WO2014123091A1 - Porous metal complex, method for producing polymer using same, and vinyl ester copolymer - Google Patents

Abstract

The object of the invention is to provide a method for producing a polymer having high solvent resistance and to provide a vinyl ester copolymer having high solvent resistance. Provided as a means for attaining the above object are: a method for producing a polymer, characterized in that a monomer (V) having unsaturated double bonds is polymerized in the pores of a porous metal complex containing an aromatic polycarboxylic acid compound (L1) having at least two substituents that have terminal alkenyl groups, and containing at least one type of metal ion selected from ions of metals belonging to groups 1-14 of the periodic table, and a polymer containing the aromatic polycarboxylic acid compound (L1) in the monomer units is obtained; and a vinyl ester copolymer with the aromatic compound (L1) having at least two substituents that have terminal alkenyl groups, the copolymer being characterized in that a polymer chain containing the vinyl ester monomer in the main chain is crosslinked by the aromatic compound (L1) and oriented in one dimension.

Description

Porous metal complex, method for producing polymer using the metal complex, and vinyl ester copolymer

[Cross-reference of related applications]
This application includes Japanese Patent Application No. 2013-023432 filed on Feb. 8, 2013 and Japanese Patent Application No. 2013-023408 filed on Feb. 8, 2013 ( The entire disclosures of which are incorporated herein by reference).

The present invention relates to a polymer production method in which a monomer is adsorbed in the pores of a porous metal complex and copolymerized with a ligand constituting the metal complex. The present invention also relates to a porous metal complex that can be used in the production method.

The present invention also relates to a vinyl ester copolymer. More specifically, the present invention relates to a vinyl ester copolymer obtained by copolymerizing a vinyl ester monomer adsorbed in the pores of a porous metal complex with a ligand of the porous metal complex.

Polymers are materials that have an excellent balance of performance such as lightness and strength, and are often used as molded products because they can be molded at low temperatures compared to metals. There is injection molding as one of general-purpose molding methods. However, when a polymer is molded by injection molding, internal stress (residual strain or the like) tends to remain in the molded product. Deformed, cracked, cracked, etc. are likely to occur in molded products with remaining internal stress, especially when exposed to organic solvents such as alcohols, fuel oils, wax removers, etc. It becomes easy. From this point, the polymer is required to have high solvent resistance. As a polymer with improved solvent resistance, for example, an ionomer resin is disclosed (see Patent Document 1).

On the other hand, a method is known in which a monomer is polymerized by adsorbing a low-molecular compound in the pores using a porous metal complex composed of an organic ligand and a metal ion (Patent Documents 2 to 5, non-patent documents). Reference 1). According to these methods, it is disclosed that a polymer having a controlled molecular weight distribution and stereoregularity can be obtained, but there is no description regarding solvent resistance.

Polyvinyl acetate, which is a general-purpose polyvinyl ester, is widely used as an intermediate raw material for polyvinyl alcohol. Polyvinyl acetate emulsions containing polyvinyl alcohol as a protective colloid are various adhesives for paper, woodworking and plastics, various binders for impregnated paper and non-woven products, admixtures, surface treatment agents, It is used for applications such as splicing materials, paints, paper processing and textile processing, and wallpaper. In these applications, it is necessary to improve water resistance, solvent resistance, etc., and various methods have been proposed so far in order to improve the water resistance, solvent resistance, etc. of polyvinyl esters.

For example, polyvinyl esters or polyvinyl alcohols are known in which water resistance is improved by adding a crosslinkable functional group such as a carboxyl group to polyvinyl ester or saponified polyvinyl alcohol (see Patent Documents 6 and 7). ). It is also known that the solvent resistance is improved by using a paint obtained by adding a small amount of a surfactant to a polyvinyl acetate emulsion as a back surface treatment agent such as an adhesive tape (see Patent Document 8).

However, although the water resistance and solvent resistance of the polyvinyl ester or the saponified polyvinyl alcohol thereof are improved to some extent by these methods, there is still room for improvement.

On the other hand, as a method for producing a regular polymer having a side chain containing a reactive group, a method of polymerizing a monomer within the pores of a porous metal complex is known (see Patent Document 3). According to this document, a polymer having structure regularity can be obtained from a monomer having a plurality of reactive groups by using a porous metal complex having pores as one-dimensional regular nanochannels. Examples of functional molecules having a reactive group include styrene and vinyl acetate.

However, it is disclosed that the polymer obtained by the method of Patent Document 3 has rather improved solubility in a solvent because the polymer chain has a one-dimensional chain structure.

Japanese Patent Laid-Open No. 2004-224813 JP 2006-225579 A JP 2007-238874 A JP-A-9-324006 JP-A-8-217811 JP-A-8-60116 Japanese Patent Publication No. 1-31525 JP-A-9-143438

Under such circumstances, the problem to be solved by the present invention is to provide a completely new method for producing a polymer having high solvent resistance and to provide a vinyl ester copolymer having high solvent resistance.

As a result of intensive studies by the present inventors, a polymer having a high solvent resistance is obtained by polymerizing a monomer using a porous metal complex having a specific aromatic polyvalent carboxylic acid compound having at least two terminal alkenyl groups. It has been found that it can be manufactured and the above problems can be solved, and the present invention has been achieved.

That is, the present invention mainly relates to the following [1] to [23].

[1] An aromatic polycarboxylic acid compound (L1) having at least two substituents having a terminal alkenyl group, and at least one metal ion selected from ions of metals belonging to Groups 1 to 14 of the periodic table; Characterized in that a monomer (V) having an unsaturated double bond is polymerized in the pores of a porous metal complex containing a polymer to obtain a polymer containing the aromatic polyvalent carboxylic acid compound (L1) as a constituent unit. A method for producing a polymer.

[2] The method for producing a polymer according to [1], wherein the aromatic polyvalent carboxylic acid compound (L1) is a compound represented by the following general formula (1) or (2):

(In the formula, A ¹ and A ² are carboxyl groups, and at least two of B ¹ to B ⁴ are the same or different, and the following general formula (3)

^{(Y 1} and ^{Y 2} are the same or different oxygen atom, a sulfur atom or -O-CO-, ^[Y 1 - _{(CH 2) a]} is ^{Y 1} and a is the same or different from each other in each repeating unit A is 1 to 5, b is 0 to 5, c is 0 or 1, and d is an integer of 0 to 5. R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxycarbonyl group. is there)
The substituents having a terminal alkenyl group represented by general formula (3) among B ¹ to B ⁴ are the same or different and have a hydrogen atom, a halogen atom or a substituent. Selected from the group consisting of an alkyl group, an alkoxy group, a thioalkyl group, a formyl group, an acyloxy group, an alkoxycarbonyl group, a nitro group, a cyano group, an amino group, a monoalkylamino group, a dialkylamino group, an acylamino group, and a carboxyl group Is any substituent. )

[3] The method for producing a polymer according to [1] or [2], wherein the porous metal complex further contains a polyvalent carboxylic acid compound (D) different from the aromatic polyvalent carboxylic acid compound (L1). .

[4] The method for producing a polymer according to [3], wherein the polyvalent carboxylic acid compound (D) is an aromatic dicarboxylic acid compound having no terminal alkenyl group.

[5] The content of the aromatic polyvalent carboxylic acid compound (L1) in the porous metal complex is 100 mol% in total of the aromatic polyvalent carboxylic acid compound (L1) and the polyvalent carboxylic acid compound (D). The method for producing a polymer according to [3] or [4], which is in the range of 0.1 to 99.9 mol%.

[6] The method for producing a polymer according to any one of [1] to [5], wherein the porous metal complex further contains an organic ligand capable of multidentate coordination with the metal ion.

[7] The method for producing a polymer according to any one of [1] to [6], wherein the monomer (V) having an unsaturated double bond is a vinyl ester.

[8] The method for producing a polymer according to [7], wherein the monomer (V) is vinyl acetate.

[9] The method for producing a polymer according to [7] or [8], further including a saponification step after the polymerization of the monomer (V).

[10] A method for producing a carbon material, wherein the polymer obtained by the method according to any one of [1] to [8] is heat-treated at a temperature of 400 ° C. to 600 ° C.

[11] A copolymer of a vinyl ester monomer and an aromatic compound (L) represented by the following general formula (1) or (2) having at least two substituents having a terminal alkenyl group, A vinyl ester copolymer, wherein a polymer chain containing a vinyl ester monomer in a main chain is crosslinked with an aromatic compound (L).

(In the formula, A ¹ and A ² are the same or different and have the following general formula:

A carboxyl group represented by

A pyridyl group represented by

An imidazolyl group represented by:

A triazolyl group represented by

And X is a hydrogen atom or an alkali metal atom. At least two of B ¹ to B ⁴ are substituents having the same or different terminal alkenyl groups, and the others are hydrogen atom, halogen atom, alkyl group, alkoxy group, thioalkyl group, formyl group, acyloxy group, alkoxycarbonyl A substituent selected from the group consisting of a group, a nitro group, a cyano group, an amino group, a monoalkylamino group, a dialkylamino group, an acylamino group, a carboxyl group, and an alkali metal salt of a carboxyl group. )

[12] The vinyl ester copolymer according to [11], wherein the polymer chain is one-dimensionally oriented.

[13] The substituent having the terminal alkenyl group is represented by the following general formula (3):

(Wherein, ^{Y 1} and ^{Y 2} are the same or different oxygen atom, a sulfur atom or -O-CO-, ^[Y 1 - _{(CH 2) a]} are the same or ^{Y 1} and a is in each repeating unit A is 1 to 5, b is 0 to 5, c is 0 or 1, and d is an integer of 0 to 5. R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or alkoxycarbonyl Base)
The vinyl ester copolymer according to [11] or [12], which is a substituent represented by:

[14] The vinyl ester copolymer according to any one of [11] to [13], wherein the content of the monomer unit derived from the aromatic compound (L) is 0.1 to 50 mol%.

[15] The vinyl ester system according to any one of [11] to [14], wherein the polymer chain distance of the polymer chain containing the vinyl ester monomer in the main chain is in the range of 0.4 to 0.6 nm. Copolymer.

[16] The vinyl ester copolymer according to any one of [11] to [15], wherein the vinyl ester monomer is vinyl acetate.

[17] A polyvinyl copolymer obtained by saponifying the copolymer according to any one of [11] to [16].

[18] An aromatic polycarboxylic acid compound (L1) having at least two substituents having a terminal alkenyl group, a polyvalent carboxylic acid compound (D) different from the aromatic polycarboxylic acid compound (D1), and a metal belonging to Groups 1 to 14 of the periodic table A porous metal complex comprising at least one metal ion selected from the ions of:

[19] The porous metal complex according to [18], wherein the aromatic polyvalent carboxylic acid compound (L1) is a compound represented by the following general formula (1) or (2);

(In the formula, A ¹ and A ² are carboxyl groups, and at least two of B ¹ to B ⁴ are the same or different, and the following general formula (3)

(In Formula (3), Y ¹ and Y ² are the same or different and are an oxygen atom, a sulfur atom, or —O—CO—, and [Y ¹ — (CH ₂ ) _a ] represents Y ¹ and a for each repeating unit. May be the same or different, a is 1 to 5, b is 0 to 5, c is 0 or 1, and d is an integer of 0 to 5. R is a hydrogen atom, an alkyl having 1 to 5 carbon atoms Group or alkoxycarbonyl group)
The substituents having a terminal alkenyl group represented by general formula (3) among B ¹ to B ⁴ are the same or different and have a hydrogen atom, a halogen atom or a substituent. Selected from the group consisting of an alkyl group, an alkoxy group, a thioalkyl group, a formyl group, an acyloxy group, an alkoxycarbonyl group, a nitro group, a cyano group, an amino group, a monoalkylamino group, a dialkylamino group, an acylamino group, and a carboxyl group Is any substituent. ).

[20] The substituent having the terminal alkenyl group is represented by the following general formula (4):

The porous metal complex according to [19], wherein O is an oxygen atom and d is an integer of 1 to 5 in the formula (4).

[21] The porous metal complex according to any one of [18] to [20], wherein the polyvalent carboxylic acid compound (D) is an aromatic dicarboxylic acid compound having no terminal alkenyl group.

[22] The content of the aromatic polyvalent carboxylic acid compound (L1) is 0.1 to 0.1% with respect to 100 mol% in total of the aromatic polyvalent carboxylic acid compound (L1) and the polyvalent carboxylic acid compound (D). The porous metal complex according to any one of [18] to [21], which is in the range of 99.9 mol%.

[23] The porous metal complex according to any one of [18] to [22], wherein the porous metal complex further contains an organic ligand capable of multidentate coordination with the metal ion.

According to the production method of the present invention, it is possible to produce a polymer having high solvent resistance, which has significantly improved resistance to solvents as compared with polymers obtained by conventional polymerization methods. In addition, the polymer obtained by the production method of the present invention has a main chain that is one-dimensionally oriented and has a pseudocrystalline structure in the polymer, so that it can have a high density. Furthermore, the polymer obtained by the production method of the present invention is excellent in heat resistance, mechanical strength, and the like.

According to the present invention, it is also possible to obtain a vinyl ester copolymer with significantly improved resistance to solvents. The vinyl ester copolymer of the present invention is superior in solvent resistance, heat resistance, mechanical strength and the like as compared with a vinyl ester copolymer obtained by ordinary solution polymerization.

The schematic diagram of a porous metal complex is shown. The schematic diagram of superposition | polymerization in a porous metal complex is shown. In the figure, (a) porous metal complex, (b) aromatic compound (L) (for example, aromatic polycarboxylic acid compound (L1)), (c) monomer (V) (for example, vinyl ester monomer). ); And (i) monomer adsorption, (ii) polymerization, and (iii) decomposition / removal of the porous metal complex. The powder X-ray-diffraction pattern of the porous metal complex obtained by the synthesis example 1 is shown. The powder X-ray diffraction pattern of the porous metal complex obtained in Synthesis Example 2 is shown. The powder X-ray-diffraction pattern of the porous metal complex obtained by the synthesis example 3 is shown. The powder X-ray-diffraction pattern of the porous metal complex obtained by the synthesis example 4 is shown. The crystal structure of the porous metal complex obtained in Comparative Synthesis Example 1 is shown. The powder X-ray-diffraction pattern of the metal complex obtained by the comparative synthesis example 1 is shown. An IR chart is shown. (a) An IR chart of the vinyl acetate-2,5-di (allyloxy) terephthalic acid copolymer obtained in Example 1 is shown (bottom). (b) An IR chart of polyvinyl acetate (solution polymerized product) synthesized by solution polymerization is shown (top).

3 to 6 and 8, the vertical axis represents the intensity.

1. Porous metal complex The metal complex of the present invention is an aromatic compound (L) having at least two substituents having a terminal alkenyl group and at least one selected from ions of metals belonging to Groups 1 to 14 of the periodic table. Metal ions.

The aromatic compound (L) is a compound represented by the following general formula (1) or (2) having at least two substituents having a terminal alkenyl group.

In the above formula, A ¹ and A ² are the same or different, and

A carboxyl group represented by

A pyridyl group represented by

An imidazolyl group represented by:

A triazolyl group represented by

X is a hydrogen atom or an alkali metal atom (for example, a sodium atom, a potassium atom, etc.). At least two of B ¹ to B ⁴ are each a substituent having the same or different terminal alkenyl group, and the others are a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an alkoxy group, a thioalkyl group Group, formyl group, acyloxy group, alkoxycarbonyl group, nitro group, cyano group, amino group, monoalkylamino group, dialkylamino group, acylamino group, hydroxyl group, carboxyl group, and alkali metal salt of carboxyl group Any of the substituents. The number of carbon atoms contained in the substituent is preferably in the range of 0 to 5, more preferably in the range of 0 to 2.

Examples of halogen atoms include fluorine, chlorine, bromine and iodine atoms, and examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert Examples of the alkoxy group having a linear or branched alkyl group such as butyl group or pentyl group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert- The butoxy group is a thioalkyl group such as a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, an isobutylthio group, or a tert-butylthio group. Examples of an acyloxy group include an acetoxy group, n -Propanoyloxy group, n-butanoyloxy group, pivaloyloxy group, benzoyl Examples of the alkoxy group include an alkoxycarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group, and an n-butoxycarbonyl group, examples of a monoalkylamino group include a methylamino group, and examples of a dialkylamino group include dimethylamino. An example of the acylamino group is an acetylamino group. Examples of the substituent that the alkyl group may have include an alkoxy group (methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group). Etc.), amino group, monoalkylamino group (such as methylamino group), dialkylamino group (such as dimethylamino group), formyl group, epoxy group, acyloxy group (acetoxy group, n-propanoyloxy group, n-butanoyl) Oxy group, pivaloyloxy group, benzoyloxy group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, etc.), carboxylic acid anhydride group (—CO—O—CO—R group) (R Is an alkyl group having 1 to 5 carbon atoms). The number of substituents on the alkyl group is preferably 1 to 3, more preferably 1.

The aromatic compound (L) is preferably an aromatic polyvalent carboxylic acid compound (L1), particularly preferably a benzene polyvalent carboxylic acid compound. In this case, A ¹ and A ² are a carboxyl group or a salt thereof.

In this specification, the “carboxyl group” includes a group represented by —COOH and a group represented by —COO 2 ^— . When the aromatic compound (L) is an aromatic polyvalent carboxylic acid compound (L1), in the porous metal complex, the carboxyl group is mainly in the form of a carboxylate (—COO ⁻ ) from which a proton has been eliminated. Exists.

A ¹ and A ² may be the same or different, but are preferably the same.

At least two of B ¹ to B ⁴ are each a substituent having the same or different terminal alkenyl group. The substituent having the terminal alkenyl group is not particularly limited as long as the alkenyl group represented by —CR═CH ₂ is bonded to the terminal of the substituent. By copolymerizing the alkenyl group moiety with the monomer (V) accommodated in the pores of the metal complex, the target polymer can be obtained. The substituent having a terminal alkenyl group is preferably the following general formula (3)

It is a substituent represented by these. In the general formula (3), Y ¹ and Y ² are the same or different and are an oxygen atom, a sulfur atom or —O—CO—, and [Y ¹ — (CH ₂ ) _a ] represents Y ¹ and a for each repeating unit. May be the same or different, a is an integer of 1 to 5, b is 0 to 5, c is 0 or 1, and d is an integer of 0 to 5. a is preferably in the range of 1 to 3, more preferably in the range of 1 to 2. b is preferably in the range of 0 to 2, more preferably 0 or 1. c is preferably 1. d is preferably in the range of 0 to 3, and more preferably in the range of 0 to 1. R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxycarbonyl group.

Specific examples of the substituent having a terminal alkenyl group include a vinyl group, isopropenyl group, allyl group, methallyl group, 3-butenyl group, vinyloxy group, isopropenyloxy group, allyloxy group, methallyloxy group, ( And allyloxy) methoxy group.

Preferable examples of the substituent having a terminal alkenyl group also include a substituent having a terminal alkenyl group represented by the following general formula (4).

(In formula (4), O is an oxygen atom and d is an integer of 1 to 5)
Specific examples of the aromatic compound (L) include 2,5-divinyl terephthalic acid, 2,5-diisopropenyl terephthalic acid, 2,5-diallyl terephthalic acid, 2,5-dimethallyl terephthalic acid, 2,5-di (vinyloxy) terephthalic acid, 2,5-di (isopropenyloxy) terephthalic acid, 2,5-di (allyloxy) terephthalic acid, 2,5-di (methallyloxy) terephthalic acid, 4, Examples thereof include 6-divinylisophthalic acid.

As the metal ions selected from Groups 1 to 14 of the periodic table, those that form a porous metal complex with a structural unit derived from the aromatic compound (L) are suitable. Examples of metal ions include lithium ions, sodium ions, potassium ions, magnesium ions, calcium ions, barium ions, scandium ions, lanthanoid ions, titanium ions, zirconium ions, vanadium ions, chromium ions, manganese ions, iron ions, and cobalt. Ions, nickel ions, copper ions, zinc ions, cadmium ions, aluminum ions and the like can be used, and copper ions and zinc ions are more preferable. The metal ion is preferably a single metal ion, but may contain two or more kinds of metal ions. Moreover, the porous metal complex of this invention can also mix and use two or more types of porous metal complexes which consist of a single metal ion.

The porous metal complex may further contain a polyvalent carboxylic acid compound (D) different from the aromatic compound (L). As the polyvalent carboxylic acid compound (D), those having no terminal alkenyl group are preferred. Preferable specific examples of the polyvalent carboxylic acid compound (D) include, for example, succinic acid, 1,4-cyclohexanedicarboxylic acid, fumaric acid, muconic acid, 2,3-pyrazinedicarboxylic acid, terephthalic acid, isophthalic acid, 1, 4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 2,5-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, 2,5-thiophenedicarboxylic acid, 2,2 Aromatic dicarboxylic acid compounds such as '-dithiophene dicarboxylic acid; trimesic acid, trimellitic acid, biphenyl-3,4', 5-tricarboxylic acid, 1,3,5-tris (4-carboxyphenyl) benzene, 1, Aromatic tricals such as 3,5-tris (4'-carboxy [1,1'-biphenyl] -4-yl) benzene Acid compounds; pyromellitic acid, [1,1 ′: 4 ′, 1 ″] terphenyl-3,3 ″, 5,5 ″ -tetracarboxylic acid, 1,2,4,5-tetrakis (4- Aromatic tetracarboxylic acid compounds such as carboxyphenyl) benzene; and the like. Among these, dicarboxylic acid compounds are preferable, and aromatic dicarboxylic acid compounds are more preferable. The polyvalent carboxylic acid compound (D) may be used alone, or two or more polyvalent carboxylic acid compounds may be mixed and used. In the porous metal complex, the polyvalent carboxylic acid compound (D) exists mainly in a carboxylate state in which protons are eliminated from the carboxylic acid sites.

The polyvalent carboxylic acid compound (D) may further have a substituent other than the carboxyl group. The polyvalent carboxylic acid having a substituent is preferably an aromatic polyvalent carboxylic acid, and the substituent is preferably bonded to the aromatic ring of the aromatic polyvalent carboxylic acid. The number of substituents may be 1, 2 or 3. The substituent is not particularly limited as long as it does not have a terminal alkenyl group. For example, a halogen atom, an alkyl group which may have a substituent, an alkoxy group, a thioalkyl group, a formyl group, Examples include acyloxy group, alkoxycarbonyl group, nitro group, cyano group, amino group, monoalkylamino group, dialkylamino group, acylamino group, hydroxyl group and the like. Specific examples of the polyvalent carboxylic acid compound (D) include 2-nitroterephthalic acid, 2-fluoroterephthalic acid, 2,3,5,6-tetrafluoroterephthalic acid, 2,4,6-trifluoro- Examples include 1,3,5-benzenetricarboxylic acid.

When the porous metal complex contains the polyvalent carboxylic acid compound (D), the ratio is not particularly limited, but the aromatic compound (L) and the polyvalent carboxylic acid compound (D) contained in the metal complex. The content ratio of the aromatic compound (L) is preferably in the range of 0.1 to 99.9 mol%, more preferably in the range of 0.5 to 90 mol% with respect to the total mol (100 mol%) of A range of 1 to 50 mol% is particularly preferable. The content ratio of the polyvalent carboxylic acid compound (D) is preferably in the range of 99.9 to 0.1 mol%, more preferably in the range of 99.5 to 10 mol%, and 99 to 50 mol%. Within the range is particularly preferred. When the content rate of an aromatic compound (L) is too low, the solvent resistance of the polymer obtained may not be enough. If the content of the aromatic compound (L) is too high, a polymer having a high solvent resistance is obtained, but the polymer yield tends to decrease.

The porous metal complex of the present invention may contain an organic ligand capable of bidentate coordination different from the aromatic compound (L) and the polyvalent carboxylic acid compound (D). The organic ligand capable of bidentate coordination means a neutral ligand having two portions coordinated to a metal ion by a lone pair, for example, 1,4-diazabicyclo [2. 2.2] octane, pyrazine, 2,5-dimethylpyrazine, 4,4′-bipyridyl, 2,2′-dimethyl-4,4′-bipyridine, 1,2-bis (4-pyridyl) ethyne, 1, 4-bis (4-pyridyl) butadiyne, 1,4-bis (4-pyridyl) benzene, 3,6-di (4-pyridyl) -1,2,4,5-tetrazine, 2,2′-bi- 1,6-naphthyridine, phenazine, diazapyrene, trans-1,2-bis (4-pyridyl) ethene, 4,4′-azopyridine, 1,2-bis (4-pyridyl) ethane, 1,2-bis (4 -Pyridyl) propane, 1,2-bis (4-pyridyl) Glycol, N- (4-pyridyl) isonicotinamide, 2,6-di (4-pyridyl) -benzo [1,2-c: 4,5-c ′] dipyrrole-1,3,5,7 (2H , 6H) -Tetron, 4,4′-bis (4-pyridyl) biphenyl, N, N′-di (4-pyridyl) -1,4,5,8-naphthalenetetracarboxydiimide, 1,2-bis ( 1-imidazolyl) ethane, 1,2-bis (1,2,4-triazolyl) ethane, 1,2-bis (1,2,3,4-tetrazolyl) ethane, 1,2-bis (1-imidazolyl) Propane, 1,2-bis (1,2,4-triazolyl) propane, 1,2-bis (1,2,3,4-tetrazolyl) propane, 1,2-bis (1-imidazolyl) butane, 1, 2-bis (1,2,4-triazolyl) butane, 1, -Bis (1,2,3,4-tetrazolyl) butane, 1,4-bis (benzimidazol-1-ylmethyl) -2,4,5,6-tetramethylbenzene, 1,4-bis (4-pyridyl) Methyl) -2,3,5,6-tetramethylbenzene, 1,3-bis (imidazol-1-ylmethyl) -2,4,6-trimethylbenzene, 1,3-bis (4-pyridylmethyl) -2 4,6-trimethylbenzene and the like.

The porous metal complex used in the present invention is preferably one in which the pores of the porous metal complex have a one-dimensional structure. Examples of porous metal complexes having one-dimensional pores include porous metals composed of zinc ions, terephthalate ions, and 1,4-diazabicyclo [2.2.2] octane described in Non-Patent Document 2. A complex. The schematic diagram is shown in FIG. In the metal complex, bidentate 1,4-diazabicyclo [2.2.2] octane is coordinated to the axial position of the zinc ion of a two-dimensional lattice-like sheet composed of a carboxylate ion of terephthalic acid and zinc. Thus, a three-dimensional structure in which the sheets are connected to each other is formed. In the structure, the two-dimensional sheet structure is formed with pores extending one-dimensionally in the vertical direction. Similarly, an example of forming a three-dimensional structure having one-dimensional pores includes a porous metal complex composed of aluminum ions and terephthalate ions. However, the porous metal complex having one-dimensional pores is not limited to those forming a three-dimensional structure, and may be a two-dimensional structure or a one-dimensional structure. As an example, a porous metal complex composed of a copper ion, 2,5-dihydroxyterephthalate ion, and 4,4′-bipyridyl described in Non-Patent Document 3 can be given. Although the porous metal complex has a sheet-like two-dimensional structure, one-dimensional pores are formed by the integrated structure of the sheet.

However, as a porous metal complex that can be used in the present invention, it is not sufficient that the pores have a one-dimensional structure, and as described above, an aromatic polyvalent having at least two substituents having a terminal alkenyl group. It is necessary to include the carboxylic acid compound (L1) in the structure. Specific examples include porous metal complexes composed of zinc ions, 2,5-di (allyloxy) terephthalate ions, and 1,4-diazabicyclo [2.2.2] octane. The crystal structure has one-dimensional pores, similar to the porous metal complex composed of zinc ion, terephthalate ion and 1,4-diazabicyclo [2.2.2] octane described in Non-Patent Document 2. A three-dimensional integrated structure is formed.

The particle diameter of the porous metal complex used in the present invention is preferably 10 nm to 100 μm, more preferably 100 nm to 100 μm. When the particle diameter is smaller than 10 nm, the polymer chain length obtained is short when used for polymer production, and the solvent resistance tends to be poor. Methods for measuring the particle size include a method of taking a particle image with a scanning electron microscope or the like, and a method of obtaining a particle size distribution with a laser diffraction particle size measuring device.

The pore size of the porous metal complex used in the present invention is preferably 3 to 20 mm, more preferably 3 to 15 mm, and still more preferably 5 to 10 mm. As a method for measuring pores, the structure is determined by single crystal X-ray diffraction or powder X-ray diffraction, and the pore size can be obtained from this structure. The pore size can also be measured by gas adsorption measurement.

The porous metal complex used in the present invention has at least one selected from an aromatic compound (L) having at least two substituents having a terminal alkenyl group and a salt of a metal belonging to Groups 1 to 14 of the periodic table. Reaction of a metal salt of a seed with an organic ligand capable of bidentate coordination with the metal ion and a polyvalent carboxylic acid compound (D), if necessary, in a gas phase, a liquid phase or a solid phase However, it is preferable to produce it by allowing it to react for several hours to several days in a solvent under normal pressure and to precipitate it. At this time, the reaction may be performed under ultrasonic wave or microwave irradiation.

Examples of the metal salts belonging to Groups 1 to 14 of the periodic table used for the production of the porous metal complex include lithium salt, sodium salt, potassium salt, magnesium salt, calcium salt, barium salt, scandium salt, lanthanoid salt, titanium salt, Zirconium salt, vanadium salt, chromium salt, manganese salt, iron salt, cobalt salt, nickel salt, copper salt, zinc salt, cadmium salt and aluminum salt can be used, and copper salt and zinc salt are more preferable. The metal salt is preferably a single metal salt, but two or more metal salts may be mixed and used. Further, as these metal salts, organic acid salts such as acetates and formates, inorganic acid salts such as sulfates, nitrates, carbonates, hydrochlorides and hydrobromides can be used.

The mixing ratio of the metal salt and the aromatic compound (L) when producing the porous metal complex is preferably within the range of the molar ratio of metal salt: aromatic compound (L) = 1: 5 to 8: 1. : More preferably in the range of 3-6: 1. When an organic ligand capable of multidentate coordination is used, the mixing ratio of the metal salt to the organic ligand capable of multidentate coordination is as follows: metal salt: organic ligand capable of multidentate coordination = 1: The molar ratio is preferably within a range of 3 to 3: 1, and more preferably within a range of 1: 2 to 2: 1. When the polyvalent carboxylic acid compound (D) is used, a molar ratio range of the aromatic compound (L): the polyvalent carboxylic acid compound (D) = 0.1: 99.9 to 99.9: 0.1 Is preferably within the range of 0.5: 99.5 to 70:30.

When the metal complex is produced in a solvent, the molar concentration of the metal salt in the solvent is preferably 0.005 to 5.0 mol / L, more preferably 0.01 to 2.0 mol / L. Even if the reaction is performed at a concentration lower than this, the desired metal complex can be obtained, but this is not preferable because the yield decreases. Further, at a concentration higher than this, unreacted metal salt remains, and purification of the obtained metal complex becomes difficult.

When the metal complex is produced in a solvent, the total molar concentration of the aromatic compound (L) and the polyvalent carboxylic acid compound (D) in the solvent is preferably 0.001 to 5.0 mol / L, 0.005 More preferable is -2.0 mol / L. Even if the reaction is performed at a concentration lower than this, the desired metal complex can be obtained, but this is not preferable because the yield decreases. If the concentration is higher than this, the solubility is lowered and the reaction does not proceed smoothly.

As the solvent used for the production of the metal complex, an organic solvent, water, or a mixed solvent thereof can be used. Specifically, methanol, ethanol, propanol, diethyl ether, dimethoxyethane, tetrahydrofuran, hexane, cyclohexane, heptane, benzene, toluene, methylene chloride, chloroform, acetone, ethyl acetate, acetonitrile, N, N-dimethylformamide, water or These mixed solvents can be used.

The reaction temperature for producing the metal complex is preferably −20 to 150 ° C.

The completion of the reaction for producing the metal complex can be confirmed by quantifying the remaining amount of the raw material by gas chromatography or high performance liquid chromatography, but is not limited thereto. After completion of the reaction, the obtained mixed solution is subjected to suction filtration to collect a precipitate, washed with an organic solvent, and then vacuum-dried at a temperature at which the metal complex is not decomposed (for example, 25 to 250 ° C.) for several hours. Thus, the porous metal complex used in the present invention can be obtained. Cleaning with an organic solvent and vacuum drying can be replaced by cleaning with supercritical carbon dioxide, which is more effective.

The composition ratio of each component constituting the metal complex can be confirmed by, for example, single crystal X-ray structure analysis, powder X-ray crystal structure analysis or elemental analysis, but is not limited thereto.

The porous metal complex of the present invention can be suitably used for a polymer production method described later, a vinyl ester copolymer production described later, and the like.

2. Polymer Production Method The polymer production method of the present invention comprises an aromatic compound (L) having at least two substituents having a terminal alkenyl group (for example, an aromatic polyvalent carboxylic acid compound (L1)), A porous metal complex containing a monomer (V) having an unsaturated double bond in the pores of a porous metal complex containing at least one metal ion selected from ions of metals belonging to groups 1 to 14 The aromatic compound (L) and the monomer (V) present therein are copolymerized.

At least one metal selected from an aromatic compound (L) having at least two substituents having a terminal alkenyl group and a metal ion belonging to groups 1 to 14 of the periodic table used in the method for producing a polymer of the present invention As the porous metal complex containing ions, the porous metal complex described in the aforementioned “1.” column can be suitably used. Among them, it is preferable to select a monomer having a structure in which a polymer chain to be grown substantially in a one-dimensional direction when a monomer is contained in the pores and polymerized. That is, it is preferable that the pores of the porous metal complex have a one-dimensional structure.

In the production method of the present invention, the monomer (V) having an unsaturated double bond is polymerized in the pores of the aforementioned porous metal complex, whereby the aromatic compound (L) in the porous metal complex is monomerized. A polymer containing a unit is synthesized. That is, the terminal alkenyl group of the aromatic compound (L) is copolymerized with the unsaturated double bond of the monomer (V).

The monomer (V) having an unsaturated double bond used in the present invention is not particularly limited as long as it is a size that can be accommodated in the pores of the porous metal complex. A compound having a saturated double bond is preferred. For example, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl formate, vinyl butyrate, vinyl n-caproate, vinyl isocaproate, vinyl octoate, vinyl trimethyl acetate, vinyl chloroacetate, vinyl trichloroacetate, vinyl trifluoroacetate, Vinyl esters such as vinyl benzoate; vinyl halides such as vinyl chloride and vinyl bromide, ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, butadiene, cyclopentene, cyclohexene, vinylcyclohexane, norbornene, norbornadiene Aliphatic alkenes such as; acrylic acid, methyl acrylate, methacrylic acid, methyl methacrylate and other (meth) acrylic acid and esters thereof; nitriles such as acrylonitrile and methacrylonitrile; Ren, vinyl naphthalene, aromatic vinyl compounds such as 4-vinylpyridine; and the like. Monomers may be used alone or in combination of two or more. Among these monomers, vinyl esters, (meth) acrylic acid and esters thereof are preferable from the viewpoint that functional sites can be imparted by saponification or modification, and vinyl esters are particularly preferable. In the present specification, “(meth) acrylic acid” means acrylic acid or methacrylic acid.

The monomer (V) needs to be accommodated in the pores of the porous metal complex. For example, the monomer (V) may be adsorbed in the pores of the porous metal complex. . As a method of adsorbing, when the monomer is a liquid, a method of directly contacting the porous metal complex with the monomer can be mentioned. At that time, it is preferable that necessary additives such as a radical polymerization initiator and a chain transfer agent described later are dissolved in the monomer and adsorbed simultaneously. Further, when the monomer is a gas, a method in which the porous metal complex and the monomer are brought into direct contact is preferable. Moreover, after dissolving a monomer in a suitable solvent, you may make it contact with a porous metal complex. Examples of the solvent used here include, for example, alcohols such as water, methanol, ethanol, pentane, hexane, heptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, decalin, and the like. Aliphatic hydrocarbons such as benzene, toluene, xylene, cumene, ethylbenzene, monochlorobenzene, and dichlorobenzene, and halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, and dichloroethane.

The monomer (V) is contained in the pores of the porous metal complex and the polymerization reaction of the monomer (V) proceeds in the pores of the porous metal complex. Verification can be made by powder X-ray diffraction according to the method.

Before the monomer is adsorbed in the pores of the porous metal complex, it is preferable to perform preliminary drying in a vacuum in order to remove moisture and solvent adsorbed on the porous metal complex.

As a method for initiating polymerization, a general method is used. For example, there is a method of irradiating with heating, ultraviolet rays or radiation in the presence of a radical polymerization initiator. There is also a method of heating or irradiating without the radical polymerization initiator present. There is also a method of performing cationic polymerization by acting an acidic substance.

Examples of the radical polymerization initiator used include compounds usually used as an initiator for radical polymerization. For example, di-tert-butyl peroxide, lauroyl peroxide, stearyl peroxide, benzoyl peroxide, tert-butyl peroxyneodecanate, tert-butyl peroxypivalate, dilauroyl peroxide, dicumyl peroxide, tert Organics such as butyl peroxy-2-ethylhexanoate, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane Peroxides: 2,2′-azobisisobutyronitrile, 2,2′-azobisisovaleronitrile, 1,1-azobis (1-cyclohexanecarbonitrile), 2,2′-azobis-4-methoxy -2,4-azobisisobutyronitrile, 2, Azo radical polymerization initiators such as' -azobis-2,4-dimethylvaleronitrile, 2,2'-azobis-2-methylbutyronitrile; alkylphenone-based photopolymerization initiators such as 1-hydroxy-cyclohexyl-phenyl-ketone Agents: triethylborane and the like. A polymerization initiator can be used individually by 1 type or in combination of 2 or more types. When the radical polymerization initiator is used, the radical polymerization reaction proceeds advantageously by accommodating the monomer (V) in the pores of the porous metal complex.

When performing radical polymerization, a chain transfer agent may be added to adjust the molecular weight. Examples of the chain transfer agent include n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, α-methylstyrene dimer, terpinolene, 1,4-butanedithiol, 1,6-hexanedithiol, ethylene glycol bisthiopropio Nate, butanediol bisthioglycolate, butanediol bisthiopropionate, hexanediol bisthioglycolate, hexanediol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, etc. Can be mentioned. A chain transfer agent can be used individually by 1 type or in combination of 2 or more types.

As the acidic substance used for initiating the polymerization, compounds usually used as an initiator for cationic polymerization are used. For example, Lewis acid such as aluminum chloride; Bronsted acid such as sulfuric acid and hydrochloric acid, triphenylsulfonium trifluoromethanesulfonate Photoacid generators such as; and the like. An acidic substance can be used individually by 1 type or in combination of 2 or more types.

The temperature at the time of copolymerization is selected in such a range that the polymerization proceeds, the monomer does not desorb from the porous metal complex, and the depolymerization of the polymer or the decomposition of the porous metal complex does not proceed. The range is preferably −50 to 400 ° C., more preferably 0 to 300 ° C., and still more preferably 0 to 200 ° C.

The polymer obtained by the production method of the present invention is usually obtained in a state of being accommodated in a porous metal complex. In the case of taking out only the polymer, for example, there is a method in which the porous metal complex is decomposed with an aqueous solution of a compound that coordinates to a metal ion such as aqueous ammonia or ethylenediaminetetraacetic acid, an acid or an alkaline aqueous solution. Since metal or the like may remain in the polymer, it is preferable to perform a washing operation with pure water, filter and dry.

When the aromatic compound (L) is an aromatic polyvalent carboxylic acid compound (L1), the polymer obtained by the production method of the present invention has a carboxyl group derived from the aromatic polyvalent carboxylic acid compound (L1). In the resulting polymer, the carboxyl group may be —COOH or a salt thereof. When the carboxyl group is in a salt state, it is preferably an alkali metal salt such as sodium or potassium.

FIG. 2 schematically shows an example of how the monomer is polymerized by the production method of the present invention. In FIG. 2, the monomer is taken into the pores of the porous metal complex. When the polymerization reaction is carried out in this state, the polymerization of the monomer reflects the shape of the pores, so that the monomer is polymerized one-dimensionally and a one-dimensionally oriented polymer can be obtained. . The one-dimensional orientation means that the polymer chains (which can be called “molecular chains”) are not entangled with each other as shown in the schematic diagram at the right end of FIG. It represents the state of being aligned in one direction. At this time, when the aromatic compound (L) constituting the porous metal complex is copolymerized together, the polymer chains are connected to form a crosslinked structure. Therefore, even after the metal complex is decomposed, the state in which the polymer chain is oriented in one dimension is maintained, and the structure of the portion exhibits pseudo-crystallinity. The polymer obtained by the production method of the present invention is superior in solvent resistance as compared with a polymer obtained by a usual method such as solution polymerization, and is not affected by a solvent that usually dissolves. Have. For example, polyvinyl acetate obtained by solution polymerization is dissolved in acetone, but the vinyl acetate copolymer obtained by the method of the present invention is not affected by acetone. Furthermore, since the polymer of the present invention (for example, vinyl ester copolymer) has a site that is closely cross-linked, it is excellent in heat resistance. Furthermore, it has features such as an increase in mechanical strength in the direction of the alignment axis, a decrease in linear expansion coefficient, and an increase in density, and it can be used for various applications.

The orientation state of the polymer chain can be evaluated by, for example, powder X-ray diffraction. Since amorphous and non-oriented polymer chains do not have a regular structure, no peak is observed in the X-ray diffraction pattern. On the other hand, in the X-ray diffraction pattern of the oriented polymer, since a peak is observed at a position corresponding to the distance between the polymers, it can be judged that the polymer is oriented. Moreover, the domain structure derived from the oriented polymer chain can also be observed by high-resolution transmission electron microscope observation. The interchain distance between polymer chains is determined by the structure of the aromatic compound (L). In a preferred embodiment of the production method of the present invention, the polymer chain distance of the obtained polymer is, for example, 0.4 to 0.6 nm.

Further, when the polymer obtained by the method of the present invention has a hydrolyzable functional group such as an ester bond or an amide bond in the side chain, the polymer can be modified by hydrolysis. For example, when vinyl acetate is used as a monomer, polyvinyl acetate obtained by polymerization by the production method of the present invention is taken out by the above method, a sodium hydroxide solution is added and a saponification step is performed, whereby a vinyl alcohol copolymer is obtained. A polymer can be obtained. The vinyl alcohol copolymer thus obtained is superior in solvent resistance and heat resistance as compared with the vinyl alcohol copolymer synthesized by a usual method. It is useful for applications.

Furthermore, the polymer obtained by the method of the present invention is excellent in heat resistance as compared with a polymer obtained by a usual method such as solution polymerization. For example, polystyrene obtained by solution polymerization is completely depolymerized by heating to 400 ° C. or higher, but styrene copolymer obtained by the method of the present invention is completely depolymerized by heat treatment at 400 to 600 ° C. It does not polymerize and forms char. Further, since the char is oriented in the same manner as the polymer before heat treatment, a characteristic carbon material can be obtained by heat-treating the polymer obtained by the method of the present invention.

3. Vinyl ester copolymer The vinyl ester copolymer of the present invention is a copolymer of a vinyl ester monomer and an aromatic compound (L) having a substituent having a terminal alkenyl group. A polymer chain containing an ester monomer in the main chain is crosslinked. Preferably, in the vinyl ester copolymer of the present invention, the polymer chain is one-dimensionally oriented.

In this specification, “vinyl ester copolymer” can be rephrased as “vinyl ester copolymer” and is used interchangeably.

The vinyl ester copolymer of the present invention is, for example, an aromatic fragrance which is a ligand constituting a porous metal complex by adsorbing a vinyl ester monomer into the pores of the porous metal complex described in the above-mentioned “1.” column. It can be obtained by copolymerizing the group compound (L) and a vinyl ester monomer.

The vinyl ester monomer that constitutes the vinyl ester copolymer of the present invention is not particularly limited as long as it is a size that can be accommodated in the pores of the porous metal complex used for the production. 2 to 12 vinyl esters are preferred.

Examples of the vinyl ester monomers include vinyl acetate, vinyl propionate, vinyl pivalate, vinyl formate, vinyl butyrate, vinyl n-caproate, vinyl isocaproate, vinyl octoate, vinyl trimethyl acetate, vinyl chloroacetate, trichloroacetic acid. Examples thereof include vinyl, vinyl trifluoroacetate, vinyl benzoate and the like. Monomers may be used alone or in combination of two or more. Among these monomers, vinyl acetate and vinyl pivalate are particularly preferable.

The vinyl ester copolymer of the present invention polymerizes the vinyl ester monomer in the pores of the porous metal complex described above, and the terminal alkenyl group that the aromatic compound (L) has and the vinyl group that the vinyl ester monomer has. It can be produced by copolymerization. In one embodiment of the present invention, the vinyl ester copolymer of the present invention can be obtained, for example, by the method for producing a polymer described in the aforementioned “2.” column.

A preferred embodiment of the vinyl ester copolymer of the present invention is characterized in that polymer chains (which can be referred to as “molecular chains”) are oriented one-dimensionally. “Oriented in one dimension” represents a state in which polymer chains are not entangled and arranged side by side in an extended chain state as shown in the schematic diagram at the right end of FIG. By polymerizing the vinyl ester monomer within the pores of the porous metal complex, the polymerization proceeds by reflecting the pore shape, so that the vinyl ester monomer has a one-dimensional chain-structured polymer chain. A vinyl ester copolymer can be obtained. At this time, when the aromatic compound (L) constituting the porous metal complex is copolymerized together, the polymer chains are connected to form a crosslinked structure. Therefore, even after the metal complex is decomposed, the state in which the polymer chain is oriented in one dimension is maintained, and the structure of the portion exhibits pseudo-crystallinity. As a result, the vinyl ester copolymer of the present invention is superior in solvent resistance compared to a vinyl ester polymer obtained by a usual method such as solution polymerization, and is not affected by a solvent that normally dissolves. Have. For example, polyvinyl acetate obtained by solution polymerization dissolves in acetone, but the vinyl ester copolymer of the present invention using vinyl acetate as a monomer does not dissolve in acetone. Furthermore, since the vinyl ester copolymer of the present invention has a site that is closely cross-linked, it is excellent in heat resistance. Furthermore, it has features such as an increase in mechanical strength in the direction of the alignment axis, a decrease in linear expansion coefficient, and an increase in density, and it can be used for various applications.

It can be evaluated by, for example, powder X-ray diffraction that the polymer chain derived from the vinyl ester monomer constituting the vinyl ester copolymer of the present invention is one-dimensionally oriented. Since amorphous and non-oriented polymer chains do not have a regular structure, no peak is observed in the X-ray diffraction pattern. On the other hand, in the X-ray diffraction pattern of the oriented polymer, since a peak is observed at a position corresponding to the distance between polymer chains, it can be judged that the polymer is oriented. Moreover, the domain structure derived from the oriented polymer chain can also be observed by high-resolution transmission electron microscope observation. The interchain distance between polymer chains is determined by the structure of the aromatic compound (L). A preferred polymer chain distance is 0.4 to 0.6 nm.

Also, the vinyl ester copolymer of the present invention can be modified by hydrolysis or the like. For example, a vinyl alcohol copolymer (vinyl alcohol copolymer) can be obtained by adding an alkali such as a sodium hydroxide solution to the vinyl ester copolymer of the present invention and performing a saponification step. It is considered that the vinyl alcohol copolymer thus obtained also maintains a state in which the polymer chain is one-dimensionally oriented. Therefore, it is superior in solvent resistance and heat resistance as compared with vinyl alcohol copolymers synthesized by a usual method such as solution polymerization, and thus is useful for various uses such as a base material for valuable metal recovery materials.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In addition, this invention is not limited to a following example. Analysis and evaluation in the following examples and comparative examples were carried out by the following methods.

(1) Measurement of powder X-ray diffraction pattern Using an X-ray diffractometer, the range of diffraction angle (2θ) = 5 to 30 ° was scanned and measured by a symmetric reflection method. Details of the measurement conditions are shown below.

<Analysis conditions>
Equipment: RINT2000 Ultimate made by Rigaku Corporation
X-ray source: CuKα (λ = 1.5418Å) 40 kV 200 mA
Goniometer: Vertical goniometer Detector: Scintillation counter Step width: 0.02 °
Slit: Divergent slit = 0.5 °
Receiving slit = 0.15mm
Scattering slit = 0.5 °
Scanning speed = 6 ° / min (when measuring metal complex (porous metal complex))
1 ° / min (when measuring polymer)

(2) Single crystal X-ray crystal structure analysis The obtained single crystal was mounted on a gonio head and measured using a single crystal X-ray diffractometer. Details of the measurement conditions are shown below.

<Analysis conditions>
Apparatus: SMART APEX II Ultra X-ray source manufactured by Bruker AXS Co., Ltd .: MoKα (λ = 0.10773Å) 50 kV 24 mA
Condensing mirror: HELIOS multilayer optics for Moration
Detector: APEX II CCD
Collimator: Φ0.42mm
Analysis software: SHELX-97

(3) Content ratio (x) of aromatic compound (L) (aromatic polyvalent carboxylic acid compound (L1)) in the metal complex
The content ratio (x) of (L) in all polyvalent carboxylic acid compound units (total of aromatic compound (L) and polyvalent carboxylic acid compound (D)) constituting the metal complex is about 20 mg of metal complex. It was dissolved in about 1 g of 0.05 mol / L ethylenediaminetetraacetic acid disodium heavy aqueous solution, ¹ H NMR measurement was carried out, and the integral ratio of the obtained spectrum was calculated. Details of the analysis conditions are described below.

<Analysis conditions>
Device: JNM A-500, manufactured by JEOL Ltd.
Resonance frequency: 500 MHz
Solvent: Heavy water Temperature: 25 ° C
Pulse repetition time: 5.0 seconds Integration count: 16 times

(4) Polymerization rate of monomer (V) (vinyl ester monomer) The polymerization rate (Conv) of monomer (V) (for example, vinyl ester monomer) when polymerized in a metal complex was determined by the following equation.

Conv = {1- (W _res / W _ads )} × 100 (%)
However, W _ads is the adsorption amount (% by weight) of the monomer (V) in the complex / monomer complex before polymerization, and W _res is the residual amount (weight) of the monomer (V) in the complex / polymer complex after polymerization. %) Respectively.

The adsorption amount W _ads (% by weight) of the monomer (V) in the complex / monomer complex before polymerization was determined as follows. 200 mg of the metal complex was placed in a 10 mL flask and vacuum dried at 25 ° C. for 4 hours. After the flask was cooled and filled with nitrogen, 1.5 mL of distilled and purified monomer (V) was added. After irradiation with ultrasonic waves for 1 minute, the mixture was allowed to stand for 30 minutes, and excess monomer (V) was distilled off under reduced pressure. The obtained sample was subjected to thermogravimetry, and W _ads was calculated from the weight W _I0 before the start of measurement and the weight W _{I200 at} 200 ° C. according to the following equation.

W _ads = {1- (W _I200 / W _I0 )} × 100 (%)
The residual amount W _res (% by weight) of the monomer (V) in the complex / polymer complex after polymerization was determined as follows. Thermogravimetry of the complex / polymer complex after polymerization was performed, and W _res was calculated from the weight W _P0 before the start of measurement and the weight W _{P200 at} 200 ° C. according to the following formula.

W _res = {1- (W _P200 / W _P0 )} × 100 (%)
Details of the analysis conditions for thermogravimetry used to calculate W _ads and W _res are shown below.

<Analysis conditions>
Apparatus: Thermo plus TG 8120 manufactured by Rigaku Corporation
Sample pan: Aluminum heating rate: 10 ° C / min Measurement range: 25 ° C to 500 ° C
Atmosphere: Nitrogen (50 mL / min)

(5) Copolymerization composition of aromatic compound (L) in polymer (C)
The copolymer composition (content of aromatic compound (L)) C (mol%) of the aromatic compound (L) (for example, aromatic polycarboxylic acid compound (L1)) in the polymer is determined by the following formula. It was.

_{C = {(1-W ads} ) y · f L / M L} / {(W ads -W res) / M V + (1-W ads) y · f L / M L}
However, f _L represents the weight fraction of the compound in the complex (L), it was calculated from the value of x. W _ads is the adsorption amount (wt%) of the monomer V in the complex / monomer complex before polymerization, W _res is the residual quantity (wt%) of the monomer V in the complex / polymer complex after polymerization, y is the mole fraction incorporated into the polymer by polymerization of the compound in the complex _(L), M L is the molecular weight of the compound (L), M _V respectively represent the molecular weight of the monomer V.

Of the compound (L) in the complex, the molar fraction (y) taken into the polymer by polymerization (copolymerization) was determined as follows. From the integral ratio of the spectrum and the value of x obtained by ¹ H NMR measurement of the solution from which the complex / polymer complex after polymerization was decomposed with 0.05 mol / L aqueous solution of disodium ethylenediaminetetraacetate and the precipitate was removed. Calculated. The measurement conditions for ¹ H NMR were the same as those described in (2) above.

(6) Solvent resistance of polymer 10 mg of the obtained polymer was immersed in 1 mL of acetone, and the change of the polymer after stirring for 3 minutes was visually determined.

Y: When there is no change in the appearance of the polymer N: When the polymer is dissolved or swollen in acetone

(7) IR measurement Measurement was performed using a Fourier transform infrared spectrophotometer (FT-IR) to analyze the polymer composition. Details of the measurement conditions are shown below.

<Analysis conditions>
Apparatus: Fourier transform infrared spectrophotometer JIR-5500 (manufactured by JEOL)
Mode: attenuated total reflection (ATR) method Measurement range: 500 to 4000 cm ⁻¹
Integration count: 128 times

In the following synthesis examples, examples and comparative examples, the anion derived from terephthalic acid is tp, the anion derived from 2,5-di (allyloxy) terephthalic acid is datp, and the anion derived from 2,5-divinylterephthalic acid is used. dvtp, 1,4-diazabicyclo [2.2.2] octane is expressed as ted.

(Synthesis Example 1)
133 mg (0.48 mmol) of 2,5-di (allyloxy) terephthalic acid and 452 mg (2.72 mmol) of terephthalic acid were put into a 250 ml flask, and 200 ml of dehydrated dimethylformamide was added and dissolved. Thereto was added 799 mg (3.2 mmol) of copper sulfate pentahydrate dissolved in 30 mL of dehydrated methanol, and the mixture was stirred at 25 ° C. for 48 hours. The product was removed by centrifugation, dispersed in 20 mL of dehydrated dimethylformamide, 359 mg (1.6 mmol) of 1,4-diazabicyclo [2.2.2] octane was dissolved in 13 mL of toluene and added at 130 ° C. for 24 hours. Stir. The deposited metal complex is centrifuged, washed with dehydrated dimethylformamide and dehydrated methanol, and then vacuum-dried at 130 ° C. and expressed by the chemical formula [Cu (tp) _1-x (datt) _x (ted) _0.5 ] _n Obtained 935 mg of the metal complex. The powder X-ray diffraction pattern of the obtained metal complex is shown in FIG. Further, the content x of 2,5-di (allyloxy) terephthalic acid (L) in all polyvalent carboxylic acid compound units in the metal complex was 0.01 (1 mol%).

(Synthesis Example 2)
178 mg (0.64 mmol) of 2,5-di (allyloxy) terephthalic acid and 425 mg (2.56 mmol) of terephthalic acid were put into a 250 ml flask, and 200 ml of dehydrated dimethylformamide was added and dissolved. Thereto was added 799 mg (3.2 mmol) of copper sulfate pentahydrate dissolved in 30 mL of dehydrated methanol, and the mixture was stirred at 25 ° C. for 48 hours. The product was removed by centrifugation, dispersed in 20 mL of dehydrated dimethylformamide, 359 mg (1.6 mmol) of 1,4-diazabicyclo [2.2.2] octane was dissolved in 13 mL of toluene and added at 130 ° C. for 24 hours. Stir. The deposited metal complex is centrifuged, washed with dehydrated dimethylformamide and dehydrated methanol, and then vacuum-dried at 130 ° C. and expressed by the chemical formula [Cu (tp) _1-x (datt) _x (ted) _0.5 ] _n Obtained 889 mg of the metal complex. The powder X-ray diffraction pattern of the obtained metal complex is shown in FIG. The content ratio x of 2,5-di (allyloxy) terephthalic acid (L) in all the polyvalent carboxylic acid compound units in the metal complex was 0.02 (2 mol%).

(Synthesis Example 3)
222 mg (0.8 mmol) of 2,5-di (allyloxy) terephthalic acid and 398 mg (2.4 mmol) of terephthalic acid were put into a 250 ml flask, and 200 ml of dehydrated dimethylformamide was added and dissolved. Thereto was added 799 mg (3.2 mmol) of copper sulfate pentahydrate dissolved in 30 mL of dehydrated methanol, and the mixture was stirred at 25 ° C. for 48 hours. The product was removed by centrifugation, dispersed in 20 mL of dehydrated dimethylformamide, 359 mg (1.6 mmol) of 1,4-diazabicyclo [2.2.2] octane was dissolved in 13 mL of toluene and added at 130 ° C. for 24 hours. Stir. The deposited metal complex is centrifuged, washed with dehydrated dimethylformamide and dehydrated methanol, and then vacuum-dried at 130 ° C. and expressed by the chemical formula [Cu (tp) _1-x (datt) _x (ted) _0.5 ] _n Obtained 868 mg of the metal complex. FIG. 5 shows a powder X-ray diffraction pattern of the obtained metal complex. Further, the content x of 2,5-di (allyloxy) terephthalic acid (L) in all the polyvalent carboxylic acid compound units in the metal complex was 0.03 (3 mol%).

(Synthesis Example 4)
119 mg (0.64 mmol) of 2,5-divinylterephthalic acid, 425 mg (2.56 mmol) of terephthalic acid, 606 mg (3.2 mmol) of zinc nitrate, 359 mg (1.6 mmol) of 1,4-diazabicyclo [2.2.2] octane ) Was added to a 250 ml flask, 200 ml of dehydrated dimethylformamide was added, and the mixture was stirred at 130 ° C. for 72 hours. The precipitated metal complex is centrifuged, washed with dehydrated methanol, and then vacuum-dried at 130 ° C. to express the metal complex represented by the chemical formula [Zn (tp) _1-x (dvtp) _x (ted) _0.5 ] _n 872 mg was obtained. The powder X-ray diffraction pattern of the obtained metal complex is shown in FIG. Further, the content x of 2,5-divinylterephthalic acid (L) in all the polyvalent carboxylic acid compound units in the metal complex was 0.05 (5 mol%).

(Comparative Synthesis Example 1)
531 mg (3.2 mmol) of terephthalic acid, 606 mg (3.2 mmol) of zinc nitrate and 359 mg of 1,4-diazabicyclo [2.2.2] octane (1.6 mmol) were put into a 250 ml flask, and 200 ml of dehydrated dimethylformamide was added. The mixture was stirred at 130 ° C. for 72 hours. The results of single crystal X-ray structural analysis of the metal complex obtained by centrifuging the deposited metal complex are shown below. The crystal structure was a three-dimensional integrated structure having one-dimensional pores as shown in FIG. Further, the precipitated crystals were washed with dehydrated methanol and then vacuum dried at 130 ° C. to obtain 1037 mg of a porous metal complex represented by the chemical formula [Zn (tp) (ted) _0.5 ] _n . FIG. 7 shows a powder X-ray diffraction pattern of the obtained metal complex.
Tetragonal (I4 / mcm)
a = 15.063 (2) Å
c = 19.247 (5) Å
V = 4367.1 (14) Å 3
Z = 4
R ₁ = 0.0414
GOF = 1.073

By comparing FIGS. 3 to 6 with FIG. 8, the crystal structure of the porous metal complex obtained in Synthesis Examples 1 to 4 is consistent with the crystal structure of the porous metal complex obtained in Comparative Synthesis Example 1. It was confirmed that the structure was a three-dimensional integrated structure having one-dimensional pores.

Example 1
200 mg of the metal complex obtained in Synthesis Example 1 was placed in a 10 mL flask and vacuum dried at 25 ° C. for 4 hours. After the flask was cooled and filled with nitrogen, 3.6 mg of 2,2′-azobisisobutyronitrile dissolved in 1.5 mL of distilled and purified vinyl acetate was added. After irradiating with ultrasonic waves for 1 minute, the mixture was allowed to stand for 30 minutes, and vinyl acetate that was not taken into the metal complex was removed under reduced pressure at a pressure of 2 kPa. The flask was again filled with nitrogen and heated at 70 ° C. for 48 hours to polymerize vinyl acetate. As a result of measuring a polymerization rate using a part of the obtained complex / polymer complex, it was 35%. To the obtained complex / polymer complex, 20 mL of 0.05 mol / L aqueous solution of disodium ethylenediaminetetraacetate was added and stirred at 25 ° C. for 16 hours. The produced white solid was removed by centrifugation, and then washed with distilled water until the washing solution became neutral. Then, the mixture was acidified with 2N hydrochloric acid, centrifuged and washed with distilled water three times, and vacuum dried to obtain 15 mg of vinyl acetate-2,5-di (allyloxy) terephthalic acid copolymer.

The results of IR measurement of the obtained copolymer are shown in FIG. The obtained vinyl acetate-2,5-di (allyloxy) terephthalic acid copolymer is a polymer mainly containing vinyl acetate-derived structural units because the peak pattern coincided with the polyvinyl acetate synthesized by solution polymerization. It was confirmed that there was. Further, the content of 2,5-di (allyloxy) terephthalic acid in the obtained polymer was 2 mol%.

Example 2
200 mg of the metal complex obtained in Synthesis Example 2 was placed in a 10 mL flask and vacuum dried at 25 ° C. for 4 hours. After the flask was cooled and filled with nitrogen, 3.6 mg of 2,2′-azobisisobutyronitrile dissolved in 1.5 mL of distilled and purified vinyl acetate was added. After irradiating with ultrasonic waves for 1 minute, the mixture was allowed to stand for 30 minutes, and vinyl acetate that was not taken into the metal complex was removed under reduced pressure at a pressure of 2 kPa. The flask was again filled with nitrogen and heated at 70 ° C. for 48 hours to polymerize vinyl acetate. As a result of measuring the polymerization rate using a part of the obtained complex / polymer complex, it was 28%. To the obtained complex / polymer complex, 20 mL of 0.05 mol / L aqueous solution of disodium ethylenediaminetetraacetate was added and stirred at 25 ° C. for 16 hours. The produced white solid was removed by centrifugation, and then washed with distilled water until the washing solution became neutral. Thereafter, the mixture was acidified with 2N hydrochloric acid, centrifuged and washed with distilled water three times, and vacuum dried to obtain 12 mg of vinyl acetate-2,5-di (allyloxy) terephthalic acid copolymer.

As in Example 1, it was confirmed by IR measurement that the main component of the obtained copolymer was polyvinyl acetate. Further, the content of 2,5-di (allyloxy) terephthalic acid in the obtained polymer was 3 mol%.

Example 3
200 mg of the metal complex obtained in Synthesis Example 3 was placed in a 10 mL flask and vacuum-dried at 25 ° C. for 4 hours. After the flask was cooled and filled with nitrogen, 3.6 mg of 2,2′-azobisisobutyronitrile dissolved in 1.5 mL of distilled and purified vinyl acetate was added. After irradiating with ultrasonic waves for 1 minute, the mixture was allowed to stand for 30 minutes, and vinyl acetate that was not taken into the metal complex was removed under reduced pressure at a pressure of 2 kPa. The flask was again filled with nitrogen and heated at 70 ° C. for 48 hours to polymerize vinyl acetate. As a result of measuring the polymerization rate using a part of the obtained complex / polymer complex, it was 30%. To the obtained complex / polymer complex, 20 mL of 0.05 mol / L aqueous solution of disodium ethylenediaminetetraacetate was added and stirred at 25 ° C. for 16 hours. The produced white solid was removed by centrifugation, and then washed with distilled water until the washing solution became neutral. Thereafter, the mixture was acidified with 2N hydrochloric acid, centrifuged and washed with distilled water three times, and vacuum dried to obtain 13 mg of vinyl acetate-2,5-di (allyloxy) terephthalic acid copolymer.

As in Example 1, it was confirmed by IR measurement that the main component of the obtained copolymer was polyvinyl acetate. Further, the content of 2,5-di (allyloxy) terephthalic acid in the obtained polymer was 4 mol%.

Example 4
200 mg of the metal complex obtained in Synthesis Example 4 was placed in a 10 mL flask and vacuum dried at 25 ° C. for 4 hours. After the flask was cooled and filled with nitrogen, 3.6 mg of 2,2′-azobisisobutyronitrile dissolved in 1.5 mL of distilled and purified methyl methacrylate was added. After irradiation with ultrasonic waves for 1 minute, the mixture was allowed to stand for 30 minutes, and methyl methacrylate that was not taken into the metal complex at a pressure of 2 kPa was distilled off under reduced pressure. The flask was again filled with nitrogen and heated at 70 ° C. for 24 hours to polymerize methyl methacrylate. As a result of measuring the polymerization rate using a part of the obtained complex / polymer complex, it was 69%. To the obtained complex / polymer complex, 20 mL of 0.05 mol / L aqueous solution of disodium ethylenediaminetetraacetate was added and stirred at 25 ° C. for 16 hours. The produced white solid was removed by centrifugation, and then washed with distilled water until the washing solution became neutral. Thereafter, the mixture was acidified with 2N hydrochloric acid, centrifuged and washed with distilled water three times, and vacuum-dried to obtain 26 mg of methyl methacrylate-2,5-divinylterephthalic acid copolymer.

In the same manner as in Example 1, it was confirmed by IR measurement that the main component of the obtained copolymer was polymethyl methacrylate. Further, the content of 2,5-divinylterephthalic acid in the obtained polymer was 5 mol%.

Example 5
200 mg of the complex obtained in Synthesis Example 4 was placed in a 10 mL flask and vacuum dried at 25 ° C. for 4 hours. After the flask was cooled and filled with nitrogen, 3.6 mg of 2,2′-azobisisobutyronitrile dissolved in 1.5 mL of distilled styrene was added. After irradiation with ultrasonic waves for 1 minute, the mixture was allowed to stand for 30 minutes, and styrene was distilled off under reduced pressure at 2 kPa. The flask was again filled with nitrogen and heated at 70 ° C. for 24 hours to polymerize the monomer. As a result of measuring a polymerization rate using a part of the obtained complex / polymer complex, it was 38%. 20 ml of a 0.05 mol / L aqueous solution of disodium ethylenediaminetetraacetate was added to the remaining complex / polymer complex, and the mixture was stirred at 25 ° C. for 16 hours. The produced white solid was taken out by centrifugation, and washed with distilled water until the washing solution became neutral. Thereafter, the mixture was acidified with 2N hydrochloric acid, centrifuged and washed with distilled water three times, and vacuum dried to obtain 18 mg of a styrene-2,5-divinylterephthalic acid copolymer.

As in Example 1, it was confirmed by IR measurement that the main component of the obtained copolymer was styrene. The content of 2,5-divinylterephthalic acid in the obtained polymer was 8 mol%.

The styrene-2,5-divinylterephthalic acid copolymer (15 mg) obtained above was heat-treated at 500 ° C. for 30 minutes in a nitrogen atmosphere to obtain 6 mg of black char. The distance between the chains of the polymer constituting the char was measured and found to be 4.8 mm.

All of the copolymers obtained by the methods described in Examples 1 to 5 above were measured for powder X-ray diffraction patterns, and clear peaks were observed. Based on the value of Bragg from the value of 2θ, the distance between polymer chains (distance between molecular chains) could be obtained. The polymer chain distance d was determined from d = λ / (2 sin θ) where θ is the angle formed by the polymer chain and the X-ray, and λ is the wavelength of the X-ray. In any measurement result, a peak was observed at 2θ = 18 °, and thus the polymer chain distance was 0.49 nm. This is because 2,5-di (allyloxy) terephthalic acid or 2,5-di (allyloxy) terephthalic acid in a state where the polymer chain of the structural unit derived from the monomer (V) (vinyl ester monomer) is oriented with a distance of 0.49 nm between the chains. This is considered to indicate that it has a structure crosslinked by a structural unit derived from divinylterephthalic acid.

Comparative Example 1
200 mg of the metal complex obtained in Comparative Synthesis Example 1 was placed in a 10 mL flask and vacuum dried at 25 ° C. for 4 hours. After the flask was cooled and filled with nitrogen, 3.6 mg of 2,2′-azobisisobutyronitrile dissolved in 1.5 mL of distilled and purified vinyl acetate was added. After irradiating with ultrasonic waves for 1 minute, the mixture was allowed to stand for 30 minutes, and vinyl acetate that was not taken into the metal complex was removed under reduced pressure at a pressure of 2 kPa. The flask was again filled with nitrogen and heated at 70 ° C. for 48 hours to polymerize vinyl acetate. As a result of measuring a polymerization rate using a part of the obtained complex / polymer complex, it was 38%. To the obtained complex / polymer complex, 20 mL of 0.05 mol / L aqueous solution of disodium ethylenediaminetetraacetate was added and stirred at 25 ° C. for 16 hours. The produced white solid was removed by centrifugation, and then washed with distilled water until the washing solution became neutral. Thereafter, the solution was acidified with 2N hydrochloric acid, centrifuged and washed with distilled water three times, and vacuum dried to obtain 19 mg of polyvinyl acetate.

As in Example 1, since the peak patterns of the obtained polyvinyl acetate and the polyvinyl acetate synthesized by solution polymerization matched by IR measurement, it was confirmed to be polyvinyl acetate.

Comparative Example 2
To a 100 mL flask, 4.75 g of vinyl acetate, 0.25 g of divinylbenzene, and 100 mg of 2,2′-azobisisobutyronitrile were added and dissolved in 5 g of toluene, and the system was purged with nitrogen. By heating at 70 ° C. for 6 hours, vinyl acetate was polymerized. After completion of the reaction, the polymer was reprecipitated by putting the reaction solution into 100 mL of hexane, filtered and vacuum dried to obtain 0.9 g of a polyvinyl acetate-divinylbenzene copolymer.

When the powders obtained by the methods described in Comparative Examples 1 and 2 were measured for the powder X-ray diffraction pattern, no clear peak was observed, and the polymer chain was not oriented.

Various physical properties of the polymers obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were measured and evaluated under the measurement conditions described above. The results are shown in Table 1.

From the results of Examples 1 to 4, the polymer (vinyl ester copolymer) obtained by the production method of the present invention is a polymer chain having a structural unit derived from the monomer (V) (vinyl acetate or methyl methacrylate) as the main chain. Has a structure crosslinked with a structural unit derived from 2,5-di (allyloxy) terephthalic acid or 2,5-divinylterephthalic acid in an oriented state with an interchain distance of 0.49 nm. It became clear that it was excellent in solvent property. The reason why such an effect can be obtained is not clear, but when the polymer chain is regularly oriented and crosslinked by the aromatic polyvalent carboxylic acid compound (L1), the part has crystallinity, We believe that the solvent resistance of the polymer (vinyl ester copolymer) as a whole has improved.

On the other hand, from Comparative Example 1, when the metal complex as the reaction field does not contain the aromatic polyvalent carboxylic acid compound (L1) having two or more substituents having a terminal alkenyl group, the monomer (V) (vinyl acetate) ) Proceeds but the polymer chain is not cross-linked by the compound (L1), so the orientation of the polymer chain cannot be maintained, resulting in poor solvent resistance. Further, from Comparative Example 2, a monomer (V) (vinyl acetate) and an aromatic polyvalent carboxylic acid compound (L1) having two or more substituents having a terminal alkenyl group were used without using a porous metal complex. When polymerized, the polymer chain was not oriented, and the resulting polymer was inferior in solvent resistance.

Further, from Example 5, it was revealed that the polymer obtained by the production method of the present invention is excellent in heat resistance and can be carbonized by heat treatment at a high temperature of 500 ° C.

Claims (15)

1. A porous material comprising an aromatic polyvalent carboxylic acid compound (L1) having at least two substituents having a terminal alkenyl group and at least one metal ion selected from ions of metals belonging to Groups 1 to 14 of the periodic table A polymer comprising a monomer (V) having an unsaturated double bond in the pores of a conductive metal complex to obtain a polymer containing the aromatic polyvalent carboxylic acid compound (L1) as a constituent unit Manufacturing method.
2. The method for producing a polymer according to claim 1, wherein the aromatic polycarboxylic acid compound (L1) is a compound represented by the following general formula (1) or (2):
   

   

   

   (In the formula, A ¹ and A ² are carboxyl groups, and at least two of B ¹ to B ⁴ are the same or different, and the following general formula (3)
   

   

   ^{(Y 1} and ^{Y 2} are the same or different oxygen atom, a sulfur atom or -O-CO-, ^[Y 1 - _{(CH 2) a]} is ^{Y 1} and a is the same or different from each other in each repeating unit A is 1 to 5, b is 0 to 5, c is 0 or 1, and d is an integer of 0 to 5. R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxycarbonyl group. is there)
   The substituents having a terminal alkenyl group represented by general formula (3) among B ¹ to B ⁴ are the same or different and have a hydrogen atom, a halogen atom or a substituent. Selected from the group consisting of an alkyl group, an alkoxy group, a thioalkyl group, a formyl group, an acyloxy group, an alkoxycarbonyl group, a nitro group, a cyano group, an amino group, a monoalkylamino group, a dialkylamino group, an acylamino group, and a carboxyl group Is any substituent. )
3. The method for producing a polymer according to claim 1 or 2, wherein the porous metal complex further contains a polyvalent carboxylic acid compound (D) different from the aromatic polyvalent carboxylic acid compound (L1).
4. The method for producing a polymer according to claim 3, wherein the polyvalent carboxylic acid compound (D) is an aromatic dicarboxylic acid compound having no terminal alkenyl group.
5. The method for producing a polymer according to any one of claims 1 to 4, wherein the porous metal complex further contains an organic ligand capable of multidentate coordination with the metal ion.
6. The method for producing a polymer according to any one of claims 1 to 5, wherein the monomer (V) having an unsaturated double bond is a vinyl ester.
7. A method for producing a carbon material, wherein the polymer obtained by the method according to any one of claims 1 to 6 is heat-treated at a temperature of 400 ° C to 600 ° C.
8. A copolymer of a vinyl ester monomer and an aromatic compound (L) represented by the following general formula (1) or (2) having at least two substituents having a terminal alkenyl group, the aromatic compound A vinyl ester copolymer characterized in that a polymer chain containing a vinyl ester monomer in the main chain is crosslinked by (L).
   

   

   

   (In the formula, A ¹ and A ² are the same or different and have the following general formula:
   

   

   A carboxyl group represented by
   

   

   A pyridyl group represented by
   

   

   An imidazolyl group represented by:
   

   

   A triazolyl group represented by
   

   

   And X is a hydrogen atom or an alkali metal atom. At least two of B ¹ to B ⁴ are substituents having the same or different terminal alkenyl groups, and the others are hydrogen atom, halogen atom, alkyl group, alkoxy group, thioalkyl group, formyl group, acyloxy group, alkoxycarbonyl A substituent selected from the group consisting of a group, a nitro group, a cyano group, an amino group, a monoalkylamino group, a dialkylamino group, an acylamino group, a carboxyl group, and an alkali metal salt of a carboxyl group. )
9. The vinyl ester copolymer according to claim 8, wherein the polymer chain is one-dimensionally oriented.
10. The substituent having the terminal alkenyl group is represented by the following general formula (3):
    

    

    (Wherein, ^{Y 1} and ^{Y 2} are the same or different oxygen atom, a sulfur atom or -O-CO-, ^[Y 1 - _{(CH 2) a]} are the same or ^{Y 1} and a is in each repeating unit A is 1 to 5, b is 0 to 5, c is 0 or 1, and d is an integer of 0 to 5. R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or alkoxycarbonyl Base)
    The vinyl ester copolymer according to claim 8 or 9, which is a substituent represented by:
11. A polyvinyl copolymer obtained by saponifying the copolymer according to any one of claims 8 to 10.
12. An aromatic polycarboxylic acid compound (L1) having at least two substituents having a terminal alkenyl group, a polyvalent carboxylic acid compound (D) different from the aromatic polycarboxylic acid compound (L1), and ions of metals belonging to Groups 1 to 14 of the periodic table A porous metal complex comprising at least one metal ion selected.
13. The porous metal complex according to claim 12, wherein the aromatic polycarboxylic acid compound (L1) is a compound represented by the following general formula (1) or (2):
    

    

    

    (In the formula, A ¹ and A ² are carboxyl groups, and at least two of B ¹ to B ⁴ are the same or different, and the following general formula (3)
    

    

    (In Formula (3), Y ¹ and Y ² are the same or different and are an oxygen atom, a sulfur atom, or —O—CO—, and [Y ¹ — (CH ₂ ) _a ] represents Y ¹ and a for each repeating unit. May be the same or different, a is 1 to 5, b is 0 to 5, c is 0 or 1, and d is an integer of 0 to 5. R is a hydrogen atom, an alkyl having 1 to 5 carbon atoms Group or alkoxycarbonyl group)
    The substituents having a terminal alkenyl group represented by general formula (3) among B ¹ to B ⁴ are the same or different and have a hydrogen atom, a halogen atom or a substituent. Selected from the group consisting of an alkyl group, an alkoxy group, a thioalkyl group, a formyl group, an acyloxy group, an alkoxycarbonyl group, a nitro group, a cyano group, an amino group, a monoalkylamino group, a dialkylamino group, an acylamino group, and a carboxyl group Is any substituent. ).
14. The porous metal complex according to claim 12 or 13, wherein the polyvalent carboxylic acid compound (D) is an aromatic dicarboxylic acid compound having no terminal alkenyl group.
15. The porous metal complex according to any one of claims 12 to 14, wherein the porous metal complex further comprises an organic ligand capable of multidentate coordination with the metal ion.

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