KR101075258B1 - Porous Adamantane -Based Polymers and the Method for Preparing the Same - Google Patents

Abstract

The present invention relates to porous adamantane-based compounds and polymers and methods for their preparation. Specifically, 1-bromo adamantane and phenyl halide are modified to prepare a building block of porous polymer, and microporous is prepared by reacting them under a palladium (II) (Pd (II)) and a copper iodide (CuI) catalyst. The present invention relates to a porous compound prepared by reacting a microporous porous compound, an adamantane derivative, and a boronic acid derivative under a Pd (II) catalyst. Porous compounds prepared from this material have high specific surface areas and small pore sizes.

Porous material, extreme surface area, adamantane, microporous, gas storage, pollutant adsorption

Description

Porous Adamantane-Based Compounds and Methods for Preparing the Same {Porous Adamantane -Based Polymers and the Method for Preparing the Same}

The present invention relates to the synthesis of adamantane-based compounds and to the preparation of polymers thereof. Specifically, 1-bromoadamantane (1-bromoadamantane) and phenyl halide (modified phenyl halide) to prepare a building block of a porous polymer And palladium, a microporous porous compound prepared by reacting these under a palladium (II) (Pd (II)) and a copper iodide (CuI) catalyst, an adamantane derivative and a boronic acid derivative. The present invention relates to a porous compound prepared by reacting under a (II) (Pd (II)) catalyst and a method for producing the same. The specific surface area and pore size can be controlled by changing the phenyl halide and boronic acid derivatives. The porous compound thus prepared may be used for adsorption of gases such as hydrogen, carbon dioxide, and methane and removal of contaminants.

As the environmental pollution and energy depletion caused by industrialization have emerged, the use of porous materials for the purification of pollutants and the storage of gas fuel has been attracting attention. Contaminants can be removed by adsorbing the contaminants into the pores or removing the contaminants by catalytic reaction. Porous materials can adsorb a lot of materials due to their high specific surface area, and can control the storage and separation of compounds by controlling mutual attraction of the adsorbents and the inner wall of the pores.

Due to high oil prices due to the depletion of fossil fuels, the development of next-generation green alternative energy is indispensable for the survival of humanity. In addition, global warming is progressing rapidly due to greenhouse gases such as carbon dioxide. To solve this problem, new energy without greenhouse gas emission is needed. Among the candidates, hydrogen gas is the most attracting substance. However, hydrogen requires very low temperatures or very high pressures for liquefaction. This liquefaction condition is a big obstacle in storing and using hydrogen as energy. Especially in vehicles such as cars, stability is of paramount importance. To this end, the hydrogen storage medium should have high hydrogen storage capacity at room temperature and atmospheric pressure. To this end, Yaghi et al., UCLA, USA, prepared a structure using a metal salt as a metal source and substitution reaction of ligand ions. The metal-organic framwork thus prepared has a high specific surface area of 400-4500 m ² / g and a small pore size of 0.6-2 nm [Andrew R. Millward, Omar M. Yaghi, J. AM. . CHEM. SOC. 2005, 127, 17998-17999]. However, in the metal-organic structure, overcoming the coordination bond between the metal and the organic ligand is easily broken by water or acid, which remains a big challenge. Budd et al. Of Manchester University, England, prepared a porous polymer having nano-sized pores by crosslinking organic polymers and measured their hydrogen storage ability [Peter M. Budd, Neil B. McKeownb and Detlev Fritsch, J. Mater. Chem., 2005, 15, 1977.1986]. The porous polymer thus prepared overcomes the instability of the structure, which is a disadvantage of the metal-organic structure, but exhibits a lower specific surface area and hydrogen storage ability than the metal-organic structure. Therefore, the present inventors have tried to prepare a porous material having a high specific surface area, high gas storage capacity and structural stability, and for this purpose, modified mann halide and various phenyl halides, which can be used as a building block of a porous body. The present invention was completed by polymerizing the building blocks thus prepared in the presence of Pd (II) and CuI or Pd (II) and K ₂ CO ₃ to prepare a porous compound.

The present invention is to provide a porous compound having a high gas storage capacity and structural stability using a building block prepared by modifying adamantane and phenyl halide.

In order to solve the above problems, according to a preferred embodiment of the present invention, there is provided a porous compound having a structure of formula (I).

(I)

In Formula I, R ₁ is _one selected from the group consisting of 1,4-phenylene and 4,4-biphenylene and R ₂ is 1,4-phenylene, 4,4-biphenylene, 2,6 It is 1 type selected from the group which consists of naphthalene.

According to another suitable embodiment of the present invention, there is provided a process for preparing the porous compound of claim 1 by reacting a compound of formula II with palladium (II) (Pd (II)) and copper iodide (CuI) in the presence of to provide.

[Formula II]

R ₃ in Formula II is one selected from the group consisting of 4-iodinephenyl, 4-bromophenyl, 4-iodinebiphenyl, 4-bromobiphenyl.

[Formula III]

R ₂ in Formula III is one selected from the group consisting of 1,4-phenylene, 4,4-biphenylene and 2,6-naphthalene and n is 2.

According to another suitable embodiment of the present invention, a porous compound having the structure of formula IV is provided.

[Formula IV]

R ₁ in Chemical Formula IV is _one selected from the group consisting of 1,4-phenylene and 4,4-biphenylene, R ₄ is 1 type selected from the group consisting of 1,4-phenylene, 4,4-biphenylene and 2,6-naphthalene.

According to another suitable embodiment of the invention, the compound of formula II is reacted with the compound of formula V in the presence of palladium (II) (Pd (II)) and potassium carbonate (K ₂ CO ₃ ) to Provided are methods for preparing the compounds.

[Formula Ⅴ]

In Formula V, n is 2, and R ₄ is 1 type selected from the group consisting of 1,4-phenylene, 4,4-biphenylene and 2,6-naphthalene.

The porous compound provided by the present invention can be used for storing gas, purifying pollutants or supporting catalyst due to high specific surface area and small pore size, and replacement is made of covalent bonds having high chemical and thermal stability. Thus, high durability can be provided.

In the present invention, four phenyl groups were introduced into 1-bromoadamantane and then modified with halogen, and acetylene groups were introduced into various phenyl halides to synthesize porous building blocks. Thus prepared building blocks were polymerized in the presence of Pd (II) and CuI or Pd (II) and boronic acid derivatives, and the specific surface area and pore size of the porous bodies were similar to those of phenylene or boronic acid derivatives with acetylene. Adjustment was made by changing the size.

The present invention largely consists of synthesizing a building block of a porous body by modifying adamantane and phenyl halide and preparing a porous polymer compound by polymerizing these building blocks, which will be described in more detail below.

The adamantane derivatives substituted with aromatics of the present invention have the structure of formula (II).

[Formula II]

R ₃ in Formula II is one selected from the group consisting of 4-iodinephenyl, 4-bromophenyl, 4-iodinebiphenyl, 4-bromobiphenyl.

In addition, the phenyl derivative in which acetylene is introduced has a structure of Formula III.

[Formula III]

R ₂ in Formula III is one selected from the group consisting of 1,4-phenylene, 4,4-biphenylene and 2,6-naphthalene, and n is 2.

In addition, the boronic acid derivative has the structure of Formula (V).

[Formula Ⅴ]

In Formula V, n is 2, and R ₄ is one selected from the group consisting of 1,4-phenylene, 4,4-biphenylene and 2,6-naphthalene.

In addition, the structure of the porous polymer in the present invention has a structure such as formula (I) or (IV).

(I)

[Formula IV]

In the above formula R _{1 ,} R ₂ Wow R ₄ Is as defined above.

The compounds of Formula II may be prepared by the following method.

1) preparing an adamantane derivative by reacting benzene or biphenyl dissolved in an organic solvent with 1-bromoadamantane in the presence of lewis acid:

2) separating the adamantane derivative obtained in step 1):

3) dissolving the compound obtained in step 2) in an organic solvent and reacting with iodine (I ₂ ) or bromine (Br ₂ ) in the presence of bis (trifluoroacetoxy) iodo (benzene):

4) separating the adamantane derivative obtained in step 3).

The compounds of Formula I may be prepared by the following preparation method.

1) reacting a compound of formula (II) with a compound of formula (III) in the presence of palladium (II) (Pd (II)) and copper iodide (CuI) to prepare a porous crosslink: 2) porous crosslinking obtained in step 1) Separating and purifying the sieve.

The compounds of formula IV may be prepared by the following preparation method.

1) reacting a compound of formula (II) with a compound of formula (V) in the presence of palladium (II) (Pd (II)), K ₂ CO ₃ to produce a porous crosslinked product: 2) the porous crosslinked product obtained in step 1) Separating and purifying.

In the following, the present invention will be described in more detail with reference to Examples. However, the scope of the present invention is not limited by these examples.

¹ H and ¹³ C NMR spectral analyzes of the compounds of the present invention were measured using a BRUKER Avance DPX-300 and Avance 500 spectrometer, and specific surface area and pore size analysis of porous materials were performed using BELSORP-max from BEL-Japan. Hydrogen adsorption capacity was measured using MSB ISOSORP of Rubothrm GmbH, and the shape of the porous body was observed using JEOL JEMF-6330F.

[ Example  1] 1,4-ditrimethylsilylethynylbenzene (1,4-di ( trimethylsillylethynyl ) benzene ) Synthesis

In a solution of 3 g of 1,4-diiodobenzene (3 g) in 50 ml of triethylamine, 0.54 g of dichlorobis (triphenylphosphine) palladium and copper iodide ( Add 0.0067 g of copper iodine), stir at room temperature for 30 minutes, and then add 2.68 g of trimethylsillyacethylene. After stirring at room temperature for 24 hours, the salt is removed by filtration. After the solvent is removed and concentrated, the compound is separated by column chromatography.

¹ H NMR (CDCl ₃ ): δ = 7.43 (s, C ₆ H ₄ , 4H), 0.80 (s, -Si (CH ₃ ) ₃ , 18H).

[ Example  2] 1,4- Of diethynylbenzene (1,4-diethynylbenzene)  synthesis

3.3 g of 1,4-ditrimethylsilylethynylbenzene was dissolved in 50 ml of tetrahydrofuran / methanol (1: 1), and 0.83 g of KOH was added at room temperature. After stirring for hours, the salts are removed by filtration. After removing the solvent, the compound is separated by recrystallization with methanol.

¹ H NMR (CDCl ₃ ): δ = 7.43 (s, C ₆ H ₄ , 4H), 3.48 (s, ≡CH, 2H).

[ Example  3] 4,4-ditrimethylsilylethynylbiphenyl (4,4- di  Synthesis of (trimethylsillylethynyl) biphenyl)

0.14 g of dichlorobis (triphenylphosphine) palladium and copper iodide in a solution of 2 g of 4,4-diiodobiphenyl (4,4-diiodobiphenyl) in 50 ml of triethylamine. 0.02 g of copper iodine) was added thereto, stirred at room temperature for 30 minutes, and then 1.18 g of trimethylsillyacethylene was added thereto. After stirring at room temperature for 24 hours, the salt is removed by filtration. After the solvent is removed and concentrated, the compound is separated by column chromatography.

¹ H NMR (CDCl ₃ ): δ = 7.63 (d, C ₆ H ₄ , 4H), 7.63 (d, C ₆ H ₄ , 4H), 0.80 (s, -Si (CH ₃ ) ₃ , 18H).

[ Example  4] 4,4-diethynylbiphenyl (4,4- diethynylbiphenyl ) Synthesis

1.4 g of 4,4-ditrimethylsilylethynylbiphenyl (4,4-di (trimethylsillylethynyl) biphenyl) dissolved in 50 ml of tetrahydrofuran / methanol (1: 1) was added 0.70 g of KOH to room temperature for 5 hours. Stir for and filter to remove salt. After concentration by removing the solvent, the compound is separated by recrystallization with methanol.

¹ H NMR (CDCl ₃ ): δ = 7.63 (d, C ₆ H ₄ , 4H), 7.63 (d, C ₆ H ₄ , 4H), 3.48 (s, ≡CH, 2H).

[ Example  5] 2,6-ditrimethylsilylethynylnaphthalene (2,6- di  Synthesis of (trimethylsillylethynyl) napthalene)

In a solution of 2 g of 2,6-diiodonapthalene in 50 ml of triethylamine, 0.35 g of dichlorobis (triphenylphosphine) palladium and 0.38 g of copper iodide (copper) iodine) 0.05g was added and stirred at room temperature for 30 minutes, followed by adding 1.24g of trimethylsillyacethylene. After stirring at room temperature for 24 hours, the salt is removed by filtration. After the solvent is removed and concentrated, the compound is separated by column chromatography.

¹ H NMR (CDCl ₃ ): δ = 8.29 (d, C ₆ H ₄ , 2H), 7.78 (d, C ₆ H ₄ , 2H), 7.53 (d, C ₆ H ₄ , 2H) 0.80 (s,- Si (CH ₃ ) ₃ , 18H).

[ Example  6] 2,6-diethynyl naphthalene (2,6- diethynylnapthalene ) Synthesis

0.80 g of 2,6-ditrimethylsilylethynylnaphthalene (2,6-di (trimethylsillylethynyl) napthalene) was dissolved in 50 ml of tetrahydrofuran / methanol (1: 1), and KOH 0.80 g was stirred at room temperature for 5 hours. And then filtered to remove salts. After concentration by removing the solvent, the compound is separated by recrystallization with methanol.

¹ H NMR (CDCl ₃ ): δ = 8.29 (d, C ₆ H ₄ , 2H), 7.78 (d, C ₆ H ₄ , 2H), 7.53 (d, C ₆ H ₄ , 2H) 3.48 (s, ≡ CH, 2H).

[ Example  7] 1,3,5,7- Tetrakis (4-iodinephenyl) adamantane (1,3,5,7- tetrakis  Synthesis of (4-iodophenyl) adamantane)

The compounds are prepared according to the methods of the reported literature. Veronica R. Reichert and Lon J. Mathias, Macromolecules, 1994, 27, 7015-70 23.

[ Manufacturing example  1] Preparation and Post-treatment of Porous Polymer

The compounds prepared in Examples 2, 4, and 6 were dissolved in methylpyrrolidone (N-methylpyrrolidone) and triethylamine, and then Pd (II) and CuI were added thereto, Reaction with the compound produces a polymer. At this time, the volume ratio of en methylpyrrolidone and triethylamine is changed at 2: 8 to 8: 2, and the polymer is prepared while the reaction temperature is changed from room temperature to 100 ° C. The filtered compound was added to tetrahydrofuran and stirred for 48 hours to remove residual material in the pores, followed by drying in vacuum at 150 ° C. for 48 hours to remove the solvent in the pores.

[ Manufacturing example  2] Preparation and Post-treatment of Porous Polymer

The compound prepared in Example 7 was dissolved in 1,4-dioxane (1,4-dioxane), and then Pd (II) and K ₂ CO ₃ were added and reacted with the compound of Formula V to prepare a polymer. At this time, the reaction temperature was reacted while changing from room temperature to 100 ℃. The filtered compound was added to tetrahydrofuran and stirred for 48 hours to remove residual material in the pores, followed by drying in vacuum at 150 ° C. for 48 hours to remove the solvent in the pores.

[ Test Example  1] of the porous body produced by the present invention Specific surface area  And pore size analysis test

Nitrogen adsorption and desorption experiments were conducted to test the specific surface area and pore size of the porous compounds prepared in Preparation Examples 1 and 2. As a result, the specific surface area of the polymer of Formula I in which R ₁ is phenyl and R ₂ is phenyl was 900 m ² / g, and the average pore size was 3.77 nm. The results are shown in Figs. In the formula (IV), the specific surface area of the polymer wherein R ₁ is phenyl and R ₃ is phenyl was 700 m ² / g, and the average size of the pores was 2.35 nm, respectively. The results are shown in Figures 3-4.

[ Test Example  2] shape control experiment of porous body produced by the present invention

In [Production Example 1] it is possible to control the form of the porous polymer by changing the volume ratio and temperature of the organic solvent. The morphology of the controlled polymer is shown in FIGS. 5 and 6.

The porous material provided by the present invention has a high specific surface area and a small pore size. As a result, the material can be used as a storage medium for gases such as hydrogen and methane or as an adsorbent for pollutants such as carbon dioxide and environmental hormones. In addition, the specific surface area and pore size can be controlled by controlling the size of the building block, thereby enabling the application of a specific material as a selective adsorbent.

1 is a graph of nitrogen adsorption (a) desorption (b) of a polymer of formula I according to the present invention wherein R ₁ is 1,4-phenylene and R ₂ is 1,4-phenylene.

2 is a HK (Horvath-Kawazoe) plot of a polymer in which R ₁ is 1,4-phenylene and R ₂ is 1,4-phenylene in formula (I) according to the present invention.

3 is a graph of adsorption (a) desorption (b) of a polymer in which R ₁ is 1,4-phenylene and R ₄ is 1,4-phenylene in formula (IV) according to the present invention.

4 is a HK (Horvath-Kawazoe) plot of a polymer in which R ₁ is 1,4-phenylene and R ₄ is 1,4-phenylene in formula (IV) according to the present invention.

5 is a scanning electron microscope (FE-SEM, Field Emission) of a polymer prepared in a polymer of formula I according to the invention R ₁ is 1,4-phenylene, R ₂ is 1,4-phenylene at 25 ℃ Scanning Electron Microscope).

6 is a scanning electron micrograph of a polymer prepared at 100 ° C. in a polymer of Formula IV according to the present invention, wherein R ₁ is 1,4-phenylene and R ₄ is 1,4-phenylene.

Claims (4)

A porous compound having the structure of formula (I) (I)

(In the above formula, R ₁ is _one selected from the group consisting of 1,4-phenylene and 4,4-biphenylene and R ₂ is 1,4-phenylene, 4,4-biphenylene and 2,6 It is one selected from the group consisting of naphthalene.) A process for preparing the porous compound of claim 1 by reacting a compound of formula II with the following formula III in the presence of palladium (II) (Pd (II)) and copper iodide (CuI). [Formula II]

(In the above formula, R ₃ is one selected from the group consisting of 4-iodinephenyl, 4-bromophenyl, 4-iodinebiphenyl, 4-bromobiphenyl.) [Formula III]

(In the above formula, R ₂ is one selected from the group consisting of 1,4-biphenyl, 4,4-biphenylene and 2,6-naphthalene and n is 2.) A porous compound having the structure of formula IV. [Formula IV]

(In the above formula, R ₁ is one selected from the group consisting of 1,4-phenylene and 4,4-biphenylene, R ₄ is one selected from the group consisting of 1,4-phenylene, 1,4-biphenylene and 2,6-naphthalene.) A process for preparing the porous compound of claim 3 by reacting a compound of formula II with a compound of formula V in the presence of palladium (II) (Pd (II)) and potassium carbonate (K ₂ CO ₃ ). [Formula II]

(In the above formula, R ₃ is one selected from the group consisting of 4-iodinephenyl, 4-bromophenyl, 4-iodinebiphenyl and 4-bromobiphenyl.) [Formula Ⅴ]

(In the above formula, n is 2, and R ₄ is one selected from the group consisting of 1,4-phenylene, 4,4-biphenylene and 2,6-naphthalene.)

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