WO2012133737A1

WO2012133737A1 - Crosslinkable amine compound, polymer membrane using crosslinkable amine compound, and method for producing polymer membrane

Info

Publication number: WO2012133737A1
Application number: PCT/JP2012/058521
Authority: WO
Inventors: 育雄谷口; 照彦甲斐; 淑紅段; 伸吾風間
Original assignee: 公益財団法人地球環境産業技術研究機構
Priority date: 2011-03-31
Filing date: 2012-03-30
Publication date: 2012-10-04

Abstract

Provided are: a novel crosslinkable amine compound for producing a polymer membrane for separating carbon dioxide from another gas with high selectivity; a polymer membrane using the compound; a method for producing the polymer membrane; and a gas separation method using the polymer membrane. This crosslinkable amine compound is characterized by having three or more acryloyl groups and/or methacryloyl groups in each molecule, said acryloyl groups and/or methacryloyl groups being respectively at the ends of branches.

Description

Crosslinkable amine compound, polymer film using the compound, and method for producing the same

The present invention relates to a novel crosslinkable amine compound, a polymer membrane for separating carbon dioxide from a mixed gas containing carbon dioxide using the compound, a method for producing the polymer membrane, and a gas using the polymer membrane It relates to a separation method.

Conventionally, since a polymer material has gas permeability unique to the material, it is known that a gas component can be separated by a film composed of the polymer material (see, for example, Non-Patent Document 1). . In particular, a gas component separation technique using a membrane has advantages such as low energy consumption, miniaturization of the apparatus, and easy maintenance of the apparatus, and is used in various fields.
In recent years, a technique for selectively separating carbon dioxide among techniques for separating a gas component by a membrane has been energetically studied. This technology can be used to separate and recover carbon dioxide from off-gas in oil fields, waste incineration, exhaust gas from thermal power generation, natural gas, and the like.

However, conventional polymer membranes and composite membranes have insufficient carbon dioxide selectivity (the membrane permeation rate of carbon dioxide / the membrane permeation rate of the separation target gas other than carbon dioxide), and carbon dioxide is recovered at a target concentration. I couldn't. Therefore, development of a separation membrane having excellent carbon dioxide selectivity has been desired.
In order to obtain such a membrane, it has been proposed to use a material having a high selective affinity for carbon dioxide. For example, a separation membrane in which a polyamidoamine dendrimer that is a liquid substance at room temperature is impregnated in a microporous support has been proposed (Non-patent Documents 2 and 3). When the separation performance of the impregnated membrane was measured using a method called a helium carrier method in which no pressure difference was provided in the membrane, excellent carbon dioxide selectivity exceeding 1000 was shown.
However, in a separation membrane in which a polyamidoamine dendrimer, which is a liquid substance, is impregnated in a microporous support, when the membrane is pressurized, the contained dendrimer causes phase separation between the polymer matrix and time, and the polymer matrix It is difficult to put it into practical use because the performance cannot be maintained.

Therefore, it has been desired to develop a polymer membrane and a composite membrane capable of immobilizing a substance having a strong and selective affinity for carbon dioxide such as a polyamidoamine dendrimer and applying a practical pressure difference.

Therefore, the present inventors have developed a polymer film disclosed in Patent Document 1, for example. On the other hand, in order to practically exhibit gas separation performance, it is necessary to increase the gas permeation rate, and in order to increase the permeation rate, it is necessary to reduce the film thickness. The polymer membrane of Patent Document 1 discloses a film thickness of about 500 μm or more. However, when a membrane of 250 μm or less is produced, phase separation occurs and the polyamidoamine dendrimer is easily detached from the polymer membrane. In addition, since the polymer film of Document 1 may be damaged under pressure, further improvement has been demanded for practical use.

JP 2009-185118 A

The present invention is a novel cross-linking for producing a polymer membrane capable of separating carbon dioxide from other gases with high selectivity at a pressure difference for practical use and causing no phase separation even when the film thickness is reduced. It is an object to provide a functional amine compound, a polymer membrane using the compound, a method for producing the polymer membrane, and a gas separation method using the polymer membrane.

As a result of intensive studies to solve the above problems, the present inventors have found that a novel crosslinking property having 3 or more branching ends in the molecule having a methacrylic group as a polymerizable functional group in the presence of a specific amine compound. By using an amine compound as a crosslinking agent and polymerizing a polyfunctional polymerizable monomer to obtain a high molecular weight polymer, it has high selectivity to carbon dioxide and can withstand a pressure difference (for example, 0.7 MPa It was found that a polymer membrane that is not damaged under pressure) and that can be put to practical use is obtained. Here, the term “crosslinkability” refers to having the ability to act as a crosslinking agent. The present invention has been completed by further studies based on this finding.

That is, the present invention relates to the following inventions.
[1] A crosslinkable amine compound having three or more acryl groups and / or methacryl groups in the molecule at the branch ends.
[2] The following formula (1)

(In the formula, A ¹ represents a divalent organic residue having 1 to 3 carbon atoms, and p represents an integer of 0 or 1.)
A group represented by formula (2):

(In the formula, A ² represents a divalent organic residue having 1 to 3 carbon atoms, and q represents an integer of 0 or 1.)
A group represented by formula (3):

(In the formula, A ³ and A ⁴ represent a divalent organic residue having 1 to 3 carbon atoms, and r and s represent an integer of 0 or 1.)
And a group represented by the following formula (4)

(In the formula, A ⁵ and A ⁶ represent a divalent organic residue having 1 to 3 carbon atoms, and t represents an integer of 0 or 1.)
Obtained by reacting an amine compound (A) having one or more groups selected from the group consisting of groups represented by the following groups with one or more compounds selected from the following groups (i) and (ii): The crosslinkable amine compound as described in [1] above.
(i) a compound obtained by reacting an acrylic ester and / or methacrylic ester with a haloformate;
(ii) an acrylic ester having at least one group selected from the group consisting of a hydroxyl group, a carboxylic acid group, a glycidyl group, an isocyanate group, an isocyanurate group, a carbodiimide group, an aldehyde group, an amino group, and an alkoxysilyl group; Or methacrylate.
[3] The crosslinkability according to [2], wherein the amine compound (A) has three or more groups selected from the group consisting of groups represented by the formulas (1) to (4). Amine compounds.
[4] The bridge according to [3], wherein the haloformate is a haloformate having an aromatic ring group which may have a substituent or a heterocyclic group which may have a substituent. Amine compounds.
[5] The bridge according to [4], wherein the haloformate having an aromatic ring group which may have a substituent is an aromatic chloroformate which may have a substituent. Amine compounds.
[6] In the above [5], the aromatic chloroformate which may have a substituent is 2,4,5-trichlorophenyl chloroformate or p-nitrophenyl chloroformate The crosslinkable amine compound as described.
[7] The crosslinkable amine compound is represented by the following formula (5):

A compound represented by the following formula (6):

A compound represented by the following formula (7):

A compound which is a polyamidoamine represented by the following formula (8):

A compound that is not a polyamidoamine represented by formula (9):

A compound which is not a polyamidoamine represented by the following formula (10):

A compound which is not a polyamidoamine represented by formula (11):

The crosslinkable amine compound according to the above [1], which is at least one compound selected from the group consisting of compounds other than the polyamidoamine represented by formula (1).
[8] In a polymer obtained by polymerizing a polyfunctional polymerizable monomer, which is crosslinked using the crosslinkable amine compound according to any one of [1] to [7] as a crosslinking agent. The following formula (1)

(In the formula, A ⁵ and A ⁶ represent a divalent organic residue having 1 to 3 carbon atoms, and t represents an integer of 0 or 1.)
A polymer film comprising an amine compound (B) having at least one group selected from the group consisting of groups represented by the formula:
[9] The polymer film according to [8], wherein the amine compound (B) has three or more groups selected from the group consisting of groups represented by the formulas (1) to (4). .
[10] The polymer film according to [8] or [9], wherein the amine compound (B) is a polyamidoamine-based dendrimer.
[11] The polyamidoamine-based dendrimer has the following formula

[10] The polymer film as described in [10] above, which is at least one kind of 0th generation dendrimer selected from the group consisting of 1st to 5th generation dendrimers corresponding thereto.
[12] The polyfunctional polymerizable monomer is one or more selected from the group consisting of polyfunctional (meth) acrylamide, polyfunctional (meth) acrylate, polyfunctional vinyl ether and divinylbenzene. [8] The polymer membrane according to any one of [11].
[13] The high function according to [12], wherein the polyfunctional (meth) acrylate is di (meth) acrylate, tri (meth) acrylate, tetra (meth) acrylate, or epoxyalkyl (meth) acrylate. Molecular film.
[14] Di (meth) acrylate is (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane di (meth) ) The polymer film as described in [13] above, which is at least one selected from the group consisting of acrylate and pentaerythritol di (meth) acrylate.
[15] Any one of the above [8] to [14], wherein the polymer is obtained by polymerizing a polyfunctional polymerizable monomer with a monofunctional polymerizable monomer added thereto. The polymer film described in 1.
[16] Monofunctional polymerizable monomer is monofunctional (meth) acrylamide, monofunctional (meth) acrylate, monofunctional vinyl ether, monofunctional N-vinyl compound, monofunctional vinyl compound and monofunctional α, β-unsaturated The polymer film as described in [15] above, which is at least one selected from the group consisting of compounds.
[17] Monofunctional (meth) acrylate is methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, methoxyethyl (meth) acrylate, Selected from the group consisting of methoxypolyethylene glycol (meth) acrylate, (meth) acrylic acid, N, N-dimethylaminoethyl (meth) acrylate, (poly) ethylene glycol (meth) acrylate and (poly) propylene glycol (meth) acrylate The polymer film as described in [16] above, wherein the polymer film is at least one kind.
[18] The polymer film according to [17], wherein the monofunctional polymerizable monomer is polyethylene glycol methacrylate, and the polyfunctional polymerizable monomer is polyethylene glycol dimethacrylate.
[19] The polymer membrane as described in any one of [8] to [18], wherein the polymer membrane is a gas separation membrane.
[20] The crosslinkable amine compound according to any one of [1] to [7] and the following formula (1)

(In the formula, A ⁵ and A ⁶ represent a divalent organic residue having 1 to 3 carbon atoms, and t represents an integer of 0 or 1.)
In the presence of an amine compound (B) having one or more groups selected from the group consisting of the groups represented by the above formula, the amine is introduced into the polymer produced by polymerizing a polyfunctional polymerizable monomer. A method for producing a polymer film, comprising a step of immobilizing the compound (B).
[21] Prior to the polymerization reaction, the following formula (1)

(In the formula, A ⁵ and A ⁶ represent a divalent organic residue having 1 to 3 carbon atoms, and t represents an integer of 0 or 1.)
A step of reacting an amine compound (A) having one or more groups selected from the group consisting of groups represented by formula (1) and one or more compounds selected from the group consisting of (i) and (ii) below: The manufacturing method according to [20] above, comprising:
(i) a crosslinking compound obtained by reacting an acrylic ester and / or methacrylic ester with a haloformate;
(ii) Acrylic acid ester having at least one group selected from the group consisting of hydroxyl group, carboxyl group, glycidyl group, isocyanate group, isocyanurate group, carbodiimide group, aldehyde group, amino group and alkoxysilyl group, and / or Methacrylic acid ester.
[22] The method for producing a polymer film according to [20] or [21], wherein the amine compound (B) is a polyamidoamine-based dendrimer.
[23] The polyamidoamine dendrimer is represented by the following formula:

The method for producing a polymer film as described in [22] above, which is at least one kind of 0th generation dendrimer selected from the group consisting of 1st to 5th generation dendrimers corresponding thereto.
[24] including a step of bringing a mixed gas containing carbon dioxide into contact with the polymer membrane according to any one of [8] to [19] to selectively permeate carbon dioxide in the mixed gas. A carbon dioxide separation method characterized by the above.
[25] Any one of the above [8] to [19], wherein the scattering vector has no peak at 0.6 nm ⁻¹ or more by X-ray small angle scattering using CuKα rays (wavelength 0.1542 nm) The polymer membrane described.

According to the present invention, a polymer membrane capable of separating carbon dioxide from other gases with high selectivity at a pressure difference for practical use and a method for producing the polymer membrane are provided. The present invention also provides a method for efficiently separating carbon dioxide from other gases using the polymer membrane.

In the polymer membrane using the crosslinkable amine compound of the present invention, the amine compound having carbon dioxide separation ability is not supported on the surface of the polymer membrane, but is immobilized in the polymer membrane, Even if the film is thinned, it does not cause phase separation and has a feature of excellent stability. By making the film thinner, the gas permeation rate can be increased and gas separation can be performed efficiently. Further, the polymer membrane obtained in the present invention does not cause phase separation even when pressure is applied, the amine compound (B) does not leak, and the membrane does not break down, and is stable for a long time. It can be used and is useful as a practical gas separation membrane.

It is the schematic of a gas separation apparatus. In the figure, GC means gas chromatography. It is the schematic of the structure of the conventional polymer film. In the figure, a circle indicates an amine compound. It is the schematic of the structure of the polymer film of this invention. In the figure, a circle indicates an amine compound. 6 is a scanning electron microscope image of Test Example 4. The left shows the comparative product 1 and the right shows the product 15 of the present invention. 10 is a fluorescence image of Test Example 5. The left shows the comparative product 8 and the right shows the product 16 of the present invention. 10 is a graph showing measurement results of X-ray small angle scattering in Test Example 6.

The crosslinkable amine compound of the present invention is characterized by having 3 or more acrylic groups and / or methacrylic groups in the molecule at the branch ends. The crosslinkable amine compound is not particularly limited as long as the effect of the present invention is not hindered.
Following formula (1)

(In the formula, A ³ and A ⁴ represent a divalent organic residue having 1 to 3 carbon atoms, and r and s represent an integer of 0 or 1.)
And a group represented by the following formula (4)
(In the formula, A ⁵ and A ⁶ represent a divalent organic residue having 1 to 3 carbon atoms, and t represents an integer of 0 or 1.)
Obtained by reacting an amine compound (A) having one or more groups selected from the group consisting of groups represented by the following groups with one or more compounds selected from the following groups (i) and (ii): The crosslinkable amine compound is preferred.
(i) a compound obtained by reacting an acrylic ester and / or methacrylic ester with a haloformate (hereinafter also referred to as compound (i));
(ii) Acrylic acid ester having at least one group selected from the group consisting of hydroxyl group, carboxyl group, glycidyl group, isocyanate group, isocyanurate group, carbodiimide group, aldehyde group, amino group and alkoxysilyl group, and / or Methacrylic acid ester (hereinafter also referred to as compound (ii)).

Specific examples of the crosslinkable amine compound include:
Following formula (5)

A compound represented by formula (6):

A compound represented by formula (7):

A compound represented by formula (8):

A compound represented by formula (9):

A compound represented by formula (10):

And a compound represented by the following formula (11)

Preferred examples include compounds represented by:

The crosslinkable amine compound of the present invention is a compound having 3 or more acrylic groups and / or methacryl groups in the molecule at the branch end. From the viewpoint of improving the crosslink density and preventing phase separation, an acrylic group is present at the branch end. A compound having 4 or more methacrylic groups in the molecule is more preferred. Further, the crosslinkable amine compound of the present invention may contain a metal atom, but it is preferable to exclude one containing a metal atom (particularly a trivalent or higher-valent metal atom).

By using the crosslinkable amine compound of the present invention, the amine compound (B) is immobilized in the polymer without causing phase separation. Therefore, when a polymer membrane of 100 μm or less is produced, the phase separation is performed. The cloudiness which shows is not produced. Moreover, since the crosslink density can be increased by using the crosslinkable amine compound, there is no possibility of breakage under high pressure, and a practical polymer membrane for gas separation can be obtained.

Hereinafter, the reaction of acrylic ester and / or methacrylic ester with haloformate will be described with respect to the compound (i). The ester used for the reaction with the haloformate is more preferably a methacrylic acid ester from the viewpoint that a stronger crosslinked structure can be obtained for the produced polymer film.

The acrylic ester is not particularly limited, and examples thereof include methyl acrylate, ethyl acrylate, (n- or i-) propyl acrylate, (n-, i-, sec- or t-) butyl acrylate, amyl acrylate, -Ethylhexyl acrylate, dodecyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 5-hydroxypentyl acrylate, cyclohexyl acrylate, allyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl Acrylate, methoxybenzyl acrylate, chlorobenzyl acrylate, 2- (p-hydroxyphenyl) ethyla Examples include relate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, chlorophenyl acrylate, sulfamoylphenyl acrylate, and the like. 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 5-hydroxypentyl acrylate and 2- (p- Acrylic acid esters having one or more hydroxy groups selected from hydroxyphenyl) ethyl acrylate are preferred. The acrylic ester may be used alone or in combination of two or more.

The methacrylic acid ester is not particularly limited. For example, methyl methacrylate, ethyl methacrylate, (n- or i-) propyl methacrylate, (n-, i-, sec- or t-) butyl methacrylate, amyl methacrylate, 2 -Ethylhexyl methacrylate, dodecyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 5-hydroxypentyl methacrylate, cyclohexyl methacrylate, allyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, methoxy Benzyl methacrylate, chlorobenzyl methacrylate, 2- (p-hydroxyl Nyl) ethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, chlorophenyl methacrylate, sulfamoyl phenyl methacrylate, and the like, such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 5-hydroxypentyl methacrylate and 2- A methacrylic acid ester having one or more hydroxy groups selected from (p-hydroxyphenyl) ethyl methacrylate is preferred. The methacrylic acid esters may be used alone or in combination of two or more.

The haloformate is not particularly limited, and examples thereof include a haloformate having an aromatic ring group which may have a substituent or a heterocyclic group which may have a substituent, and the like. Preferred are haloformates having an aromatic ring group. The haloformate group in the haloformate has the following formula: —OC (═O) X
(In the formula, X means Cl, Br or I.)
It is group shown by these. Although it does not specifically limit as a haloformate which has the aromatic ring group which may have the said substituent, The aromatic chloroformate which may have a substituent is preferable. The aromatic chloroformate which may have a substituent is not particularly limited, but a chloroformate having a phenyl group which may have a substituent is preferable, and 2,4,5-trichlorophenylchloro Formate (chloroformate 2,4,5-trichlorophenyl) or p-nitrophenyl chloroformate is particularly preferred. The substituent in the above-described compound is not particularly limited as long as the effect of the present invention is not hindered. For example, a nitro group, amino group, halogen atom (fluorine atom, chlorine atom, bromine atom or iodine atom), hydrocarbon group ( C1-10), halogenated hydrocarbon group (C1-10), cyano group, sulfo group, carboxyl group and the like. The amount of the haloformate used is usually about 1.0 to 5.0 moles, preferably about 1.2 to 2.0 moles per mole of acrylic acid ester and / or methacrylic acid ester.

The temperature of the reaction is not particularly limited, but is usually about 20 ° C to 60 ° C. The reaction time is not particularly limited, but is usually about 3 hours to 1 day. The reaction of the acrylic ester and / or methacrylic ester with haloformate is preferably carried out in the presence of a catalyst, and the catalyst used in the reaction is not particularly limited, but N, N-dimethyl-4-aminopyridine is used. (DMAP) or 4-pyrrolidinepyridine. The amount of the catalyst used is not particularly limited, but is preferably 1 × 10 ⁻⁸ to 1 × 10 ⁻³ equivalents per 1 mol of the acrylic ester and / or methacrylic ester of the raw material, and 1 × 10 ⁻⁷ to 5 × 10. ^-4 equivalents are more preferred. The solvent used in the reaction is not particularly limited, and examples thereof include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene. Can be mentioned. Any of these may be used alone or in combination of two or more at any ratio.

The compound (ii) has one or more groups selected from the group consisting of a hydroxyl group, a carboxylic acid group, a glycidyl group, an isocyanate group, an isocyanurate group, a carbodiimide group, an aldehyde group, an amino group, and an alkoxysilyl group. Although it is not particularly limited as long as it is an acrylic acid ester and / or a methacrylic acid ester, the reaction with the amine compound proceeds under mild conditions, and there is no reverse reaction in the reaction. Acrylic acid ester and / or methacrylic acid ester having a glycidyl group is preferable from the viewpoint of increasing affinity with a certain polyethylene glycol compound and the like. Specific examples of the crosslinking compound (ii) include dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, alkyl methacrylamide (for example, methacrylamide, dimethylmethacrylamide, N-isopropylmethacrylamide, n-butylmethacrylamide, tert-butyl methacrylamide and tert-octyl methacrylamide), 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth) acrylic acid, 3-butenoic acid, allyl isothiocyanate, isothiocyanate 3- Examples include buten-1-yl, allyl glycidyl ether, and glycidyl methacrylate, and glycidyl methacrylate is particularly preferable.

The reaction between the amine compound (A) and one or more compounds selected from the group consisting of the compounds (i) and (ii) will be described. The amount of the compounds (i) and (ii) to be used is not particularly limited, but is usually about 1.0 to 10 mol, preferably 1.2 to 2. mol per mol of the amine compound (A). About 0 mole. The temperature of the reaction is not particularly limited, but is usually about 20 ° C to 60 ° C. The reaction time is not particularly limited, but is usually about 3 hours to 1 day. Regarding the reaction between the amine compound (A) and one or more compounds selected from the group consisting of the compounds (i) and (ii), the solvent used in the reaction is not particularly limited. Examples include formamide, chloroform, dichloromethane, methylene chloride, ethyl acetate, dimethyl sulfoxide, dioxane, benzene, toluene, tetrahydrofuran, water, methanol, ethanol, isopropanol, etc., and these may be used alone or in combination of two or more. Good. Moreover, the said reaction may be performed in absence of a catalyst and may be performed in presence of a catalyst. The catalyst is not particularly limited. For example, a small amount (about 10 ⁻⁴ to 10 ⁻³ mol per 1 mol of the amine compound (A)) hydrochloric acid, an aqueous sodium hydroxide solution and DMAP (N, N-dimethyl- 4-aminopyridine) and the like. By the reaction, the cross-linking agent of the present invention can be obtained.

The amine compound (A) is an amine compound having one or more groups selected from the group consisting of the groups represented by the formulas (1) to (4). In the formulas (1) to (4), Examples of the divalent organic residue having 1 to 3 carbon atoms represented by A ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ⁶ include, for example, linear or branched C 1 to 3 carbon atoms. An alkylene group is mentioned. Specific examples of such alkylene _{_{_{_{groups, -CH 2 -, - CH 2}}}} -CH 2 -, - CH 2 -CH 2 -CH 2 -, - CH 2 -CH (CH 3) - , and the like, Of these, —CH ₂ — is particularly preferable. In the amine compound of the present invention, the number of the groups is not particularly limited as long as at least one group represented by the formulas (1) to (4) is contained, but preferably 2 to 4096 groups, More preferably, those having 3 to 128 groups are exemplified.

The polymer film of the present invention has the following formula (1) in a polymer obtained by polymerizing a polyfunctional polymerizable monomer that is crosslinked using the crosslinkable amine compound as a crosslinking agent.

(In the formula, A ⁵ and A ⁶ represent a divalent organic residue having 1 to 3 carbon atoms, and t represents an integer of 0 or 1.)
A polymer film characterized in that an amine compound (B) having one or more groups selected from the group consisting of the groups shown above is physically or chemically immobilized.

The amount of the crosslinkable amine compound used in the production of the polymer is not particularly limited as long as the effect of the present invention is not hindered, but is usually 5 to 95 wt% with respect to the polyfunctional polymerizable monomer. From the viewpoint of improving the durability of the resulting polymer film and the stability of the amine compound (B), it is preferably 10 to 80 wt%, more preferably 15 to 50 wt%.

In the amine compound (B), the weight fraction occupied by one or more groups selected from the group consisting of the groups represented by the formulas (1) to (4) is not particularly limited, but carbon dioxide and hydrogen From the viewpoint of improving the separation ability of the amine compound, it is preferable that the weight fraction of one or more groups selected from the group consisting of groups represented by formulas (1) to (4) in the amine compound is 5% or more. More preferred is 10 to 94%, and further preferred is 15 to 53%.

In the amine compound (B), examples of the skeleton to which one or more groups selected from the group consisting of groups represented by formulas (1) to (4) are bonded include the following.

[Wherein n represents an integer of 0 to 10. ]

That is, in the amine compound (B), one or more groups selected from the group consisting of groups represented by the formulas (1) to (4) are present in a part or all of the rice-marked binders in the above formula, A bond which is bonded directly or via an alkylene group and is not bonded with one or more groups selected from the group consisting of the groups represented by formulas (1) to (4) includes a hydrogen atom, an alkyl group, amino A compound in which an alkyl group, a hydroxyalkyl group or the like is bonded.

Examples of the amine compound (B) include 0th generation polyamidoamine dendrimers represented by the following formula, and 1st generation or more corresponding to these 0 th generation polyamidoamine dendrimers.

Among the polyamidoamine dendrimers, examples of particularly suitable compounds include the following polyamidoamine dendrimers.

The polyamidoamine-based dendrimers used in the present invention include those having all equal branch lengths and those having at least one of them substituted with a hydroxyalkyl group or an alkyl group and having different branch lengths. As the polyamidoamine dendrimer, various polyamidoamine dendrimers having different numbers of surface groups [namely, groups represented by the formula (1), (2), (3) or (4)] can be used. . The relationship between the number of surface groups and the generation of the polyamidoamine-based dendrimer is as follows. If the number of the 0th generation surface groups is a (a represents an integer of 3 or more), the b generation (b represents an integer). The number c of surface groups is as follows.

In the present invention, commercially available products (for example, 0th to 10th generation PAMAM dendrimers manufactured by Aldrich) can be used, and in particular, 0th to 5th generation polyamidoamine dendrimers can be preferably used. Table 1 below shows the number of surface groups for each generation when the number of surface groups of the 0th generation is four. As the polyamidoamine dendrimer, the first generation or higher is preferable from the viewpoint of increasing the crosslink density of the obtained polymer film. In order to further improve the crosslink density of the obtained polymer film, the second generation or higher is particularly preferable. preferable.

The amine compound having a group represented by the formula (1) can be produced according to a known organic synthesis method. As an example of the method for synthesizing the amine compound, a method of reacting a mother nucleus compound having a methyl ester group with an amine compound represented by the following formula (1a) is exemplified. According to this method, the methyl ester group of a compound having a methyl ester group is converted to a group represented by the formula (1a), and an amine compound having a group represented by the formula (1) can be produced. The following formula is a formula in which a methyl ester group is converted into a group represented by formula (1) in the synthesis method.

(In the formula, A ¹ and p have the same meaning as described above.)

The reaction between the compound having a methyl ester group and the amine compound represented by the formula (1a) is usually carried out by adding 3 to 20 mol of the amine compound represented by the formula (1a) with respect to 1 mol of the compound having a methyl ester group. , Preferably 5 to 10 moles. The reaction between the compound having a methyl ester group and the amine compound represented by the formula (1a) is usually carried out in a suitable solvent. As the solvent, known solvents can be widely used as long as they do not inhibit the reaction. Examples of such a solvent include methanol, ethanol, 2-propanol, tetrahydrofuran, 1,4-dioxane and the like. These solvents do not prevent water from being contained. The reaction between the compound having a methyl ester group and the amine compound represented by (1a) is usually continued at 0 to 40 ° C., preferably 20 to 30 ° C., for 90 to 180 hours, preferably 160 to 170 hours. Is done. As the compound having a methyl ester group used as a raw material and the amine compound represented by the formula (1a), compounds of known compounds can be used. The reaction mixture obtained by the above reaction is cooled, for example, and then subjected to an isolation operation such as filtration, concentration, extraction, etc. to separate the crude reaction product, and if necessary, column chromatography, recrystallization, etc. The amine compound having a group represented by the formula (1) can be isolated and purified by performing a normal purification operation.

The amine compound having a group represented by the formula (2) is obtained by reacting, for example, a mother nucleus compound having an amino group and an amine compound having a methyl ester group at the terminal represented by the following formula (2a) in the same manner as described above. Can be manufactured.

(In the formula, A ² and q have the same meaning as described above.)

The amine compound having a group represented by the formula (3) is, for example, a mother nucleus compound having an alkenyl group at the terminal represented by the following formula (3a) and a diamine compound represented by the following formula (3b) in the same manner as described above. It can be produced by reacting.

(In the formula, A ³ , A ⁴ , r and s have the same meaning as described above.)

The amine compound having a group represented by the formula (4), for example, reacts a mother nucleus compound having a carbonyl group represented by the following formula (4a) and a diamine compound represented by the following formula (4b) in the same manner as described above. Can be manufactured.

(In the formula, A ⁵ , A ⁶ and t have the same meaning as described above, and A ⁷ represents an organic residue.)
Preferable examples of the organic residue having 1 to 3 carbon atoms represented by A ⁷ include a linear or branched alkyl group having 1 to 3 carbon atoms (methyl group, ethyl group, propyl group). .

The polyfunctional polymerizable monomer used in the present invention is not particularly limited as long as it is a polymerizable compound having two or more carbon-carbon unsaturated bonds. Examples thereof include polyfunctional acrylic monomers such as polyfunctional (meth) acrylamide and polyfunctional (meth) acrylate, and polyfunctional vinyl monomers such as polyfunctional vinyl ether or divinylbenzene. These polyfunctional polymerizable monomers can be used alone or in combination of two or more.

Examples of the polyfunctional (meth) acrylamides include N, N ′-(1,2-dihydroxyethylene) bisacrylamide, ethidium bromide-N, N′-bisacrylamide, and ethidium. Examples include bromide-N, N′-bismethacrylamide, N, N′-ethylenebisacrylamide, N, N′-methylenebisacrylamide, and the like.
Examples of the polyfunctional (meth) acrylates include di (meth) acrylates, tri (meth) acrylates, and tetra (meth) acrylates.

Examples of the di (meth) acrylates include (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane di (meth) And alkylene glycol di (meth) acrylates such as acrylate and pentaerythritol di (meth) acrylate.

Examples of the tri (meth) acrylates include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, and the like. .

Examples of the tetra (meth) acrylates include ditrimethylolpropane tetra (meth) acrylate and pentaerythritol tetra (meth) acrylate.
Examples of the polyfunctional vinyl ethers include trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, and the like.

Further, if necessary, the polymerization reaction may be carried out by using the polyfunctional polymerizable monomer and the monofunctional polymerizable monomer in combination. By using in combination, the size of the network in the polymer can be adjusted.

Monofunctional polymerizable monomers include monofunctional acrylic monomers such as monofunctional (meth) acrylamides and monofunctional (meth) acrylates, monofunctional vinyl ethers, monofunctional N-vinyl compounds or monofunctional vinyl compounds. And monofunctional vinyl monomers and monofunctional α, β-unsaturated compounds.

Examples of the monofunctional (meth) acrylamide include 2-acetamidoacrylic acid, (meth) acrylamide, 2-acrylamide-2-methylpropanesulfonic acid, N- (butoxymethyl) acrylamide, N-tert-butylacrylamide, and diacetone acrylamide. N, N-dimethylacrylamide, N- [3- (dimethylamino) propyl] methacrylamide, and the like.

Examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, methoxyethyl (meth) acrylate, methoxy Examples include polyethylene glycol (meth) acrylate, (meth) acrylic acid, N, N-dimethylaminoethyl (meth) acrylate, (poly) ethylene glycol methacrylate, and polypropylene glycol (meth) acrylate.
Examples of the monofunctional vinyl ethers include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, and methoxypolyethylene glycol vinyl ether.

Examples of the monofunctional N-vinyl compounds include N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinylacetamide and the like.
Examples of the monofunctional vinyl compounds include styrene, α-methylstyrene, vinyl acetate and the like.

Examples of the monofunctional α, β-unsaturated compounds include maleic anhydride, maleic acid, dimethyl maleate, diethyl maleate, fumaric acid, dimethyl fumarate, diethyl fumarate, monomethyl fumarate, monoethyl fumarate, and itaconic anhydride. Examples thereof include acid, itaconic acid, dimethyl itaconate, methylene malonic acid, dimethyl methylene malonate, cinnamic acid, methyl cinnamate, crotonic acid, and methyl crotonic acid.

The amount of the amine compound (B) having one or more groups selected from the group consisting of the groups represented by the formulas (1) to (4) immobilized in the polymer is determined by the polymer 100 The amount is usually about 2 to 400 parts by weight, preferably about 25 to 250 parts by weight, more preferably about 40 to 100 parts by weight from the viewpoint of obtaining sufficient gas separation performance.

The thickness of the polymer membrane of the present invention is not particularly limited as long as the effects of the present invention are not hindered, but is usually about 1000 μm or less from the viewpoints of high gas permeation rate and preferable performance of gas separation. About 600 μm or less, more preferably about 250 μm or less, and even more preferably about 100 μm or less. The lower limit of the film thickness is not particularly limited as long as gas separation can be effectively performed, but is preferably about 5 μm or more, and more preferably about 10 μm or more from the viewpoint of durability. In particular, the film thickness when used as a self-supporting film having no support is not particularly limited as long as the effects of the present invention are not hindered. More preferably, it is about 100 μm or more and 250 μm or less. The film thickness when used as a composite film having a support is not particularly limited as long as the effects of the present invention are not hindered, but is preferably about 5 μm or more and 150 μm or less from the viewpoint of the strength of the film and the gas permeation rate, More preferably, it is about 10 μm or more and 100 μm or less.

Further, the gas permeation rate when using the polymer membrane of the present invention is not particularly limited as long as the effect of the present invention is not hindered, but is about 1 × 10 ⁻¹³ m ³ from the viewpoint of gas separation efficiency. (STP) / (m ² Spa) or more is preferable, and about 1 × 10 ⁻¹² m ³ (STP) / (m ² Spa) or more is more preferable. The pressure applied to the membrane when using the polymer membrane of the present invention is preferably about 0.1 MPa or more, more preferably about 1 to 4 MPa.

Since the polymer membrane of the present invention is self-supporting, a support is not essential, but a support may be provided as necessary. As the support, a porous support membrane is preferably used from the viewpoint of gas separation. The thickness of the porous support membrane is not particularly limited as long as the effect of the present invention is not hindered, but is preferably about 50 μm to 1000 μm, more preferably about 100 μm to 500 μm from the viewpoint of strength and gas permeation rate. The porous support membrane and the polymer membrane integrally formed can be used as a gas separation composite membrane. In the present invention, the composite membrane refers to one in which a polymer membrane having gas separation ability and a porous support membrane are integrally formed. The porous support membrane used in the present invention can be produced using, for example, a polymer described later, and ceramics, polyethylene phthalate (PET) film, and the like can also be used. Specifically, when producing using a polymer, the polymer is dissolved in a solvent to obtain a raw material solution, and then the raw material solution is brought into contact with a coagulation liquid (a mixed solution of a solvent and a non-solvent). A porous support membrane can be produced by a method of inducing phase separation by increasing the solvent concentration (non-solvent induced phase separation method; NIPS method, see Japanese Patent Publication No. 1-2003). Examples of the ceramic include alumina, zirconia, titania, and silica.

Examples of the polymer used for the production of the porous support membrane include polyethersulfone (PES), polysulfone (PSF), polyphenylenesulfone, triacetylcellulose, cellulose acetate, carbon, polyacrylonitrile, polyvinylidene fluoride, aromatic nylon, and polyethylene. Examples thereof include phthalate (PET), polyethylene naphthalate, polyarylate, polyimide, polyether, cellophane, aromatic polyamide, polyethylene, and polypropylene. Examples of the solvent include N-methylpyrrolidone (NMP), acetone, dimethylformamide and the like. There is no particular limitation as long as the solvent dissolves in the coagulation liquid during coagulation. Examples of the non-solvent include water, monohydric alcohol, polyhydric alcohol, ethylene glycol, and tetraethylene glycol. In preparing the raw material solution, it is preferable to add a swelling agent to increase the number of through-holes in the support film after solidification and improve gas permeability. As the swelling agent, for example, one or a mixture of two or more selected from polyethylene glycol, polyvinyl pyrrolidone, hydroxypropyl cellulose, sodium chloride, lithium chloride, and magnesium bromide can be used. Among these swelling agents, polyethylene glycol is preferable, and polyethylene glycol having a weight average molecular weight of 400 to 800 is particularly preferable. The concentration of the raw material solution and the coagulation liquid is not particularly limited as long as the concentration is such that the raw material solution and the coagulation liquid are brought into contact with each other and a porous support membrane can be obtained by a non-solvent induced phase separation method. When polyethersulfone (PES) is used, the raw material solution is preferably a 20 to 35 wt% PES solution in view of film forming properties.

The method for contacting the raw material solution with the coagulating liquid is not particularly limited, and examples thereof include a method of immersing the raw material solution in the coagulating liquid. The concentration of the solvent in the coagulation liquid is not particularly limited, but by changing the solvent concentration in the coagulation liquid in the coagulation of the raw material solution, the structure of the support film can be changed and the pressure resistance can be increased. The pore diameter of the pores of the porous support membrane is preferably 100 nm or less, more preferably 10 nm or less. The thickness of the porous support membrane is not particularly limited as long as the gas permeability of the polymer membrane does not become larger than the gas permeability of the porous support membrane.

Below, the manufacturing method of the polymer film of this invention is demonstrated.
As a first aspect of the method for producing a polymer film of the present invention,
[I] A crosslinkable amine compound having 3 or more branched ends having an acrylic group and / or methacrylic group as a polymerizable functional group, and the following formula (1)

(In the formula, A ⁵ and A ⁶ represent a divalent organic residue having 1 to 3 carbon atoms, and t represents an integer of 0 or 1.)
In the presence of an amine compound (B) having one or more groups selected from the group consisting of the groups represented by the above formula, the amine is introduced into the polymer produced by polymerizing a polyfunctional polymerizable monomer. Examples include a method including a step of immobilizing the compound (B) to form a polymer film (step [I]). Moreover, the process (process [II]) which laminates | stacks the obtained polymer film on a porous support film may be provided as needed.

<Process [I]>
This step is a polyfunctional polymerizable compound in the presence of the crosslinkable amine compound having three or more branched ends with the acrylic group and / or methacrylic group as the polymerizable functional group in the molecule, and the amine compound (B). This is a step of forming a polymer film by immobilizing the amine compound in the polymer polymer produced by polymerizing the monomer. The polymerization reaction is not particularly limited as long as the effects of the present invention are not hindered. For example, the polymerization reaction may be thermal polymerization or photopolymerization. In this case, a polymerization initiator is usually used (heat or light).

As the thermal polymerization initiator, known ones can be used. Specifically, methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxide Organic peroxides such as octoate, t-butylperoxybenzoate, and lauroyl peroxide; azo compounds such as azobisisobutyronitrile are suitable. In addition, a curing accelerator may be used by mixing at the time of thermal polymerization, and as the curing accelerator, cobalt naphthenate, cobalt octylate, etc., or tertiary amine is suitable. The addition amount of the thermal polymerization initiator is preferably about 0.01 to 10 parts by weight with respect to 100 parts by weight of the polyfunctional polymerizable monomer. More preferably, it is about 0.1 to 1 part by weight.

As the photopolymerization initiator, known ones can be used, and specifically, the following compounds are suitable. These are used alone or as a mixture of two or more.
Benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4- (1 -T-butyldioxy-1-methylethyl) acetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one and 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -butanone-1, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2 -Professional Le) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] acetophenone such as propanone oligomer.

Anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3,4-dimethyl-9H-thioxanthone Thioxanthones such as -9-one mesochloride; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzoph Non, 3,3 ', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxylcarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyl) Benzophenones such as (oxy) ethyl] benzenemethananium bromide and (4-benzoylbenzyl) trimethylammonium chloride; acylphosphine oxides and xanthones.

Benzyldimethyl ketal (BDK) (eg, 2,2-dimethoxy-1,2-diphenylethane-1-one), α-hydroxyalkylphenone (eg, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2 -Methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one), α-aminoalkylphenone (eg, 2-methyl-1- (4 -Methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinofe Nyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone) Initiators; acyl phosphine oxide photopolymerization initiators such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; bis (η5- Titanocene photopolymerization initiators such as 2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium; oxime esters (for example, 1 2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethi -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime)), oxyphenylacetic acid ester (for example, oxyphenylacetic acid, 2- [2-oxo-2- Other photopolymerization initiators such as phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid, 2- (2-hydroxyethoxy) ethyl ester).

The addition amount of the photopolymerization initiator is preferably about 0.5 to 10 parts by weight with respect to 100 parts by weight of the polyfunctional polymerizable monomer. More preferably, it is about 2 to 3 parts by weight.

When the polyfunctional polymerizable monomer used in the present invention is cured by light, a basic compound can be used as a sensitizer together with a photopolymerization initiator. As the basic compound, an amine compound is preferably used, and the amine compound is not particularly limited. Specifically, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dimethylpropyl are used. Examples include amine, monoethanolamine, diethanolamine, ethylenediamine, diethylenetriamine, dimethylaminoethyl methacrylate, and polyethyleneimine. Of these, tertiary amine compounds are particularly preferred.

Examples of the tertiary amine compound include triethanolamine, triisopropanolamine, tributanolamine, methyldiethanolamine, methyldiisopropanolamine, methyldibutanolamine, ethyldiethanolamine, ethyldiisopropanolamine, ethyldibutanolamine, propyldiethanolamine, propyl Diisopropanolamine, propyldibutanolamine, dimethylethanolamine, dimethylisopropanolamine, dimethylbutanolamine, diethylethanolamine, diethylisopropanolamine, diethylbutanolamine, dipropylethanolamine, dipropylisopropanolamine, dipropylbutanolamine, dibutylethanol Amine, dibutylisopropano Triethanolamine, dibutyl butanolamine, methyl ethyl ethanolamine, methyl ethyl isopropanolamine, methyl ethyl butanol amine, benzyl diethanolamine, N- phenyl-diethanolamine, tetraethanol ethylenediamine, tetramethylenediamine propanol ethylenediamine, and the like. These hydroxyl group-containing tertiary amine compounds are added with ethylene oxide to introduce a polyethylene glycol chain, and the hydroxyl group-containing tertiary amine compound is added with a monomer containing a functional group reactive with a hydroxyl group to obtain a polymerizable group. What introduced the heavy bond, what introduce | transduced the tertiary amino group to the polymer or the oligomer, etc. can also be used. These amine compounds can be used alone or in combination of two or more.

The amount of the sensitizer used is preferably about 1 to 10 parts by weight with respect to 100 parts by weight of the photopolymerization initiator. More preferably, it is about 5 to 8 parts by weight.

The polymerization reaction is preferably carried out in a suitable solvent by heating in the case of thermal polymerization and by irradiation with ultraviolet rays in the case of photopolymerization. The solvent is not particularly limited as long as it dissolves the amine compound and the polyfunctional polymerizable monomer, but usually an alcohol (for example, methanol, ethanol, etc.) can be preferably used. Heating in the thermal polymerization is usually performed at about 40 to 90 ° C., preferably about 60 to 70 ° C., usually about 2 to 24 hours, preferably about 5 to 10 hours. The ultraviolet irradiation of the photopolymerization is usually performed for about 30 seconds to 10 minutes, preferably about 1 to 3 minutes, using a wavelength of about 200 to 400 nm, preferably about 250 to 360 nm. In addition, thermal polymerization and photopolymerization can be performed in combination. For example, photopolymerization can be performed after thermal polymerization, thermal polymerization can be performed after photopolymerization, or photopolymerization and thermal polymerization can be performed simultaneously. .

Thus, a polymer film is obtained in which the amine compound (B) is physically or chemically immobilized in the polymer at the same time as the polymer is produced. Suitable examples of the obtained polymer film include those in which the amine compound (B) is sealed and fixed in the network structure of the polymer having the three-dimensional network structure. When the high molecular polymer has a cross-linked structure of the cross-linkable amine compound, a high polymer film having excellent strength and gas separation property can be obtained. By using the crosslinkable amine compound, the amine compound (B) having carbon dioxide gas separation performance does not phase-separate even if the film thickness is reduced, the membrane is subjected to high pressure, etc. A gas separation membrane that is preferable in this respect is obtained. The presence / absence of phase separation can be confirmed, for example, by X-ray small angle scattering using CuKα rays (wavelength 0.1542 nm). When no peak is observed at a scattering vector of 0.6 nm ⁻¹ or more, it can be seen that a particularly excellent gas separation performance can be maintained because there is no structure due to a phase separation structure of 200 nm or less.

<Process [II]>
As described above, the polymer membrane of the present invention may be provided with a support as necessary. The process in the case of providing a support as needed is shown below. This step is a step of obtaining a composite membrane obtained by laminating the polymer membrane obtained in the step (1) and a porous support membrane. As a method of laminating the polymer membrane and the porous support membrane, a method known per se can be employed, and examples thereof include a laminating method. Examples of the laminating method include known dry laminating and hot melt laminating. Is mentioned. Specifically, the polymer membrane and the porous support membrane are usually cut to have a diameter (diameter) of 20 to 60 mm, preferably about 25 to 50 mm, and bonded together using an adhesive or an adhesive film.

The adhesive used for laminating is not particularly limited, but an aqueous adhesive (eg, α-olefin adhesive, aqueous polymer-isocyanate adhesive, etc.), an aqueous dispersion adhesive (eg, acrylic resin emulsion adhesive) , Epoxy resin emulsion adhesives, vinyl acetate resin emulsion adhesives, etc.), solvent adhesives (eg, nitrocellulose adhesives, vinyl chloride resin solvent adhesives, chloroprene rubber adhesives, etc.), reactive adhesives (eg, , Cyanoacrylate adhesives, acrylic resin adhesives, silicone adhesives, etc.), hot melt adhesives (eg, ethylene-vinyl acetate resin hot melt adhesives, polyamide resin hot melt adhesives, polyamide resin hot melt adhesives) , Polyolefin resin hot melt adhesive, etc.). Examples of the adhesive film include films made of a thermoplastic transparent resin such as polyvinyl butyral, polyurethane, and ethylene-vinyl acetate copolymer resin. The thickness of the adhesive or adhesive film layer is not particularly limited as long as it does not interfere with the gas permeability of the polymer membrane of the present invention and the gas permeability of the porous support membrane.

Another aspect of the present invention is a method for separating carbon dioxide from a mixed gas containing carbon dioxide using the polymer membrane or composite membrane obtained above. That is, the gas separation method of the present invention includes a step of bringing the mixed gas containing carbon dioxide into contact with the polymer membrane or the composite membrane obtained above to selectively permeate carbon dioxide in the mixed gas. Features. In the gas separation method, it is preferable to provide a pressure difference between the gas supply side and the gas permeation side of the separation membrane. This pressure difference is usually provided by reducing the pressure on the gas permeation side. In addition, it is desirable to carry out the separation method under a temperature condition of usually 5 to 80 ° C., preferably room temperature to 50 ° C.

The mixed gas applicable to the separation method of the present invention is not particularly limited as long as it is a mixed gas containing carbon dioxide. However, in order to improve the separation performance between carbon dioxide and other gases, the relative humidity of the mixed gas is set to 30. % Or more, preferably 60 to 100%.
The gas separation method can be applied to, for example, separating carbon dioxide (CO ₂ ) from combustion exhaust gas generated in a thermal power plant, a steel plant, or the like.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

[Synthesis Example 1]
10.0 g (19.3 mmol) of PAMAM dendrimer (0th generation, manufactured by Sigma-Aldrich) was dissolved in 10 g of water. Under ice-cooling, 11.0 g (77.4 mmol) of glycidyl methacrylate was added dropwise. The reaction solution was stirred under ice-cooling for 24 hours to obtain a target compound represented by the following formula (hereinafter also abbreviated as 4GMAP).

[Synthesis Example 2]
2.0 g (1.40 mmol) of PAMAM dendrimer (1st generation, Sigma-Aldrich) was dissolved in 5 g of water. 1.59 g (11.2 mmol) of glycidyl methacrylate was added dropwise under ice cooling. The reaction solution was stirred for 24 hours under ice cooling to obtain a target compound represented by the following formula (hereinafter also abbreviated as 8GMAP).

[Synthesis Example 3]
1.0 g (0.31 mmol) of PAMAM dendrimer (2nd generation, Sigma-Aldrich) was dissolved in 2 g of water. Under ice-cooling, 0.70 g (4.91 mmol) of glycidyl methacrylate was added dropwise. The reaction solution was stirred under ice cooling for 24 hours to obtain the target compound 16GMAP (structural formula omitted).

[Synthesis Example 4]
(Synthesis of Compound (i))
50 mL of 3.02 g (23.2 mmol) of 2-hydroxyethyl methacrylate (HEMA, manufactured by Tokyo Chemical Industry Co., Ltd.) and 20 mg of N, N-dimethyl-4-aminopyridine (DMAP, manufactured by Sigma-Aldrich) as an acylation catalyst In chloroform. A solution was prepared by dissolving 5.15 g (25.5 mmol) of NPC (p-nitrophenyl chloroformate) and 2.58 g (25.5 mmol) of triethylamine in 50 mL of chloroform. This solution was added dropwise to the previous HEMA solution and stirred for 16 hours under ice cooling. After completion of the stirring, the reaction solution was rinsed with a saturated aqueous bicarbonate solution, a saturated saline solution, and water to synthesize activated HEMA represented by the following formula.

(Synthesis of crosslinkable amine compound 4UMAP)
1.0 g (1.93 mmol) of PAMAM dendrimer (0th generation, Sigma-Aldrich) was dissolved in 5 mL of dimethyl sulfoxide. 2.28 g (7.72 mmol) activated HEMA was dissolved in 5 mL dimethyl sulfoxide. These two solutions were mixed and allowed to react at room temperature for 24 hours. After completion of the reaction, the component organism was reprecipitated in hexane and extracted with ethanol to synthesize the target compound represented by the following formula (hereinafter also abbreviated as 4UMAP).

[Synthesis Example 5]
Based on the report of Wang et al. (Journal of Membrane Science, 290, (2007) 250-258), pentaerythrityl tetraethylenediamine (PETEDA) was reacted with pentaerythrityl tetrabromide (manufactured by Sigma-Aldrich) with excess ethylenediamine. ) Was synthesized and purified. Next, a solution obtained by dissolving 10 g (32.8 mmol) of PETEDA in 20 g of water was ice-cooled. To this solution, 18.7 g (131.2 mmol) of glycidyl methacrylate was added dropwise under ice cooling. The reaction solution was stirred for 24 hours under ice cooling to obtain a target compound represented by the following formula (hereinafter also abbreviated as GM4TA).

[Synthesis Example 6]
To a solution obtained by dissolving 10 g (68.5 mmol) of tris (2-aminoethyl) amine (manufactured by Tokyo Chemical Industry Co., Ltd.) in 30 g of water, 29.2 g (205.5 mmol) of glycidyl methacrylate was added dropwise under ice cooling. The reaction solution was stirred for 24 hours under ice-cooling to obtain a target compound represented by the following formula (hereinafter also abbreviated as GM3TA).

[Synthesis Example 7]
(Synthesis of triazine 3OH dendrimer)
10 g of triglycidyl isocyanurate (33.6 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 30 ml of anhydrous methanol and cooled on ice. To this solution, 36.4 g (0.40 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) of 1,3-diamino-2-propanol was added dropwise and stirred for 3 days. After completion of the reaction, the solvent and excess 1,3-diamino-2-propanol were distilled off under reduced pressure to obtain the target compound (triazine 3OH dendrimer).

(Synthesis of 3GMA6OHTA)
7.50 g (52.8 mmol) of glycidyl methacrylate was added dropwise under ice cooling to a solution of 10 g (17.6 mmol) of the triazine 3OH dendrimer dissolved in 30 g of water, and the reaction solution was stirred for 24 hours under ice cooling. The target compound represented by the following formula (hereinafter also abbreviated as 3GMA6OHTA) was obtained.

[Synthesis Example 8]
(Synthesis of 4OH-PAMAM dendrimer)
10 g (166 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) of ethylenediamine was dissolved in 30 ml of anhydrous methanol and cooled with ice. To this solution, 143 g (1.66 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise and stirred for 1 day. The solvent and excess methyl acrylate were distilled off under reduced pressure. 10 g (24.7 mmol) of the obtained compound was dissolved in 30 ml of anhydrous methanol, and 36.4 g (0.40 mol, manufactured by Tokyo Kasei Co., Ltd.) of 1,3-diamino-2-propanol was added dropwise to this solution for 7 days. Stir. After completion of the reaction, the solvent and excess 1,3-diamino-2-propanol were distilled off under reduced pressure to obtain the target compound (4OH-PAMAM dendrimer).

(Synthesis of 4GMA4OHP)
To a solution of 10 g (15.7 mmol) of 4OH-PAMAM dendrimer dissolved in 30 g of water, 8.92 g (62.8 mmol) of glycidyl methacrylate was added dropwise under ice cooling, and the reaction solution was cooled under ice cooling for 24 hours. The mixture was stirred to obtain the target compound represented by the following formula (hereinafter also abbreviated as 4GMA4OHP).

[Synthesis Example 9]
10 g of hydroxy polyethylene glycol dimethacrylate (manufactured by Sigma-Aldrich) was dissolved in 100 mL of chloroform. 1 g of fluorescein isothiocyanate (FITC, manufactured by Pierce) was added thereto and stirred at room temperature for 24 hours to obtain the target compound (FITC-PEGMA) represented by the following formula. For purification, insoluble FITC was removed by filtration, and the reaction solvent was distilled off under reduced pressure by an evaporator.

[Example 1]
Following formula

2 generation polyamidoamine (PAMAM) dendrimer (surface group: —CONHCH ₂ CH ₂ NH ₂ ; number of amino groups: 4; manufactured by Sigma-Aldrich), polyethylene glycol dimethacrylate (PEGDMA, molecular weight 750) , Sigma-Aldrich) 1.7 g (2.27 mmol) and 4 GMAP (Synthesis Example 1) 300 mg (0.28 mmol) as a crosslinking agent are dissolved in 4 g of water, and IRGACURE 2959 (trade name, BASF) is used as a polymerization initiator. 10 mg of 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one) manufactured by the company was added. This was cast so as to have a film thickness of 250 μm, and a polymer film was obtained by performing UV irradiation for 360 seconds (λ _max 312 nm, 12 mW / cm ² ). The resulting polymer membrane had a 4GMAP content of 7.5 wt%.

[Example 2]
A polymer film was obtained in the same manner as in Example 1 except that the film thickness was changed to the value shown in Table 3 (Invention products 2 to 4).

[Example 3]
A polymer film was obtained in the same manner as in Example 1 except that the film thickness was changed to the value described in Table 4. The polymer membrane and a porous support membrane (polyethersulfone ultrafiltration membrane, fractional molecular weight 300,000, manufactured by Millipore) were laminated to obtain composite membranes (Invention products 5 to 10).

[Example 4]
A composite film was obtained in the same manner as in Example 3 except that 300 mg (0.35 mol) of GM4TA obtained in Synthesis Example 5 was used instead of 4GMAP, and the film thickness was changed to 60 μm (Product 11 of the present invention).

[Example 5]
A composite film was obtained in the same manner as in Example 3 except that 300 mg (0.52 mol) of GM3TA obtained in Synthesis Example 6 was used instead of 4GMAP, and the film thickness was changed to 42 μm (Product 12 of the present invention).

[Example 6]
A composite film was obtained in the same manner as in Example 3 except that 300 mg (0.30 mol) of 3GMA6OHTA obtained in Synthesis Example 7 was used instead of 4GMAP, and the film thickness was changed to 52 μm (Product 13 of the present invention).

[Example 7]
A composite membrane was obtained in the same manner as in Example 3 except that 300 mg (0.25 mol) of 4GMA4OHP obtained in Synthesis Example 8 was used instead of 4GMAP, and the thickness was changed to 21 μm (Product 14 of the present invention).

[Example 8]
A polymer film was obtained in the same manner as in Example 1 except that 300 mg (1.17 × 10 ⁻⁴ mol) of 8GMAP obtained in Synthesis Example 2 was used instead of 4GMAP and the film thickness was changed to 340 μm (Invention Product 15 ).

[Example 9]
A polymer membrane was obtained in the same manner as in Example 1 except that 3 wt% of FITC-PEGMA obtained in Synthesis Example 9 was added in addition to 4GMAP (Product 16 of the present invention).

[Comparative Example 1]
Instead of 4GMAP, 300 mg (0.89 mmol) of trimethylolpropane trimethacrylate (TMPTMA, manufactured by Sigma-Aldrich) was used as a crosslinking agent, 4 g of ethanol was used as a polymerization solvent, and IRGACURE 2959 was used as a polymerization initiator. A polymer membrane was obtained in the same manner as in Example 1 except that 10 mg of 1-hydroxycyclohexyl phenyl ketone (manufactured by Sigma-Aldrich) was used (Comparative product 1). The obtained polymer film had a TMPTMA content of 15 wt%.

[Comparative Example 2]
A polymer membrane was obtained in the same manner as in Example 1 except that 4GMAP was not used (Comparative product 2).

[Comparative Example 3]
A polymer film was obtained in the same manner as in Comparative Example 1 except that the film thickness was changed to the value shown in Table 3 (Comparative products 3 to 5).

[Comparative Example 4]
A polymer film was obtained in the same manner as in Comparative Example 1 except that the film thickness was changed to the value shown in Table 3. The polymer membrane and a porous support membrane (polyethersulfone ultrafiltration membrane, fractional molecular weight 300,000, manufactured by Millipore) were laminated to obtain composite membranes (Comparative products 6 and 7).

[Comparative Example 5]
A polymer membrane was obtained in the same manner as in Example 9 except that 4GMAP was not used (Comparative product 8).

[Test Example 1] Separation test of carbon dioxide and hydrogen Using the polymer membrane obtained in Example 1 (Product 1 of the present invention), CO ₂ separation ability was measured using the apparatus shown schematically in FIG. That is, the polymer membrane is placed in contact with the supply gas, and a mixed gas of carbon dioxide gas and hydrogen gas having a partial pressure of CO ₂ shown in Table 2 is supplied to the polymer membrane and permeates the polymer membrane. The gas permeation rate Q _CO2 (m ³ (STP) / m ² Pas) was measured using a gas chromatography and a flow meter under the following conditions, and selectivity α was calculated according to the following equation. The polymer film used for the test was 0.8 cm ² . Moreover, the same test was done using the polymer film (Comparative products 1 and 2) obtained in Comparative Examples 1 and 2. The results are shown in Table 2. In Comparative product 2, the gas permeation rate and selectivity were not measurable due to breakage of the polymer membrane.

( _Wherein (X _CO2 ) _f means the mole fraction of CO _{2 in} the feed gas, (X _H2 ) _f means the mole fraction of H _{2 in} the feed gas, and (X _{CO 2} ) _p represents the membrane. (It means the mole fraction of CO ₂ in the permeated gas, and (X _H2 ) _p means the mole fraction of H ₂ in the gas permeated through the membrane.)

<Setting conditions of gas permeation measuring device>
Supply gas amount: about 100 ml / min,
Measurement temperature: 40 ° C.
Supply gas composition: CO ₂ / H ₂ = 80/20 (vol / vol),
Permeation side circulation gas: He (humidification, relative humidity 80%),
Relative humidity: 80%
Pressure: supply side: 560 kPa, permeation side: 0 kPa
<Gas chromatography analysis conditions>
Product: GC4000 (manufactured by GL Sciences)
He carrier gas amount: about 10 ml / min,
PDD detector pre-column: Porapak Q 80/100 SUS 1/8 ”x 2.17 mm x 1.0 m
Main column: Active Carbon 60/80 SUS 1/8 ”x 2.17 mm x 1.0 m
Discharge column: Molecular Sieve 5A 60/80 1/8 ”x 2.17 mm x 3.0 m

From the above results, it was confirmed that the polymer membrane of the present invention has strength to withstand a pressure difference and has excellent carbon dioxide selectivity.

[Test Example 2]
Using the polymer membrane obtained in Example 2 (products 2 to 4 of the present invention), the gas permeation rate and selectivity of the polymer membrane were measured using the apparatus shown schematically in FIG. That is, a gas mixture of carbon dioxide gas having a partial pressure of CO ₂ and hydrogen gas shown in Table 3 is supplied to the polymer membrane, and Q _H2 , Q _CO2 (m ³ (STP) of the gas permeated through the polymer membrane or the composite membrane. ) / M ² Pas) was measured using a gas chromatography and a flow meter under the following conditions, and selectivity α was calculated in the same manner as in Test Example 1. The polymer film used for the test was 0.8 cm ² . Further, the same test was performed using the polymer film obtained in Comparative Example 3 (Comparative products 3 to 5). The results are shown in Table 3.

<Setting conditions of gas permeation measuring device>
Supply gas amount: about 100 ml / min,
Measurement temperature: 40 ° C.
Supply gas composition: CO ₂ / H ₂ = 80/20 (vol / vol),
Permeation side circulation gas: He (humidification, relative humidity 80%),
Relative humidity: 80%
Pressure: Supply side: 100 to 700 kPa, Permeation side: 0 kPa
<Gas chromatography analysis conditions>
Product: GC4000 (manufactured by GL Sciences)
He carrier gas amount: about 10 ml / min,
PDD detector pre-column: Porapak Q 80/100 SUS 1/8 ”x 2.17 mm x 1.0 m
Main column: Active Carbon 60/80 SUS 1/8 ”x 2.17 mm x 1.0 m
Discharge column: Molecular Sieve 5A 60/80 1/8 ”x 2.17 mm x 3.0 m

From the above results, it was confirmed that the product of the present invention has higher CO ₂ selectivity than the comparative product.

[Test Example 3]
Using the composite membrane (Products 5 to 10 of the present invention) obtained in Example 3, the gas permeation rate and selectivity of the composite membrane were measured using the apparatus shown schematically in FIG. That is, the polymer membrane layer was placed in contact with the supply gas, measured under the same conditions as in Test Example 2, and the selectivity α was calculated in the same manner as in Test Example 1. In addition, the same test was performed using the polymer films obtained in Comparative Example 4 (Comparative products 6 and 7). The results are shown in Table 3.

From the above results, it was confirmed that when the film was thinned, the comparative product had no gas separation ability, whereas the product of the present invention could effectively separate carbon dioxide even when the film was thinned.

[Test Example 4]
Invention product 15 obtained in Example 8 and Comparative product 1 obtained in Comparative Example 1 were each immersed in ethanol for 1 day. FIG. 4 shows a scanning electron microscope (Hitachi S-4800) image of the polymer matrix after immersion. In the product 15 of the present invention, no vacancies were observed and a compatible state was maintained, whereas in the comparative product 1, many vacancies were observed, and phase separation was confirmed. From this, it was confirmed that the product of the present invention did not cause phase separation and could maintain excellent gas separation performance of Q _CO2 > 10 ⁻¹² (m ³ / m ² Pa s) and α> 10.

[Test Example 5]
The product 16 of the present invention obtained in Example 9 and the comparative product 8 obtained in Comparative Example 5 were observed with a confocal scan laser (LSM700 manufactured by Carl Zeiss). FIG. 5 is a fluorescent image 10 μm inside from the surface (resolution 200 nm, scale bar represents 5 μm). The bright part represents a high molecular polymer colored with FITC-PEGMA, and the dark part represents a dendrimer (amine compound (B)). The product 16 of the present invention containing 4GMAP (amine compound (A)) shows no phase separation structure, whereas the comparative product 8 containing no 4GMAP shows a phase separation structure of about several microns (macrophase separation). It was confirmed. From this, it was confirmed that the product of the present invention does not cause phase separation and can maintain excellent gas separation performance.

[Test Example 6]
The X-ray small angle scattering of the product 1 of the present invention obtained in Example 1 was measured using a Nano viewer manufactured by Rigaku Corporation. The optical path length is 1,250 mm, and scatterers of 200 nm or less can be detected. The results are shown in FIG. The vertical axis represents the scattering intensity, and the horizontal axis represents the scattering vector q (Å ⁻¹ ). No peak due to scattering was observed, and it was confirmed that there was no structure due to a phase separation structure of 200 nm or less. From this, it was confirmed that the product of the present invention does not cause phase separation and can maintain excellent gas separation performance.

The polymer membrane of the present invention is used in applications for separating carbon dioxide from other gases, and is useful for, for example, CO ₂ separation from combustion exhaust gas generated in thermal power plants, steel plants, etc. It is.

DESCRIPTION OF SYMBOLS 1 Polymer membrane 2 Gas permeation cell 3 Pressure gauge 4 Thermostatic bath 5 Humidifier 6 Back pressure valve

Claims

A crosslinkable amine compound having three or more acrylic and / or methacrylic groups in the molecule at the branch end.
Following formula (1)

(In the formula, A 1 represents a divalent organic residue having 1 to 3 carbon atoms, and p represents an integer of 0 or 1.)
A group represented by formula (2):

(In the formula, A 2 represents a divalent organic residue having 1 to 3 carbon atoms, and q represents an integer of 0 or 1.)
A group represented by formula (3):

(In the formula, A 3 and A 4 represent a divalent organic residue having 1 to 3 carbon atoms, and r and s represent an integer of 0 or 1.)
And a group represented by the following formula (4)

(In the formula, A 5 and A 6 represent a divalent organic residue having 1 to 3 carbon atoms, and t represents an integer of 0 or 1.)
Obtained by reacting an amine compound (A) having one or more groups selected from the group consisting of groups represented by the following groups with one or more compounds selected from the following groups (i) and (ii): The crosslinkable amine compound according to claim 1, wherein
(i) a compound obtained by reacting an acrylic ester and / or methacrylic ester with a haloformate;
(ii) an acrylic ester having at least one group selected from the group consisting of a hydroxyl group, a carboxylic acid group, a glycidyl group, an isocyanate group, an isocyanurate group, a carbodiimide group, an aldehyde group, an amino group, and an alkoxysilyl group; Or methacrylate.
3. The crosslinkable amine compound according to claim 2, wherein the amine compound (A) has three or more groups selected from the group consisting of groups represented by the formulas (1) to (4).
The crosslinkable amine compound is represented by the following formula (5):

A compound represented by formula (6):

A compound represented by formula (7):

A compound represented by formula (8):

A compound represented by formula (9):

A compound represented by formula (10):

And a compound represented by the following formula (11)

The crosslinkable amine compound according to claim 1, which is at least one compound selected from the group consisting of compounds represented by the formula:
A high molecular weight polymer obtained by polymerizing a polyfunctional polymerizable monomer, which is crosslinked using the crosslinkable amine compound according to any one of claims 1 to 4 as a crosslinking agent, has the following formula ( 1)

(In the formula, A 1 represents a divalent organic residue having 1 to 3 carbon atoms, and p represents an integer of 0 or 1.)
A group represented by formula (2):

(In the formula, A 2 represents a divalent organic residue having 1 to 3 carbon atoms, and q represents an integer of 0 or 1.)
A group represented by formula (3):

(In the formula, A 3 and A 4 represent a divalent organic residue having 1 to 3 carbon atoms, and r and s represent an integer of 0 or 1.)
And a group represented by the following formula (4)

(In the formula, A 5 and A 6 represent a divalent organic residue having 1 to 3 carbon atoms, and t represents an integer of 0 or 1.)
A polymer film comprising an amine compound (B) having at least one group selected from the group consisting of groups represented by the formula:
6. The polymer film according to claim 5, wherein the amine compound (B) has three or more groups selected from the group consisting of groups represented by the formulas (1) to (4).
The polymer film according to claim 5 or 6, wherein the amine compound (B) is a polyamidoamine-based dendrimer.
The polyamidoamine dendrimer has the following formula:

8. The polymer film according to claim 7, wherein the polymer film is at least one kind of 0th generation dendrimer selected from the group consisting of 1st to 5th generation dendrimers corresponding thereto.
The polyfunctional polymerizable monomer is one or more selected from the group consisting of polyfunctional (meth) acrylamide, polyfunctional (meth) acrylate, polyfunctional vinyl ether and divinylbenzene. The polymer film according to any one of the above.
The polymer according to any one of claims 5 to 9, wherein the scattering vector has no peak at 0.6 nm -1 or more by X-ray small angle scattering using CuKα rays (wavelength 0.1542 nm). film.
The polymer membrane according to any one of claims 5 to 10, wherein the polymer membrane is a gas separation membrane.
The crosslinkable amine compound according to any one of claims 1 to 4 and the following formula (1)

(In the formula, A 1 represents a divalent organic residue having 1 to 3 carbon atoms, and p represents an integer of 0 or 1.)
A group represented by formula (2):

(In the formula, A 2 represents a divalent organic residue having 1 to 3 carbon atoms, and q represents an integer of 0 or 1.)
A group represented by formula (3):

(In the formula, A 3 and A 4 represent a divalent organic residue having 1 to 3 carbon atoms, and r and s represent an integer of 0 or 1.)
And a group represented by the following formula (4)

(In the formula, A 5 and A 6 represent a divalent organic residue having 1 to 3 carbon atoms, and t represents an integer of 0 or 1.)
In the presence of an amine compound (B) having one or more groups selected from the group consisting of the groups represented by the above formula, the amine is introduced into the polymer produced by polymerizing a polyfunctional polymerizable monomer. A method for producing a polymer film, comprising a step of immobilizing the compound (B).
Prior to the polymerization reaction, the following formula (1)

(In the formula, A 1 represents a divalent organic residue having 1 to 3 carbon atoms, and p represents an integer of 0 or 1.)
A group represented by formula (2):

(In the formula, A 2 represents a divalent organic residue having 1 to 3 carbon atoms, and q represents an integer of 0 or 1.)
A group represented by formula (3):

(In the formula, A 3 and A 4 represent a divalent organic residue having 1 to 3 carbon atoms, and r and s represent an integer of 0 or 1.)
And a group represented by the following formula (4)

(In the formula, A 5 and A 6 represent a divalent organic residue having 1 to 3 carbon atoms, and t represents an integer of 0 or 1.)
A step of reacting an amine compound (A) having one or more groups selected from the group consisting of groups represented by formula (1) and one or more compounds selected from the group consisting of (i) and (ii) below: 13. The manufacturing method according to claim 12, further comprising:
(i) a crosslinking compound obtained by reacting an acrylic ester and / or methacrylic ester with a haloformate;
(ii) Acrylic acid ester having at least one group selected from the group consisting of hydroxyl group, carboxyl group, glycidyl group, isocyanate group, isocyanurate group, carbodiimide group, aldehyde group, amino group and alkoxysilyl group, and / or Methacrylic acid ester.
The method for producing a polymer film according to claim 12 or 13, wherein the amine compound (B) is a polyamidoamine-based dendrimer.
The polyamidoamine dendrimer has the following formula:

15. The method for producing a polymer film according to claim 14, wherein the polymer film is at least one kind of 0th generation dendrimer selected from the group consisting of 1st to 5th generation dendrimers.
A carbon dioxide comprising a step of bringing a mixed gas containing carbon dioxide into contact with the polymer membrane according to any one of claims 5 to 11 to selectively permeate carbon dioxide in the mixed gas. Separation method.