JP2011206671A - Carbon dioxide adsorbent composed of cyclic guanidine compound, and method for producing cyclic guanidine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cyclic guanidine compound which has excellent adsorption/desorption capability of carbon dioxide and can be inexpensively produced with a high yield.SOLUTION: The carbon dioxide adsorbent includes the cyclic guanidine compound, for example, 2-(1-butyl amino)-4, 5-dihydro-1H-imidazole, 2-benzyl amino-4, 5-dihydro-1H imidazole, 2-(1-butyl amino)-1, 4, 5, 6-tetrahydro pyrimidine or derivatives thereof. The production method includes a reaction of an alkylthio cyclic amidine salt or a derivative thereof with an amino compound in a solvent having an ether-based aprotic polar solvent as a principal component.

Description

  The present invention relates to a cyclic guanidine compound that is excellent in carbon dioxide adsorption / desorption ability and can be produced at high yield and at low cost, and a method for producing the same.

  The problem of global warming due to an increase in the concentration of carbon dioxide in the atmosphere is becoming more and more serious, and there is an urgent need for countermeasures. It is sent. As a compound that can be used for such a trap method, 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) having a cyclic amidine skeleton is known (Patent Document 1). However, DBU has a problem of insufficient carbon dioxide adsorption capacity.

Further, when 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD) of cyclic guanidine, which is a stronger base than cyclic amidine, is used, carbon dioxide adsorption power higher than that of DBU is obtained. It has been reported (Non-Patent Document 1). However, since TBD is very expensive, there is a problem that it is not suitable for an application that requires a large amount such as a carbon dioxide adsorbing material and is difficult to put into practical use.
That is, tetramethoxymethane used for the reaction of TBD is very expensive. Even if it is aside from this, there are problems in production efficiency such as requiring two days at 120 ° C. in a dimethyl sulfoxide solution, and it is not suitable for mass synthesis. Further, since TBD does not have a reactive substituent, it is difficult to carry out high molecular weight or chemical support on a carrier, and it is difficult to put carbon dioxide traps into practical use.

Moreover, it is not known that cyclic guanidine other than TBD has the ability to adsorb carbon dioxide.
Accordingly, there has been a demand for a cyclic guanidine compound that is excellent in carbon dioxide adsorption / desorption ability and that can be produced at high yield and at low cost, and a method for producing the same.
Several methods for producing cyclic guanidines have been reported, such as a method of reacting an alkylthio cyclic amidine salt with an amine (for example, Non-Patent Document 2), or a method of reacting a halloinium salt with a hydroxyethylguanidine (patent). Document 2) is known.

In the former, there are many reactions in which an amine is excessively used, and therefore, the yield is very low at around 50% particularly in the synthesis of guanidine having a six-membered ring. Recently, synthesis by microwave reaction under the condition of 160 ° C. has also been reported (Non-patent Document 3), but the yield is around 70% even when such high energy is applied.
The latter is not easy to synthesize hydroxyethyl guanidine as a raw material, and when a cyclic guanidine is produced, a by-product is produced in the same amount as a haloiminium salt, and the yield is also medium. The process by was required, and it was inferior to production efficiency.
Therefore, in order to put into practical use a cyclic guanidine having carbon dioxide adsorption power similar to TBD, it has been demanded to produce a cyclic guanidine replacing TBD at a lower cost and more efficiently.

JP 2003-261315 A JP 2000-198775 A

Tetrahedron 2008, 64, 10097-10106 J. et al. Med. Chem. 2007, 50, 6307-6315 J. et al. Org. Chem. 2004, 69, 1571-1580

  Accordingly, an object of the present invention is to provide a cyclic guanidine having a carbon dioxide adsorption ability similar to TBD, so that it is a cyclic guanidine that is an alternative to TBD, and has excellent carbon dioxide adsorption / desorption ability and high yield. An object of the present invention is to provide a cyclic guanidine compound that can be produced inexpensively and a method for producing the same.

［式中、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子、−Ｙ−Ｚ、−Ｎ（Ｒ^１１）（Ｒ^１２）であり、
Ｙは、単結合、二重結合、若しくは三重結合、又は炭素数１〜２０のアルキル基であり（前記アルキル基は、主鎖又は側鎖の炭素原子の少なくとも１つが酸素原子、窒素原子、又は硫黄原子で置換されていることがあり、また、主鎖又は側鎖の水素原子の少なくとも１つがハロゲン原子、１〜３級アミノ基、水酸基、エーテル基、カルボニル基、チオカルボニル基で置換されていることがある）、
Ｚは、水素原子、水酸基、炭素数１〜１０のアルコキシ基、ビニル基、アリール基、ヘテロアリール基であり（前記アルコキシ基、アリール基、ヘテロアリール基は、それぞれ独立して、水素原子の少なくとも１つがハロゲン原子、１〜３級アミノ基、水酸基、エーテル基、カルボニル基、チオカルボニル基で置換されていることがある）、
Ｒ^１１及びＲ^１２は、それぞれ独立して、水素原子又はメチル基であり、
Ｒ^３〜Ｒ^９は、それぞれ独立して、水素原子、炭素数１〜２０のアルキル基であるか（前記アルキル基は、主鎖又は側鎖の炭素原子の少なくとも１つが酸素原子、窒素原子、又は硫黄原子で置換されていることがあり、また、主鎖又は側鎖の水素原子の少なくとも１つがハロゲン原子、１〜３級アミノ基、水酸基、エーテル基、カルボニル基、チオカルボニル基で置換されていることがある）、あるいは、隣接する基同士で環を形成することができ、
ｎは、０〜３の整数である］
で表される環状グアニジン化合物又はその誘導体からなることを特徴とする二酸化炭素吸着剤；
［２］前記一般式（１）において、Ｒ^２〜Ｒ^９が水素原子である、［１］の二酸化炭素吸着剤；
［３］前記環状グアニジン化合物が、
２−（１−ブチルアミノ）−４，５−ジヒドロ−１Ｈ−イミダゾール、
２−ベンジルアミノ−４，５−ジヒドロ−１Ｈ−イミダゾール、
２−（１−ブチルアミノ）−１，４，５，６−テトラヒドロピリミジン、
又はこれらの誘導体である、［１］又は［２］の二酸化炭素吸着剤；
［４］［１］〜［３］のいずれかの二酸化炭素吸着剤を、粒子もしくは繊維に担持させた担持物を含む二酸化炭素吸着シート；
［５］アルキルチオ環状アミジン塩又はその誘導体とアミノ化合物を、エーテル系の非プロトン性極性溶媒を主成分とする溶媒中で反応させることを特徴とする、環状グアニジン構造を骨格とする環状グアニジン化合物の製造方法；
［６］前記エーテル系の非プロトン性極性溶媒がテトラヒドロフランである、［５］の製造方法；
［７］前記アルキルチオ環状アミジン塩が、一般式（２）：

［式中、Ｒ^３〜Ｒ^９及びｎは、前記一般式（１）における定義と同じであり、
Ｒ^１０は、水素原子、−Ｙ−Ｚ、−Ｎ（Ｒ^１１）（Ｒ^１２）であり、
Ｙ、Ｚ、Ｒ^１１及びＲ^１２は、前記一般式（１）における定義と同じであり、
Ｘは、ハロゲン原子、ＨＣＯ_２、ＣＨ_３ＣＯ_２、ＣＨ_２ＣｌＣＯ_２、ＣＦ_３ＣＯ_２、ＡｒＣＯ_２、ＣＨ_３ＳＯ_３、ＣＦ_３ＳＯ_３、ＡｒＳＯ_３である］
で表される化合物であり、前記環状グアニジン化合物が、［１］に記載の一般式（１）で表される化合物又はその誘導体である、［５］又は［６］に記載の製造方法；
［８］前記一般式（１）及び（２）において、Ｒ^２〜Ｒ^９が水素原子であり、Ｘがヨウ素原子である、［７］の製造方法；
［９］前記アルキルチオ環状アミジン塩が、
２−（１−メチルチオ）−４，５−ジヒドロ−１Ｈ−イミダゾール−ヨウ化水素塩、又は
２−（１−メチルチオ）−１，４，５，６−テトラヒドロピリミジン−ヨウ化水素塩
であり、
前記環状グアニジン化合物が、
２−（１−ブチルアミノ）−４，５−ジヒドロ−１Ｈ−イミダゾール、
２−ベンジルアミノ−４，５−ジヒドロ−１Ｈ−イミダゾール、
２−（１−ブチルアミノ）−１，４，５，６−テトラヒドロピリミジン、
又はこれらの誘導体である、［５］〜［８］のいずれかの製造方法；
［１０］［１］〜［３］のいずれかの二酸化炭素吸着剤を用いて、二酸化炭素を含むガスから二酸化炭素を吸着させることを特徴とする、二酸化炭素の処理方法；
［１１］一般式（４）：

［式中、ｐは０又は１であり、
ｍは０〜３（小数である場合を含む）であり、
ｎ＝３−ｍである］
で表される化合物
に関する。 The present invention
[1] General formula (1):

Wherein R ¹ and R ² are each independently a hydrogen atom, —Y—Z, —N (R ¹¹ ) (R ¹² ),
Y is a single bond, a double bond, or a triple bond, or an alkyl group having 1 to 20 carbon atoms (in the alkyl group, at least one of main chain or side chain carbon atoms is an oxygen atom, a nitrogen atom, or It may be substituted with a sulfur atom, and at least one of hydrogen atoms in the main chain or side chain is substituted with a halogen atom, a primary to tertiary amino group, a hydroxyl group, an ether group, a carbonyl group, or a thiocarbonyl group. Sometimes)
Z is a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, a vinyl group, an aryl group, or a heteroaryl group (the alkoxy group, aryl group, and heteroaryl group are each independently at least a hydrogen atom) One may be substituted with a halogen atom, a primary to tertiary amino group, a hydroxyl group, an ether group, a carbonyl group, or a thiocarbonyl group),
R ¹¹ and R ¹² are each independently a hydrogen atom or a methyl group,
R ^{3 to} R ⁹ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (in the alkyl group, at least one of main chain or side chain carbon atoms is an oxygen atom, a nitrogen atom, Or at least one hydrogen atom in the main chain or side chain may be substituted with a halogen atom, a primary to tertiary amino group, a hydroxyl group, an ether group, a carbonyl group, or a thiocarbonyl group. Or adjacent groups can form a ring,
n is an integer of 0 to 3]
A carbon dioxide adsorbent comprising a cyclic guanidine compound represented by the formula:
[2] The carbon dioxide adsorbent according to [1], wherein in the general formula (1), R ^{2 to} R ⁹ are hydrogen atoms;
[3] The cyclic guanidine compound is
2- (1-butylamino) -4,5-dihydro-1H-imidazole,
2-benzylamino-4,5-dihydro-1H-imidazole,
2- (1-butylamino) -1,4,5,6-tetrahydropyrimidine,
Or a carbon dioxide adsorbent according to [1] or [2], which is a derivative thereof;
[4] A carbon dioxide adsorbing sheet comprising a support in which the carbon dioxide adsorbent according to any one of [1] to [3] is supported on particles or fibers;
[5] A cyclic guanidine compound having a cyclic guanidine structure as a skeleton, wherein an alkylthio cyclic amidine salt or a derivative thereof and an amino compound are reacted in a solvent mainly composed of an ether type aprotic polar solvent. Production method;
[6] The production method of [5], wherein the ether-based aprotic polar solvent is tetrahydrofuran;
[7] The alkylthio cyclic amidine salt has the general formula (2):

[Wherein R ^{3 to} R ⁹ and n are the same as defined in the general formula (1),
R ¹⁰ is a hydrogen atom, —Y—Z, —N (R ¹¹ ) (R ¹² ),
Y, Z, R ¹¹ and R ¹² are the same as defined in the general formula (1),
X is a halogen atom, HCO ₂ , CH ₃ CO ₂ , CH ₂ ClCO ₂ , CF ₃ CO ₂ , ArCO ₂ , CH ₃ SO ₃ , CF ₃ SO ₃ , ArSO ₃ ]
The production method according to [5] or [6], wherein the cyclic guanidine compound is a compound represented by the general formula (1) according to [1] or a derivative thereof;
[8] The production method of [7], wherein in the general formulas (1) and (2), R ^{2 to} R ⁹ are hydrogen atoms and X is an iodine atom;
[9] The alkylthio cyclic amidine salt is:
2- (1-methylthio) -4,5-dihydro-1H-imidazole-hydrogen iodide salt, or 2- (1-methylthio) -1,4,5,6-tetrahydropyrimidine-hydrogen iodide salt,
The cyclic guanidine compound is
2- (1-butylamino) -4,5-dihydro-1H-imidazole,
2-benzylamino-4,5-dihydro-1H-imidazole,
2- (1-butylamino) -1,4,5,6-tetrahydropyrimidine,
Or any one of these derivatives, the production method of any of [5] to [8];
[10] A method for treating carbon dioxide, comprising adsorbing carbon dioxide from a gas containing carbon dioxide using the carbon dioxide adsorbent according to any one of [1] to [3];
[11] General formula (4):

[Wherein p is 0 or 1;
m is 0 to 3 (including the case of a decimal),
n = 3-m]
It relates to the compound represented by these.

It has become possible to provide a cyclic guanidine compound that is excellent in carbon dioxide adsorption / desorption ability and can be produced at high yield and at low cost, and a method for producing the same.
Similar to TBD, it became possible to put to practical use a cyclic guanidine having carbon dioxide adsorption ability, and it became possible to produce a cyclic guanidine replacing TBD at a lower cost and more efficiently.
According to the method for producing a cyclic guanidine compound of the present invention, the synthesis of the cyclic guanidine compound is carried out by a reaction / purification operation because the reaction proceeds quantitatively under mild conditions using an inexpensive primary amine or secondary amine. It is easy and can supply a cyclic guanidine compound in large quantities at a low cost. The raw material, methylthio cyclic amidine, can also be easily synthesized from inexpensive primary amines, carbon disulfide, and methyl iodide. In addition, since cyclic guanidine having a reactive hydroxyl group or a polymerizable vinyl group can be easily synthesized, it can be polymerized advantageously for practical use in fields such as adsorption / desorption of carbon dioxide and supported by a chemical reaction on a carrier. It can be done easily.

It is a fragmentary sectional view showing typically one mode of a carbon dioxide adsorption sheet of the present invention.

  The carbon dioxide adsorbent of the present invention is a cyclic guanidine compound having a cyclic guanidine structure represented by the general formula (1) or a derivative thereof (hereinafter, a cyclic guanidine compound represented by the general formula (1)). And their derivatives are collectively referred to as a cyclic guanidine compound that can be used in the present invention, or simply referred to as a cyclic guanidine compound).

In the general formula (1), the alkyl group having 1 to 20 carbon atoms includes a linear or branched alkyl group, and includes not only an unsubstituted alkyl group but also a substituted alkyl group. As an example of the substituted alkyl group, for example, at least one of main chain or side chain carbon atoms may be substituted with a hetero atom (for example, an oxygen atom, a nitrogen atom, and / or a sulfur atom). Further, at least one of the hydrogen atoms in the main chain or side chain of the alkyl group may be substituted with a halogen atom, a primary to tertiary amino group, a hydroxyl group, an ether group, a carbonyl group, or a thiocarbonyl group. These substitutions may be any one substitution or two or more substitutions. The primary to tertiary amino groups mean residues obtained by removing one hydrogen atom from ammonia, primary amine, and secondary amine, respectively.
Moreover, in the said C1-C10 alkoxy group in the said General formula (1), an aryl group, and heteroaryl group, it can also be unsubstituted, and at least 1 of a hydrogen atom is a halogen atom, 1-3 primary amino. It may be substituted with a group, a hydroxyl group, an ether group, a carbonyl group, or a thiocarbonyl group.

In the general formula (1), with respect to R ^{3 to} R ⁹ , two or more adjacent groups can be combined to form a ring, for example, R ³ and R ⁴ are combined, alkylene group having 2 to 5 carbon atoms (e.g., _-CH 2 CH ₂ - or _-CH 2 _CH 2 CH ₂ -) a is can, but is not limited thereto.

In the general formula (1), for example,
R ¹ and R ² are each independently a hydrogen atom, i-propyl group, t-butyl group, t-amyl group, arylmethylene group, heteroarylmethylene group, and Y is a linear alkyl having 1 to 20 carbon atoms. a group, can Z is a hydrogen atom, a hydroxyl group, a methoxy group, a group represented by -Y-Z is a vinyl _{group, -NH 2, -N (CH 3} ) is _2,
R ^{3 to} R ⁹ can each independently be a hydrogen atom, an i-propyl group, a t-butyl group, a t-amyl group, or a linear alkyl group having 1 to 20 carbon atoms,
n may be an integer from 0 to 3.

In terms of the price of the production raw material and the carbon dioxide adsorption effect, in the cyclic guanidine compound represented by the general formula (1), R ^{2 to} R ⁹ are preferably low molecular weight groups, and R ² to R ⁹ is more preferably a hydrogen atom. N is preferably 0 or 1. R ¹ is preferably a linear alkyl group having 1 to 20 carbon atoms or an arylmethylene group.
As satisfying such conditions, the cyclic guanidine compound is
2- (1-butylamino) -4,5-dihydro-1H-imidazole,
2-benzylamino-4,5-dihydro-1H-imidazole,
2- (1-butylamino) -1,4,5,6-tetrahydropyrimidine,
Or it is preferable that it is a derivative | guide_body of these compounds.

で表される、新規物質である２−［３−（トリヒドロキシシリル）プロピルアミノ］−４，５−ジヒドロ−１Ｈ−イミダゾールを挙げることができる。 As a derivative derived from the cyclic guanidine compound represented by the general formula (1), for example, in a field such as adsorption / desorption of carbon dioxide, it is possible to use a polymer that is advantageous for practical use or to be supported by a chemical reaction on a carrier. Examples thereof include those in which a group having a reactive hydroxyl group or a polymerizable vinyl group is employed for R ^{1 to} R ⁹ .
For example, a silyl group can be introduced into the terminal group of R ¹ to form a cyclic guanidine derivative that can be supported on silica.
Examples of the cyclic guanidine derivative that can be supported on silica include, for example, the formula:

2- [3- (trihydroxysilyl) propylamino] -4,5-dihydro-1H-imidazole, which is a novel substance represented by

Specific examples of the cyclic guanidine compound represented by the general formula (1) include the following cyclic guanidine compounds (in the general formula (1), R ^{2 to} R ⁹ = H, n = 0 to 1). . These cyclic guanidine compounds are all compounds that can be obtained by the production method of the present invention, as will be described later in Examples.

These cyclic guanidine compounds have an excellent carbon dioxide adsorption effect.
For example, as described in the examples below,
2- (1-butylamino) -4,5-dihydro-1H-imidazole,
2-benzylamino-4,5-dihydro-1H-imidazole,
2- (1-butylamino) -1,4,5,6-tetrahydropyrimidine
When dissolved in dry acetonitrile and bubbling indoor air, carbonate crystals can be obtained, so that the carbon dioxide adsorption effect can be confirmed.
When these three kinds of cyclic guanidine compounds are compared, the five-membered ring guanidine compound having a butyl group has a better adsorption effect than the six-membered ring guanidine compound, and is preferably a five-membered ring guanidine compound.

The method for producing a cyclic guanidine compound having a cyclic guanidine structure of the present invention comprises reacting an alkylthiocyclic amidine salt or a derivative thereof with an amino compound in a solvent mainly composed of an ether-based aprotic polar solvent. Features.
Examples of the alkylthio cyclic amidine salt used in the production method of the present invention include compounds having a structure represented by the general formula (2) as a skeleton.
From the viewpoint of the price of the production raw material and the carbon dioxide adsorption effect, in the alkylthiocyclic amidine salt represented by the general formula (2), R ^{3 to} R ⁹ are preferably low molecular weight groups, and R ³ more preferably to R ⁹ is a hydrogen atom. N is preferably 0 or 1.

Although it does not specifically limit as said alkylthio cyclic amidine salt, A hydrogen halide salt is preferable and it is more preferable that it is a hydrogen iodide salt.
As satisfying these conditions,
The alkylthio cyclic amidine salt is
2- (1-methylthio) -4,5-dihydro-1H-imidazole-hydrogen iodide salt,
2- (1-methylthio) -1,4,5,6-tetrahydropyrimidine-hydrogen iodide salt,
Or it is preferable that it is a derivative | guide_body of these compounds.

Examples of the derivative of the alkylthio cyclic amidine salt include reaction with R ^{3 to} R ⁹ so that the polymer can be polymerized and supported by a chemical reaction, which is advantageous for practical use in the field of carbon dioxide adsorption / desorption. And those using a group having a polymerizable hydroxyl group or a polymerizable vinyl group.

As said amino compound used with the manufacturing method of this invention, general formula (3):
R ¹ —NH—R ² (3)
[Wherein, R ¹ and R ² are the same as defined in the general formula (1)]
The amino compound (a primary amine compound or a secondary amine compound) represented by these, or its derivative (s) can be mentioned.
As the amino compound represented by the general formula (3), a primary amine compound in which R ² is H is preferable because the yield of cyclic guanidine production and the carbon dioxide adsorption power of cyclic guanidine are large.
Further, as illustrated in the examples described later and below, it is also possible to produce a cyclic guanidine derivative that can be supported on silica by introducing a silyl group into the terminal group of R ¹ .

  In addition, the compound represented by the general formula (4) obtained in the production of the cyclic guanidine derivative having the silyl group introduced therein is a novel substance.

  In the production method of the present invention, it is necessary to react the alkylthio cyclic amidine salt or a derivative thereof with the amino compound in a solvent containing an ether-based aprotic polar solvent as a main component. By such a method, as shown in the below-mentioned Examples, it is possible to produce a cyclic guanidine compound or a derivative thereof at a lower cost and more efficiently than a conventional production method.

Examples of the ether-based aprotic polar solvent include dioxane and tetrahydrofuran, and it is particularly preferable to use THF (tetrahydrofuran). The reason is considered that the yield of the ether-based aprotic polar solvent is improved as compared with the protic polar solvent because a by-product due to a hydroxyl group is suppressed. Moreover, it is thought that this inhibitory effect is superior to DMF and CH ₂ Cl ₂ which are the same aprotic polar solvent.
The above-mentioned “solvent having an ether-based aprotic polar solvent as a main component” refers to a solvent in which an ether-based aprotic polar solvent is mixed with another solvent and an ether-based aprotic polar solvent. It means a solvent containing 50% or more by mass.

  If the solvent is an ether-based aprotic polar solvent, a highly efficient reaction is possible even under mild conditions. For example, it can be performed at 0 to 80 ° C, and preferably 25 to 60 ° C. More preferably, it is ° C.

The carbon dioxide treatment method of the present invention is characterized in that carbon dioxide is adsorbed from a gas containing carbon dioxide using the carbon dioxide adsorbent of the present invention.
Specifically, for example, the carbon dioxide adsorbent is first granular or liquid, particles or fibers (preferably porous particles or fibers), or air permeability such as a woven fabric, a knitted fabric, or a nonwoven fabric made of the fibers. A carrier supported on the sheet is formed. Next, a carbon dioxide adsorbing sheet made of a composite material obtained by combining these supported materials or these supported materials with other materials is formed. Next, these loaded materials and carbon dioxide adsorbing sheets are used as filters to arrange them in air conditioning equipment, adsorb carbon dioxide in the atmosphere, and desorb as necessary to adjust the carbon dioxide concentration in the indoor air. be able to.

As a method of combining a support in which the carbon dioxide adsorbent of the present invention is supported on porous particles and a breathable sheet-like material, for example, a solution in which the carbon dioxide adsorbent is diluted in a solvent is prepared, After spraying this solution on activated carbon particles and stirring, drying is performed at a relatively low temperature of 50 to 100 ° C. (preferably vacuum drying) to produce impregnated activated carbon particles.
Next, as illustrated in FIG. 1, after the impregnated activated carbon particles 3 are arranged on the surface of the hot melt nonwoven fabric 10, a resin aggregation portion 2 is formed at a portion where the hot melt nonwoven fabric and the impregnated activated carbon particles 3 are in contact with each other by heat treatment. And a first step of forming a web composed of the resin agglomerated portion 2 and the connecting portion 1 made of hot melt resin, and among the attached activated carbon particles, only the attached activated carbon particles fixed to the web are left. The second step of forming the laminated unit 4 and the hot-melt nonwoven fabric 10 ″ are laminated in contact with the impregnated activated carbon particles 3 of the laminated unit 4, and then the impregnated activated carbon particles 3 ′ are arranged on the surface of the hot-melt nonwoven fabric 10 ″. Then, there is a method of sequentially performing the first step and the second step.

  According to this method, after placing the impregnated activated carbon particles 3 on the surface of the hot melt nonwoven fabric 10, the hot melt resin is plasticized by heating the laminate in this state with dry heat or moist heat, and a part thereof The relatively thin fiber component constituting the hot melt nonwoven fabric that is the raw material is melted and cut to agglomerate at the contact portion with the impregnated activated carbon particles 3 to form the resin agglomerated portion 2 while leaving the fiber form. Will be configured. Instead of the hot melt nonwoven fabric 10, a carbon dioxide adsorbent is converted into porous particles (activated carbon particles) by using a sheet in which a hot melt nonwoven fabric is attached to a breathable sheet-like material 5 and 5 ′ such as a nonwoven fabric. A carbon dioxide adsorbing sheet 13 can be obtained in which a supported material (impregnated activated carbon particles) supported and a breathable sheet material (nonwoven fabric) are combined.

Examples of the particle carrier include metal oxide particles such as flaky silica, silica gel, and zeolite in addition to activated carbon. These metal oxide particles are preferably particles having a large specific surface area.
The scale-like silica particles are concretely shaped, for example, scale-like particles having a particle size of thin primary particles of 0.05 μm or less, and the thickness of the leaf-like silica particles is 0.05-0. A scaly silica particle having an average particle diameter of 5 μm (an average particle diameter of 0.1 to 1.5 μm) can be exemplified, and commercially available ones can be applied. For example, Sunlabry C (manufactured by AGC S-Tech Co., Ltd.) (average particle size: 4 to 6 μm, specific surface area 67 m ² / g, silanol group: 55 μmol /) is a white powder in which commercially available SiO ₂ primary particles are tertiary aggregated. m ² ) can be applied.

In the present invention, when the carbon dioxide adsorbent is supported on particles or fibers made of such a metal oxide, for example, a group having a reactive hydroxyl group or a polymerizable vinyl group is adopted as R ¹ , and preferably a silyl group Silyl group and metal oxide can be chemically bonded and supported. Further, the carbon dioxide adsorbing sheet can be constituted by further supporting the carbon dioxide adsorbing particles and carbon dioxide adsorbing fibers in which the cyclic guanidine compound is bonded to the metal oxide particles on the air-permeable sheet. it can.

The air-permeable sheet is not particularly limited as long as it has air permeability, and for example, a woven fabric, a knitted fabric, a non-woven fabric, or a porous membrane can be applied.
As the non-woven fabric, for example, a binder-bonded non-woven fabric, a hydroentangled non-woven fabric, a needle punched non-woven fabric, a fiber-bonded non-woven fabric, a spunbonded non-woven fabric, or a non-woven fabric that is appropriately combined can be applied.
The material of the nonwoven fabric is not particularly limited, and polyester fibers such as polyethylene terephthalate and polybutylene terephthalate, polyamide fibers such as nylon 6 and nylon 66, polyolefin fibers such as polypropylene and polyethylene, and acrylic fibers such as polyacrylonitrile. , Not only synthetic fibers such as polyvinyl alcohol fiber and synthetic pulp, but also semi-synthetic fibers such as rayon, natural fibers such as cotton and pulp fibers, or glass fibers, ceramic fibers, metal fibers, etc. can do.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but these do not limit the scope of the present invention.

１，３−プロパンジアミン３７．１ｇ（５００ｍｍｏｌ）に９５％エタノール９０ｍＬと水９０ｍＬを加え、氷浴０℃で攪拌を開始した。次いで二硫化炭素４５．７ｇ（≒３６．３ｍＬ，６００ｍｍｏｌ）のうち４ｍＬを１５分かけて滴下した。室温に戻したのち油浴６０℃で反応液を加温し、残りの二硫化炭素３２．３ｍＬを１．５時間かけて滴下した。次に油浴を１００℃に加温し２時間攪拌後、濃塩酸４．３ｍＬを加えて１００℃で１０時間攪拌した。その後空冷・氷浴で反応液を冷却し、析出した結晶を吸引濾過した。結晶をエーテル５０ｍＬ×２で洗浄後、６０℃で２４時間真空乾燥し無色針状結晶として５１．６ｇ（収率８９％）の目的物を得た。
^１Ｈ及び^１３Ｃ ＮＭＲ分析より、純粋な目的物であることを確認した（ＧＣ９９．９％）。 Example 1
(1) Synthesis of N, N′-trimethylenethiourea

To 37.1 g (500 mmol) of 1,3-propanediamine, 90 mL of 95% ethanol and 90 mL of water were added, and stirring was started at 0 ° C. in an ice bath. Next, 4 mL of 45.7 g (≈36.3 mL, 600 mmol) of carbon disulfide was dropped over 15 minutes. After returning to room temperature, the reaction solution was heated at 60 ° C. in an oil bath, and the remaining 32.3 mL of carbon disulfide was added dropwise over 1.5 hours. Next, the oil bath was heated to 100 ° C. and stirred for 2 hours, and then 4.3 mL of concentrated hydrochloric acid was added and stirred at 100 ° C. for 10 hours. Thereafter, the reaction solution was cooled in an air cooling / ice bath, and the precipitated crystals were filtered with suction. The crystals were washed with ether (50 mL × 2) and then vacuum-dried at 60 ° C. for 24 hours to obtain 51.6 g (yield 89%) of the desired product as colorless needle crystals.
^{From 1} H and ¹³ C NMR analysis, it was confirmed to be a pure target product (GC 99.9%).

エチレンチオウレア１０．２ｇ（１００ｍｍｏｌ）と乾燥エタノール１００ｍＬの懸濁液を室温で攪拌し、そこヘヨウ化メチル１７．０ｇ（１２０ｍｍｏｌ）を加えた。少しの発熱を伴い反応液が溶解し、その後再び固体が析出した。６時間後ＴＬＣチェック（ＳｉＯ_２；ＣＨＣｌ_３／ＭｅＯＨ＝３０：１）又はＧＣ（５０℃→２００℃，サンプルはＣＨ_２Ｃｌ_２／４０％ＮａＯＨ処理）により原料の消失を確認し、反応を停止した。溶媒留去後に残渣をエーテル５０ｍＬで洗浄し、４０℃で１２時間真空乾燥し無色粉末として２４．４ｇ（収率１００％）の目的物を得た。
^１Ｈ及び^１３Ｃ ＮＭＲ分析より、純粋な目的物であることを確認した（ＧＣ＞９９．９％，サンプルはＣＨ_２Ｃｌ_２／４０％ＮａＯＨ処理後のフリーアミジン）。 (2) Synthesis of 2- (1-methylthio) -4,5-dihydro-1H-imidazole-hydrogen iodide salt

A suspension of 10.2 g (100 mmol) of ethylenethiourea and 100 mL of dry ethanol was stirred at room temperature, and 17.0 g (120 mmol) of methyl iodide was added thereto. The reaction solution dissolved with a slight exotherm, and then a solid precipitated again. 6 hours later, TLC check (SiO ₂ ; CHCl ₃ / MeOH = 30: 1) or GC (50 ° C. → 200 ° C., sample treated with CH ₂ Cl ₂ /40% NaOH) confirmed the disappearance of raw materials and stopped the reaction did. After distilling off the solvent, the residue was washed with 50 mL of ether and dried in vacuo at 40 ° C. for 12 hours to obtain 24.4 g (yield 100%) of the desired product as a colorless powder.
^{From 1} H and ¹³ C NMR analysis, it was confirmed to be a pure target product (GC> 99.9%, sample was free amidine after treatment with CH ₂ Cl ₂ /40% NaOH).

トリメチレンチオウレア１１．６ｇ（１００ｍｍｏｌ）と乾燥エタノール１００ｍＬの懸濁液を室温で攪拌し、そこヘヨウ化メチル１７．０ｇ（１２０ｍｍｏｌ）を加えた。少しの発熱を伴い反応液が溶解し、その後再び固体が析出した。６時間後ＴＬＣチェック（ＳｉＯ_２；ＣＨＣｌ_３／ＭｅＯＨ＝３０：１）又はＧＣ（５０℃→２００℃，サンプルはＣＨ_２Ｃｌ_２／４０％ＮａＯＨ処理）により原料の消失を確認し、反応を停止した。溶媒留去後に残渣をエーテル５０ｍＬで洗浄し、４０℃で１２時間真空乾燥し無色粉末として２５．８ｇ（収率１００％）の目的物を得た。
^１Ｈ及び^１３Ｃ ＮＭＲ分析より、純粋な目的物であることを確認した（ＧＣ９９．５％，サンプルはＣＨ_２Ｃｌ_２／４０％ＮａＯＨ処理後のフリーアミジン）。 (3) Synthesis of 2- (1-methylthio) -1,4,5,6-tetrahydropyrimidine-hydrogen iodide salt

A suspension of 11.6 g (100 mmol) of trimethylenethiourea and 100 mL of dry ethanol was stirred at room temperature, and 17.0 g (120 mmol) of methyl iodide was added thereto. The reaction solution dissolved with a slight exotherm, and then a solid precipitated again. 6 hours later, TLC check (SiO ₂ ; CHCl ₃ / MeOH = 30: 1) or GC (50 ° C. → 200 ° C., sample treated with CH ₂ Cl ₂ /40% NaOH) confirmed the disappearance of raw materials and stopped the reaction did. After the solvent was distilled off, the residue was washed with 50 mL of ether and dried in vacuo at 40 ° C. for 12 hours to obtain 25.8 g (yield 100%) of the desired product as a colorless powder.
^{From 1} H and ¹³ C NMR analysis, it was confirmed to be a pure target product (GC 99.5%, sample was free amidine after treatment with CH ₂ Cl ₂ /40% NaOH).

各種アミン２２ｍｍｏｌに乾燥テトラヒドロフラン２０ｍＬを加え、そこに、各種メチルチオアミジンヨウ化水素酸２０ｍｍｏｌ、すなわち、前記実施例１（２）で合成した２−（１−メチルチオ）−４，５−ジヒドロ−１Ｈ−イミダゾール−ヨウ化水素塩２０ｍｍｏｌ、又は前記実施例１（３）で合成した２−（１−メチルチオ）−１，４，５，６−テトラヒドロピリミジン−ヨウ化水素塩２０ｍｍｏｌを加えて油浴４０℃にて加熱攪拌した。ＧＣ（サンプルはＣＨ_２Ｃｌ_２／４０％ＮａＯＨａｑ処理）でメチルチオアミジンの消失を確認後、溶媒を留去した。結晶又は油状物の残さをエーテルで洗浄し（殆どの油状物もここで結晶化が起こる）、真空乾燥後にＮＭＲ測定でほぼ純粋な環状グアニジンヨウ化水素塩（９９〜１００％）を得た。得られたヨウ化水素塩に４０％ＮａＯＨ水溶液２０ｍＬを加え、更にジクロロメタン４０ｍＬ（又はアセトニトリル４０ｍＬ）を加えて５分間激しく攪拌した。分液後に水層をジクロロメタン４０ｍＬ（又はアセトニトリル４０ｍＬ）で再度抽出し、合わせた有機層を無水硫酸ナトリウムで乾燥した。溶媒を留去後真空乾燥して環状グアニジン化合物９８〜１００％を得た。 Example 2
Synthesis of five-membered and six-membered guanidine compounds

20 mL of dry tetrahydrofuran was added to 22 mmol of various amines, and 20 mmol of methylthioamidine hydroiodic acid, that is, 2- (1-methylthio) -4,5-dihydro-1H— synthesized in Example 1 (2). Add 20 mmol of imidazole-hydrogen iodide or 20 mmol of 2- (1-methylthio) -1,4,5,6-tetrahydropyrimidine-hydrogen iodide synthesized in Example 1 (3) above and add 40 ° C. in an oil bath. And stirred with heating. After confirming the disappearance of methylthioamidine by GC (sample treated with CH ₂ Cl ₂ /40% NaOHaq), the solvent was distilled off. The crystalline or oily residue was washed with ether (most oils also crystallize here) to give a nearly pure cyclic guanidine hydroiodide salt (99-100%) by NMR measurement after vacuum drying. To the obtained hydrogen iodide salt, 20 mL of a 40% NaOH aqueous solution was added, and further 40 mL of dichloromethane (or 40 mL of acetonitrile) was added and vigorously stirred for 5 minutes. After separation, the aqueous layer was extracted again with 40 mL of dichloromethane (or 40 mL of acetonitrile), and the combined organic layer was dried over anhydrous sodium sulfate. After the solvent was distilled off, the residue was vacuum-dried to obtain 98 to 100% of a cyclic guanidine compound.

The structural formula of the synthesized cyclic guanidine compound is shown below. The compound in the frame is a novel cyclic guanidine compound. In addition, “time” described under each compound is the time when various amines and various methylthioamidine hydroiodic acids are reacted, and “percentage” is the yield of the cyclic guanidine compound.
In addition, about the 5-membered ring and 6-membered ring guanidine compound which have a hydroxyl group in the post-process of reaction, the hydrogen iodide was removed by Amberlist A-26 (OH) / MeOH.

<< Comparative Example 1 >>
Synthesis of 2- (1-butylamino) -1,4,5,6-tetrahydropyrimidine by a conventional method The synthesis of 2- (1-butylamino) -1,4,5,6-tetrahydropyrimidine described in Example 2 In synthesis (using 1-butylamine as raw material and 2- (1-methylthio) -1,4,5,6-tetrahydropyrimidine-hydrogen iodide synthesized in Example 1 (3)), tetrahydrofuran is protonated. A six-membered guanidine compound was synthesized in the same manner as in Example 2 except that the polar solvent was changed to methanol.
The obtained six-membered ring guanidine compound was unsuitable for practical use in terms of purity and yield.

本実施例における反応は、前記実施例１（３）で合成した２−（１−メチルチオ）−１，４，５，６−テトラヒドロピリミジン−ヨウ化水素塩２５８ｍｇ（１ｍｍｏｌ）、乾燥溶媒１ｍＬ、１−ブチルアミン１０９μＬ（１．１ｍｍｏｌ）及び基準物質としてクロロベンゼン５０μＬ（ＧＣ分析用内部標準）を試験管に加え、２５℃（又は４０℃）で実施した。反応液をＣＨ_２Ｃｌ_２／４０％ＮａＯＨ（５：１）で処理し、ＧＣでモニタリングした。
結果を表１に示す。表１において、「生成物収率（％）」及び「原料残存率（％）」は、ＧＣ分析による測定値から算出した値であり、「副生成物（％）」は、下記式：
１００（％）−〔生成物収率（％）＋原料残存率（％）〕
により算出した値である。 Example 3
Screening of reaction conditions in the synthesis of 2- (1-butylamino) -1,4,5,6-tetrahydropyrimidine near room temperature

In this example, the reaction was carried out using 258 mg (1 mmol) of 2- (1-methylthio) -1,4,5,6-tetrahydropyrimidine-hydrogen iodide synthesized in Example 1 (3), 1 mL of dry solvent, -109 μL (1.1 mmol) of butylamine and 50 μL of chlorobenzene (GC analysis internal standard) as a reference substance were added to a test tube and carried out at 25 ° C. (or 40 ° C.). The reaction was treated with CH ₂ Cl ₂ /40% NaOH (5: 1) and monitored with GC.
The results are shown in Table 1. In Table 1, “product yield (%)” and “raw material residual rate (%)” are values calculated from the measured values by GC analysis, and “byproduct (%)” is represented by the following formula:
100 (%)-[product yield (%) + raw material remaining rate (%)]
The value calculated by

When methanol was first used, the reaction proceeded even at room temperature (run 1). However, side reactions were more dominant, and it was thought that protic polar solvents were not suitable for guanidination of six-membered rings even at room temperature. In addition, side reactions were suppressed as the series increased even with a protic polar solvent (run1-4), but side reactions were generally suppressed when aprotic polar solvents were used, and THF was the most suitable solvent among them. (Run 11-14).
In addition, when methanol is used, the yield is very low. On the other hand, when an aprotic polar solvent is used, the yield is improved. In particular, when ether, THF, which is an aprotic polar solvent, is used, the yield is improved. Was found to be very high.

アミンとして３−アミノプロピルトリメトキシシランを使用したこと以外は、実施例２に記載のグアニジン化合物の合成と同様の方法で反応させた。但しＧＣ分析はできないため、^１Ｈ ＮＭＲより反応の終了を確認した。この結果、高い収率でグアニジル化が進行することが確認された。 Example 4
(1) Guanidylation of 3-aminopropyltrimethoxysilane

The reaction was conducted in the same manner as in the synthesis of the guanidine compound described in Example 2, except that 3-aminopropyltrimethoxysilane was used as the amine. However, since GC analysis cannot be performed, the completion of the reaction was confirmed by ¹ H NMR. As a result, it was confirmed that guanidylation proceeds with a high yield.

前記実施例４（１）で得られたグアニジンヨウ化水素塩３．６６ｇ（１０ｍｍｏｌ）をメタノール２０ｍＬに溶解し、そこヘアンバーライトＩＲＡ−４００（ＯＨ）１０ｇを加えて室温で１２時間攪拌した。反応終了後にアンバーライトをろ別し、更にメタノール４０ｍＬを用いて残さを十分に洗浄した。ろ液をエバポレートした後に得られた固体を６０℃で１２時間減圧乾燥することで、遊離（フリー体）のグアニジン化合物２．０２ｇ（収率９８．４％）を無色粉末ガラス状結晶として得た。
得られたグアニジン化合物は、粉末ガラス状結晶であり、担体に担持して使用することもでき、また担持させずにそのまま、二酸化炭素吸着剤として使用することもできる。 (2) Free guanidylation of hydrogen iodide salt Synthesis of 2- [3- (trihydroxysilyl) propylamino] -4,5-dihydro-1H-imidazole

3.66 g (10 mmol) of guanidine hydrogen iodide obtained in Example 4 (1) was dissolved in 20 mL of methanol, 10 g of Hemberlite IRA-400 (OH) was added thereto, and the mixture was stirred at room temperature for 12 hours. After completion of the reaction, amberlite was filtered off, and the residue was sufficiently washed with 40 mL of methanol. The solid obtained after evaporation of the filtrate was dried under reduced pressure at 60 ° C. for 12 hours to obtain 2.02 g (yield 98.4%) of a free (free form) guanidine compound as colorless powdery glassy crystals. .
The obtained guanidine compound is a powdery glassy crystal and can be used by being supported on a carrier, or can be used as it is as a carbon dioxide adsorbent without being supported.

実施例２で得られた各種グアニジン化合物（５ｍｍｏｌ）を乾燥アセトニトリル１０ｍＬに溶解し、室温で２時間ＣＯ_２（Ｈ_２Ｏ；５ｐｐｍ）を溶液にバブリング（２００ｍＬ／ｍｉｎ）した。析出した結晶をろ過し、更に乾燥アセトニトリル１０ｍＬで２回、乾燥エーテル１０ｍＬで２回洗浄した。合わせたろ液を溶媒留去し、原料を回収した。結晶はＣＯ_２（Ｈ_２Ｏ；５ｐｐｍ）気流（２００ｍＬ／ｍｉｎ）で１２時間乾燥し、以下に示すように、無色結晶の炭酸塩又は双性イオンを得た。
すなわち、
２−（１−ブチルアミノ）−１，４，５，６−テトラヒドロピリミジン（７７６ｍｇ）から無色結晶の炭酸塩（６８５ｍｇ）が得られ（収率６３．１％）、
２−（１−ブチルアミノ）−４，５−ジヒドロ−１Ｈ−イミダゾール（７０６ｍｇ）から無色結晶の炭酸塩（６３５ｍｇ）が得られ（収率８２．２％）、
２−ベンジルアミノ−４，５−ジヒドロ−１Ｈ−イミダゾール（７０６ｍｇ）から双性イオン（７００ｍｇ）が得られた（収率９９．２％）。
このように、五員環及び六員環グアニジン化合物に優れたＣＯ_２吸着性能があることが確認された。 Example 5
CO ₂ adsorption reaction of 5-membered and 6-membered guanidine compounds

Various guanidine compounds (5 mmol) obtained in Example 2 were dissolved in 10 mL of dry acetonitrile, and CO ₂ (H ₂ O; 5 ppm) was bubbled into the solution (200 mL / min) at room temperature for 2 hours. The precipitated crystals were filtered, and further washed twice with 10 mL of dry acetonitrile and twice with 10 mL of dry ether. The combined filtrates were evaporated to recover the raw materials. The crystals were dried in a CO ₂ (H ₂ O; 5 ppm) stream (200 mL / min) for 12 hours to obtain colorless crystalline carbonates or zwitterions as shown below.
That is,
Colorless crystalline carbonate (685 mg) was obtained from 2- (1-butylamino) -1,4,5,6-tetrahydropyrimidine (776 mg) (yield 63.1%)
Colorless crystalline carbonate (635 mg) was obtained from 2- (1-butylamino) -4,5-dihydro-1H-imidazole (706 mg) (yield 82.2%)
Zwitterion (700 mg) was obtained from 2-benzylamino-4,5-dihydro-1H-imidazole (706 mg) (yield 99.2%).
Thus, it was confirmed that the 5-membered and 6-membered guanidine compounds have excellent CO ₂ adsorption performance.

上記の五員環アミジン化合物、五員環チオアミジン化合物を用いて、実施例５と同様にして、ＣＯ_２吸着反応を行った。五員環グアニジン化合物の吸着性能が８２．２％であったのに対して（前記実施例５参照）、五員環アミジン化合物（４２１ｍｇ）からは無色結晶の炭酸塩３８７ｍｇ（５３．０％）を得た。五員環チオアミジン化合物（５８１ｍｇ）は無反応であった。 << Comparative Example 2 >>
CO ₂ adsorption reaction of 5-membered ring amidine compounds and 5-membered ring thioamidine compounds

Using the above five-membered ring amidine compound and five-membered ring thioamidine compound, a CO ₂ adsorption reaction was carried out in the same manner as in Example 5. The adsorption performance of the five-membered ring guanidine compound was 82.2% (see Example 5 above), whereas from the five-membered ring amidine compound (421 mg), 387 mg (53.0%) of colorless crystalline carbonate Got. The 5-membered thioamidine compound (581 mg) was unreacted.

As these results show, the effect of the guanidine group was very large on the five-membered ring amidine compounds which were generally poor in adsorption power. This is presumably because the increase in basicity due to the enamine structure of guanidine contributes to adsorption power and carbonate stability.
Thus, it was confirmed that the CO ₂ adsorption performance (53%) of the five-membered ring amidine compound is inferior to the adsorption performance (82.2%) of the five-membered ring guanidine compound.

Example 6
A solution was prepared by diluting 2-benzylamino-4,5-dihydro-1H-imidazole synthesized in Example 2 10 times with methanol.
Next, 20 g of the above solution is sprayed on 50 g of commercially available activated carbon particles “Kuraray Coal GW 32/60 mesh” [Kuraray Chemical Co., Ltd.], and after sufficient stirring, vacuum drying is performed at 60 ° C. for 8 hours. Then, the impregnated activated carbon particles carrying 3.8 mass% of the guanidine compound were obtained.
The thermoplastic polyamide resin (melt at 190 ° C. Index: 80) by melt spinning, after forming a focal hot melt nonwoven spider surface density 20 g / m ^2, immediately the surface density 20 g / m ² It was laminated on a polyester spunbonded nonwoven fabric [Marix 70020WSO manufactured by Unitika Ltd.]. As the hot melt nonwoven fabric was cooled, it adhered to each cover material, and as shown in FIG. 1, a support having a surface density of 40 g / m ² in which the hot melt nonwoven fabric 10 was adhered to the polyester spunbond nonwoven fabric 5 was obtained. .
Next, as illustrated in FIG. 1, the impregnated activated carbon particles 3 were dispersed on the surface of the hot melt nonwoven fabric 10 so that the surface density was 130 g / m ² . Subsequently, a steam treatment of about 5 kg / cm ² is performed from the cover material 5 side (hot melt nonwoven fabric 10 side) for about 7 seconds, the hot melt nonwoven fabric 10 is plasticized and melted, and the connecting portion 1 made of hot melt resin and the resin The impregnated activated carbon particles 3 were fixed to the web constituted by the agglomerated part 2 through the resin agglomerated part 2. Subsequently, by removing the adhering activated carbon particles other than the adhering activated carbon particles, the adhering activated carbon particles 3 are adhered in accordance with the respective particle diameters, and the first laminated unit 4 adhered to the polyester spunbond nonwoven fabric 5 is obtained. It was. Further, a hot melt nonwoven fabric 10 ″ having a surface density of 20 g / m ² is stacked on the stacked unit 4 in this state, and the impregnated activated carbon particles 3 ′ are dispersed, steamed, and fixed so as to have a surface density of 150 g / m ^2. After removal of the impregnated activated carbon particles, a second layer stack unit 4 ′ was formed.
Next, 5 ′ which is a support having a surface density of 40 g / m ² in which the hot-melt nonwoven fabric 10 is adhered to the polyester spunbond nonwoven fabric 5 similar to the above-described support is placed so that the hot-melt nonwoven fabric 10 ′ side contacts the laminated unit 4 ′. Is laminated on the laminate unit 4 ′, and steam treatment at about 5 kg / cm ² is performed for about 7 seconds from the cover material 5 ′ side (hot melt nonwoven fabric 10 ′ side) to plasticize and melt the hot melt nonwoven fabric 10 ′. The carbon dioxide adsorbing sheet 13 was obtained by fixing the impregnated activated carbon particles 3 ′ to the web composed of the connecting portion 1 ′ and the resin aggregating portion 2 ′ made of hot melt resin via the resin aggregating portion 2 ′. .
The thickness of the carbon dioxide adsorbing sheet is about 1 mm, the surface density is 380 g / ^{m 2,} the amount of supported guanidine compound-impregnated activated carbon is about 280 g / ^{m 2,} air velocity 10 cm / sec. The pressure loss at 12 was 12 Pa, which was a carbon dioxide adsorbing sheet suitable as a filter.

  The carbon dioxide adsorbent of the present invention can be applied to applications in which carbon dioxide is adsorbed from a gas containing carbon dioxide.

DESCRIPTION OF SYMBOLS 1 ... Connection part; 2, 2 ', 2 "... Resin aggregation part; 3, 3' ... Impregnated activated carbon particle;
4, 4 '... laminated unit; 5, 5' ... breathable sheet, spunbonded nonwoven fabric;
10, 10 ', 10 "... hot melt nonwoven fabric; 13 ... carbon dioxide adsorption sheet.

Claims (11)

General formula (1):

Wherein R ¹ and R ² are each independently a hydrogen atom, —Y—Z, —N (R ¹¹ ) (R ¹² ),
Y is a single bond, a double bond, or a triple bond, or an alkyl group having 1 to 20 carbon atoms (in the alkyl group, at least one of main chain or side chain carbon atoms is an oxygen atom, a nitrogen atom, or It may be substituted with a sulfur atom, and at least one of hydrogen atoms in the main chain or side chain is substituted with a halogen atom, a primary to tertiary amino group, a hydroxyl group, an ether group, a carbonyl group, or a thiocarbonyl group. Sometimes)
Z is a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, a vinyl group, an aryl group, or a heteroaryl group (the alkoxy group, aryl group, and heteroaryl group are each independently at least a hydrogen atom) One may be substituted with a halogen atom, a primary to tertiary amino group, a hydroxyl group, an ether group, a carbonyl group, or a thiocarbonyl group),
R ¹¹ and R ¹² are each independently a hydrogen atom or a methyl group,
R ^{3 to} R ⁹ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (in the alkyl group, at least one of main chain or side chain carbon atoms is an oxygen atom, a nitrogen atom, Or at least one hydrogen atom in the main chain or side chain may be substituted with a halogen atom, a primary to tertiary amino group, a hydroxyl group, an ether group, a carbonyl group, or a thiocarbonyl group. Or adjacent groups can form a ring,
n is an integer of 0 to 3]
A carbon dioxide adsorbent comprising a cyclic guanidine compound represented by the formula: The carbon dioxide adsorbent according to claim 1, wherein in the general formula (1), R ^{2 to} R ⁹ are hydrogen atoms. The cyclic guanidine compound is
2- (1-butylamino) -4,5-dihydro-1H-imidazole,
2-benzylamino-4,5-dihydro-1H-imidazole,
2- (1-butylamino) -1,4,5,6-tetrahydropyrimidine,
Or the carbon dioxide adsorption agent of Claim 1 or 2 which is these derivatives.   A carbon dioxide adsorbing sheet comprising a support in which the carbon dioxide adsorbent according to any one of claims 1 to 3 is supported on particles or fibers.   A process for producing a cyclic guanidine compound having a cyclic guanidine structure, which comprises reacting an alkylthio cyclic amidine salt or a derivative thereof with an amino compound in a solvent containing an ether-based aprotic polar solvent as a main component.   The production method according to claim 5, wherein the ether-based aprotic polar solvent is tetrahydrofuran. The alkylthio cyclic amidine salt has the general formula (2):

[Wherein R ^{3 to} R ⁹ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (in the alkyl group, at least one of main chain or side chain carbon atoms is an oxygen atom) May be substituted with a nitrogen atom or a sulfur atom, and at least one of the hydrogen atoms in the main chain or side chain is a halogen atom, a primary to tertiary amino group, a hydroxyl group, an ether group, a carbonyl group, a thiocarbonyl group May be substituted with a group), or adjacent groups may form a ring,
n is an integer of 0 to 3,
R ¹⁰ is a hydrogen atom, —Y—Z, —N (R ¹¹ ) (R ¹² ),
Y is a single bond, a double bond, or a triple bond, or an alkyl group having 1 to 20 carbon atoms (in the alkyl group, at least one of main chain or side chain carbon atoms is an oxygen atom, a nitrogen atom, or It may be substituted with a sulfur atom, and at least one of hydrogen atoms in the main chain or side chain is substituted with a halogen atom, a primary to tertiary amino group, a hydroxyl group, an ether group, a carbonyl group, or a thiocarbonyl group. Sometimes)
Z is a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, a vinyl group, an aryl group, or a heteroaryl group (the alkoxy group, aryl group, and heteroaryl group are each independently at least a hydrogen atom) One may be substituted with a halogen atom, a primary to tertiary amino group, a hydroxyl group, an ether group, a carbonyl group, or a thiocarbonyl group),
R ¹¹ and R ¹² are each independently a hydrogen atom or a methyl group,
X is a halogen atom, HCO ₂ , CH ₃ CO ₂ , CH ₂ ClCO ₂ , CF ₃ CO ₂ , ArCO ₂ , CH ₃ SO ₃ , CF ₃ SO ₃ , ArSO ₃ ]
The production method according to claim 5 or 6, wherein the cyclic guanidine compound is a compound represented by the general formula (1) according to claim 1 or a derivative thereof. In the said General formula (1) and (2), R < ² > -R < ⁹ > is a hydrogen atom, The manufacturing method of Claim 7 whose X is an iodine atom. The alkylthio cyclic amidine salt is
2- (1-methylthio) -4,5-dihydro-1H-imidazole-hydrogen iodide salt, or 2- (1-methylthio) -1,4,5,6-tetrahydropyrimidine-hydrogen iodide salt,
The cyclic guanidine compound is
2- (1-butylamino) -4,5-dihydro-1H-imidazole,
2-benzylamino-4,5-dihydro-1H-imidazole,
2- (1-butylamino) -1,4,5,6-tetrahydropyrimidine,
Or the manufacturing method as described in any one of Claims 4-8 which is these derivatives.   The carbon dioxide adsorption agent as described in any one of Claims 1-3 is made to adsorb | suck carbon dioxide from the gas containing carbon dioxide, The processing method of a carbon dioxide characterized by the above-mentioned. General formula (4):

[Wherein p is 0 or 1;
m is 0-3,
n = 3-m]
A compound represented by

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