ₂ and R ₃ each independently represent a hydrogen atom,
6 represents an alkyl group or an alkanol group. X represents a counter ion of an ammonium salt. Further, ring c may be further substituted. 7. The gas adsorbent according to claim 1, wherein a polymerizable monomer represented by the formula (1) is polymerized. 9. The polymer represented by the following general formula (4): (In the formula (4), A represents an alkylene group having 3 to 8 carbon atoms or an alkoxymethylene group having 4 to 8 carbon atoms, and R ₁ , R ₂
Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkanol group. Ring d may be further substituted. The gas adsorbent according to any one of claims 1 to 6, wherein the polymerizable monomer represented by the formula (1) is polymerized, and then the ion exchange group is quaternized. 10. The gas adsorbent according to claim 7, wherein the polymerizable monomer represented by the general formula (2) is 4-bromobutylstyrene. 11. The gas adsorbent according to claim 8, wherein the polymerizable monomer represented by the general formula (3) is trimethylvinylphenylbutylammonium bromide. 12. A chemical filter using the gas adsorbent according to claim 1.