KR101694854B1 - Microporous polymers and fabrication methods of the same - Google Patents

Abstract

여기서, R은 방향족 고리화합물이다.The present invention relates to a microporous polymer and a method for producing the same. A method of manufacturing a microporous polymer according to an embodiment of the present invention includes the steps of providing a first building block, providing a second building block, and reacting the first building block and the second building block , ≪ / RTI > forming a polymeric material of formula (I)
(I)

Here, R is an aromatic ring compound.

Description

≪ Desc / Clms Page number 1 > Microporous polymers and fabrication methods thereof

TECHNICAL FIELD The present invention relates to a microporous polymer and a method for producing the same, and more particularly, to a sponge-like microporous polymer formed of a single compact having no compressibility, and a method for producing the same.

Environmental pollution caused by the industrialization has been recognized as an important problem for a long time, and the technology development to solve it has been steadily progressed. These technologies are being developed in various ways, including removal of pollutants and research on new energy resources that can reduce pollution. Among them, studies on microporous materials capable of adsorbing and removing carbon dioxide, which is designated as a greenhouse gas, and storing alternative energy such as hydrogen, have been actively conducted. The microporous material has a high specific surface area and a pore size of 2 nm or less and is capable of efficiently adsorbing gaseous molecules. In particular, the microporous polymer composed of an organic polymer is a porous material having light weight and high physicochemical stability. .

However, since the microporous polymer so far reported is obtained in the form of powder during the polymerization process, it has a limitation in practical use due to the weak mechanical properties.

Korean Laid-Open Publication No. 10-2000-0055678 Korean Patent Publication No. 10-2005-0024921 Korean Laid-Open Publication No. 10-2011-0130812

Therefore, the present inventors prepared a microporous polymer obtained by a single monolithic substance, not a powder state, and produced a microporous polymer having reversible compressibility, which is compressed without being broken by mechanical compression stress and returns to its original form when compression stress is removed Invented. The microporous polymer of the present invention can be prepared in various forms depending on the application and exhibits excellent mechanical properties, which will contribute greatly to the actual utilization and commercialization of the microporous polymer.

A problem to be solved by the present invention is to provide a method for producing a microporous polymer which has compressibility without being broken by mechanical compressive stress and returns to its original form when compressive stress is removed.

Another object to be solved by the present invention is to provide a microporous polymer produced by the above-mentioned production method.

The problems to be solved by the present invention are not limited to the above-mentioned technical problems and other technical problems which are not mentioned can be clearly understood by those skilled in the art from the following description.

According to another aspect of the present invention, there is provided a method of manufacturing a microporous polymer, comprising: providing a first building block; providing a second building block; And reacting the second building block to form a polymeric material having the following formula (I).

(I)

Here, R is an aromatic ring compound.

The polymeric material of Formula I may be formed by reacting the first and second building blocks with palladium (Pd) and copper (Cu) catalysts.

The first building block may be of formula (II).

≪ RTI ID = 0.0 &

Here, R is an aromatic ring compound, and X is either Br or I.

The second building block may be of formula (III).

(III)

The first building block may be of the formula (IV).

(IV)

Here, R ₁ is any one selected from fluorine (F) and hydrogen (H).

(IV) can be prepared by reacting 2-tributylstannyl thiophene with 1,4-dibromobenzene or 1,4-dibromo-2,5-difluoro 4-dibromo-2,5-difluorobenzene in the presence of a Pd catalyst.

The polymeric material of formula (I) may be formed in a temperature atmosphere of 90 ° C to 120 ° C.

The first building block may be of formula (V).

(V)

Wherein R < ₂ > is benzene or thiophene.

The first building block may be 1,4-diiodobenzene or 2,5-diiodothiophene.

The polymeric material of formula (I) may be formed in a temperature atmosphere of 18 ° C to 30 ° C.

The polymeric material of formula (I) may have a restoring force against an external force.

According to another aspect of the present invention, there is provided a microporous polymer according to an embodiment of the present invention.

(I)

Here, R is an aromatic ring compound.

The substance of formula (I) can adsorb carbon dioxide.

The material of formula (I) may store hydrogen.

Since the microporous polymer provided by the present invention has a high specific surface area, it can be utilized for storage of gas and molecules and purification of contaminants of existing microporous polymers, and at the same time, since the microporous polymer forms a compressible monolith, It is possible to overcome the limitations of the mechanical properties of the substrate. Specifically, it is possible to manufacture a mass of a microporous polymer having a specific shape suitable for a specific use, or more effectively store gases and molecules using the compressibility, purify contaminants, and the like.

1 is a flow chart of a method of manufacturing a microporous polymer according to an embodiment of the present invention.
2 is a nitrogen adsorption (a) - desorption (b) graph of a polymer in which R is benzene in formula (I) according to the present invention.
Figure 3 shows that when compressive stress is applied to a polymer wherein R is 2,2 ' - (2,5-difluoro-l, 4-phenylene) dicyanophene of Formula I according to the present invention, It is a photograph showing the original shape is recovered when the stress is removed.
Figure 4 is a stress-strain curve showing the compressive nature of a polymer in which R is 2,2 '- (2,5-difluoro-l, 4-phenylene) dicyanophene according to the invention.

Advantages and features of the present invention and methods of achieving them will become apparent with reference to the embodiments described in detail below. The present invention may, however, be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Is provided to fully convey the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims.

Unless defined otherwise, all terms (including technical and scientific terms) used herein may be used in a sense commonly understood by one of ordinary skill in the art to which this invention belongs. Also, commonly used predefined terms are not ideally or excessively interpreted unless explicitly defined otherwise.

Hereinafter, a microporous polymer according to embodiments of the present invention and a method for producing the same will be described. The microporous polymer of the present invention can be formed in the form of a sponge, has a high specific surface area, and has compressive properties. These mechanical properties are expected to greatly contribute to the practical application and commercialization of microporous polymers overcoming the limitations of previously reported microporous polymers.

On the other hand, one embodiment of the present invention relates to the production of a microporous polymer, which can be prepared by the following steps.

Referring to FIG. 1, a method of manufacturing a microporous polymer according to an exemplary embodiment of the present invention includes providing a first building block S1, a second building block S2, And reacting the block to form a polymeric material of formula (I) (S3). This will be described in more detail as follows.

(I)

Here, R is an aromatic ring compound.

On the other hand, the first building block may be a substance represented by the following formula (II).

≪ RTI ID = 0.0 &

Here, R is an aromatic ring compound, and X is either Br or I.

In addition, the second building block may be a substance represented by the following formula (III).

(III)

The polymeric material of Formula I may be formed by reacting a first building block, Formula II, and a second building block, Formula III, with palladium (Pd) and copper (Cu) catalysts.

For example, there can be mentioned 2-tributylstannyl thiophene and 1,4-dibromobenzene or 1,4-dibromo-2,5-difluoro A compound prepared by the Stille reaction of 1,4-dibromo-2,5-difluorobenzene is subjected to a bromination reaction with N-bromosuccinimide to form a first building, Block, and provides it.

Alternatively, 1,4-diiodobenzene or 2,5-diiodocyophene polymer may be used as the first building block.

The first building block and the second building block, 1,3,5-triethynylbenzene, are reacted in the presence of palladium and copper catalysts under the Sonogashira reaction to obtain a compound of formula (I) The microporous polymer of the polymer substance of the present invention can be produced. The microporous polymer may be in the form of a sponge, and has unique mechanical properties to form a compact having a compressibility that conventional microporous polymers do not possess.

(I)

Here, R is an aromatic ring compound.

Further, the first building block may be represented by the following formula (IV) or (V).

(IV)

Here, R ₁ is any one selected from fluorine (F) and hydrogen (H).

(V)

Wherein R < ₂ > is benzene or thiophene.

The compounds of formula (IV) may be prepared in the following manner.

1) a process for producing 2-tributylstannyl thiophene, which is dissolved in an organic solvent, with 1,4-dibromobenzene or 1,4-dibromo-2,5- A process for producing an intermediate material by subjecting 1,4-dibromo-2,5-difluorobenzene to a Stille reaction in the presence of a Pd (0) catalyst,

2) separating the intermediate material obtained in the step 1)

3) a step of preparing a building block by dissolving the intermediate material obtained in the step 2) in an organic solvent and carrying out a bromination reaction with N-bromosuccinimide,

4) separating the building block obtained in the step 3).

Meanwhile, the polymer compound of formula (I) can be prepared by the following method.

1) The compound of formula (IV) and the compound of formula (III) are reacted in the presence of palladium (II) (Pd (II)) and copper iodide (CuI) via Sonogashira reaction in a high temperature atmosphere of 90 ° C to 120 ° C, The compound of the general formula V and the compound of the general formula III are reacted with the microporous polymer in the presence of palladium (II) (Pd (II)) and copper iodide (CuI) at a temperature of 18 ° C to 30 ° C under a room temperature atmosphere in a Sonogashira reaction. Manufacturing steps:

2) separating and purifying the microporous polymer obtained in the step 1).

Hereinafter, the present invention will be described in more detail by way of examples and the like. However, the scope of the present invention is not limited by the following examples.

¹ H and ¹³ C NMR spectra of the compounds of the present invention were measured using a Bruker Advance 300 spectrometer and a Bruker Avance 400 WB spectrometer. The specific surface area of the porous material was measured using BELSORP-max of BEL-Japan, The compression properties were measured using a KES-FB3 automatic compression tester.

[Example 1] Synthesis of 2,2 '- (2,5-difluoro-1,4-phenylene) dithiophene (2,2' Synthesis of

1.50 g of 1,4-dibromo-2,5-difluorobenzene, 255 mg of tetrakis (triphenylphosphine) palladium (0) Was dissolved in 50 ml of N, N'-dimethylformamide, and 4.94 g of 2- (tributylstannyl) thiophene was added thereto. The mixture was stirred at 100 ° C for 24 hours while blocking light, The mixture is extracted with ethyl acetate, concentrated, and recrystallized from dichloromethane / ethyl alcohol (1: 9).

^{1 H NMR (300 MHz, CDCl} 3, ppm): δ 7.51 (d, J = 3.6 Hz, 2H), 7.44 (m, 4H), 7.15 (t, 2H)

[Example 2] Synthesis of 1,4-di (thiophen-2-yl) benzene (1,4-di

1.54 g of 1,4-dibromobenzene and 294 mg of tetrakis (triphenylphosphine) palladium (0) were dissolved in 50 ml of dimethylformamide (N, N'-dimethylformamide) ml, 5.70 g of 2- (tributylstannyl) thiophene was added to the solution, and the mixture was stirred at 100 ° C for 24 hours while blocking the light, extracted with ethyl acetate and concentrated And recrystallized from dichloromethane / ethyl alcohol (1: 9).

^{1 H NMR (300 MHz, CDCl} 3, ppm): δ 7.62 (s, 4H), 7.34 (d, J = 3.6 Hz, 2H), 7.29 (d, J = 5.1 Hz, 2H), 7.10 (t, 2H ).

[Example 3] Synthesis of 5,5 '- (2,5-difluoro-1,4-phenylene) bis (2-bromo isophene) -phenylene) bis (2-bromothiophene)

1.16 g of 2,2 '- (2,5-difluoro-1,4-phenylene) dithiophene (2,2' - (2,5-difluoro-1,4- N-bromosuccimide (1.49 g) was added to a solution of the compound in 50 ml of N, N'-dimethylformamide, and the mixture was stirred at room temperature for 24 hours while blocking the light. Ethyl acetate , And the residue is recrystallized from tetrahydrofuran / ethyl alcohol (1: 9).

^{1 H NMR (300 MHz, CDCl} 3, ppm): δ 7.34 (t, 2H), 7.24 (d, J = 3.9 Hz, 2H), 7.09 (d, J = 3.9 Hz, 2H).

Example 4 Synthesis of 1,4-bis (5-bromothiophen-2-yl) benzene (1,4-bis (5-bromothiophen-

To a solution of 601 mg of 1,4-di (thiophen-2-yl) benzene in 50 ml of N, N'-dimethylformamide N-bromosuccimide (882 mg) was added and the mixture was stirred at room temperature for 24 hours while blocking the light. The mixture was extracted with ethyl acetate and concentrated to obtain tetrahydrofuran / ethyl alcohol ethyl alcohol) (1: 9).

^{1 H NMR (300 MHz, CDCl} 3, ppm): δ 7.51 (s, 4H), 7.08 (d, J = 3.9 Hz, 2H), 7.05 (d, J = 3.9 Hz, 2H).

[Preparation Example 1] Preparation of microporous polymer at high temperature

The compound of the formula IV prepared in Examples 3 and 4 was dissolved in degassed toluene / dimethylformamide (1: 1) and toluene The compound represented by the formula (III), Pd (II) and CuI are added, and triethylamine is added thereto. The reaction is carried out at 100 ° C for 24 hours to prepare a microporous polymer. The prepared microporous polymer was washed with methyl alcohol, water, tetrahydrofuran, and acetone, and then subjected to Soxhlet extraction with methanol to remove residual substances in the pores, followed by vacuum drying at 120 ° C. And the solvent in the pores is removed by drying.

[Preparation Example 2] Preparation of microporous polymer sponge at room temperature

The compound of the above formula (V) was dissolved in a degassed toluene / triethylamine (2: 1) solvent, and the compound represented by the formula (III), Pd (II) and CuI were added thereto and reacted at room temperature for 24 hours Thereby preparing a microporous polymer. The prepared microporous polymer was washed with methyl alcohol, water, tetrahydrofuran, and acetone, and then subjected to Soxhlet extraction with methanol to remove residual substances in the pores, followed by vacuum drying at 120 ° C. And the solvent in the pores is removed by drying.

[Experimental Example 1] The specific surface area analysis test of the microporous polymer produced by the present invention

Nitrogen adsorption / desorption experiments were carried out to measure the specific surface area of the microporous polymer prepared in Preparation Example 1 above. As a result, the specific surface area of the polymer in which R is benzene in the formula (I) was 1090 m ² / g, and the results are shown in FIG.

[Experimental Example 2] The shape control and working test of the microporous polymer monolith prepared by the present invention

For the purpose of controlling the shape of the microporous polymer prepared in Preparation Example 1, a microporous polymer having a shape according to the shape of a glass bottle was prepared. For the shape processing of the microporous polymer prepared in Preparation Example 1, a microporous polymer having a specific shape was prepared by carving it into a specific shape using a knife.

[Experimental Example 3] Compression property test of the microporous polymer prepared by the present invention

For the compressive properties of the microporous polymer prepared in Preparation Example 1, when the compressive stress was applied, the microporous polymer was compressed and returned to the original shape when the compressive stress was released. As a result, 3. The compression properties of the microporous polymer were not significantly impaired even after this process was repeated several times, and the quantitative compression properties of the microporous polymer are shown in FIG.

The microporous polymer provided by the present invention has a characteristic of forming a monolith having a high specific surface area and compressibility. By using these features, a large microporous polymer having mechanical stability and desired shape can be produced. Such a microporous polymer can be used as a gas storage medium such as hydrogen, or as an adsorbent for pollutants such as carbon dioxide, and as an adsorbent for selectively absorbing hydrophobic liquids such as oil.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (14)

Providing a first building block;
Providing a second building block; And
Reacting the first building block with the second building block to form a polymeric material of Formula I,
Wherein the first building block is represented by the following formula (IV).
(I)

Here, R is an aromatic ring compound.
(IV)

Here, R ₁ is any one selected from fluorine (F) and hydrogen (H). The method according to claim 1,
Wherein the polymeric material of Formula (I) is formed by reacting the first building block and the second building block with palladium (Pd) and copper (Cu) catalyst. delete The method according to claim 1,
Wherein the second building block is represented by the following formula (III).
(III)

delete The method according to claim 1,
(IV) can be prepared by reacting 2-tributylstannyl thiophene with 1,4-dibromobenzene or 1,4-dibromo-2,5-difluoro And reacting 1,4-dibromo-2,5-difluorobenzene in the presence of a Pd catalyst to produce a microporous polymer. The method according to claim 1,
Wherein the polymeric material of Formula (I) is formed in a temperature atmosphere of 90 占 폚 to 120 占 폚. Providing a first building block;
Providing a second building block; And
Reacting the first building block with the second building block to form a polymeric material of Formula I,
Wherein the first building block is represented by the following formula (V).
(I)

Here, R is an aromatic ring compound.
(V)

Wherein R < ₂ > is a thiophene. 9. The method of claim 8,
Wherein the first building block is 2,5-diiodothiophene. 9. The method of claim 8,
Wherein the polymeric material of Formula (I) is formed in a temperature atmosphere of 18 ° C to 30 ° C. The method according to claim 1,
Wherein the polymeric material of Formula (I) has a restoring force against an external force. A microporous polymer of formula (I) as defined in any one of claims 1, 2, 4 and 6 to 11.
(I)

Here, R is an aromatic ring compound. 13. The method of claim 12,
Wherein the substance of formula (I) adsorbs carbon dioxide. 13. The method of claim 12,
Wherein the substance of formula (I) stores hydrogen.

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