KR100393177B1 - Porous polymer obtained by the polymerization of liquid crystal material having columnar structure and preparing method thereof - Google Patents

Abstract

The present invention provides a porous polymer obtained through polymerization of a liquid crystal material having a columnar structure and a method of manufacturing the same. The porous polymer is characterized in that it is obtained by polymerizing in a liquid crystal state from a liquid crystal material having a columnar structure obtained through hydrogen bonding between a template molecule and a polymerizable monomer, and removing the template molecule from the polymerization product. In the porous polymer of the present invention, since pores of a predetermined size are regularly arranged, when the metal is included in the pores, the metal particles of a predetermined size may be uniformly arranged. In addition, the liquid crystal material before the polymerization has the advantage that it is possible to spin-coating and polymerize the resulting product it is easy to make a polymer thin film. Such polymer thin films can be used as industrially valuable porous materials or membranes, and in particular, can be applied as functional membranes that can recognize and separate only specific materials according to template molecules. In addition, the porous polymer of the present invention can be used as a template molecule in the synthesis of a polymer having different physical properties, and a compound obtained by inserting a metal into the pores of the porous polymer can be used as a catalyst. In addition, unlike the conventional method for producing a porous material, the porous polymer of the present invention can be easily produced without undergoing harsh conditions of high temperature and high pressure.

Description

Porous polymer obtained by the polymerization of liquid crystal material having columnar structure and preparing method

The present invention relates to a porous polymer and a method for manufacturing the same, and more particularly, to polymerize a liquid crystal material having a columnar structure to obtain a polymer having a liquid crystal phase, and to remove a template molecule from the polymer to prepare a porous polymer. It relates to a porous polymer obtained according to this method.

Porous materials may be classified into microporous materials, mesoporous materials, and macroporous materials according to pore sizes. Here, the microporous material has a pore size of 2 nm or less, the mesoporous material has a pore size of 2 to 50 nm, and the macroporous material has a pore size of 50 nm or more. These porous materials can be used in ion exchange resins, adsorbents, catalysts, and fillers of chromatographies depending on the pore size, and can also be widely used in fields such as solid phase synthesis, enzyme fixation, and medicine.

As a method of preparing a porous material, a sol-gel synthesis method using template molecules is widely used. However, this method is a method for producing a porous material made of an inorganic material, there is a disadvantage that must be subjected to the process of high temperature and high pressure when removing the template molecules that determine the size of the pores, there is a limit to apply industrially. Therefore, the need for development of a method for producing a porous material that does not require harsh conditions of high pressure and high temperature is gradually increasing.

On the other hand, if it is possible to thin the porous material, it can be used as a membrane used in the industrial separation process. However, in the case of a functional membrane such as Nafion, the pores are not structurally well arranged, whereas a membrane in which the pores are structurally well arranged is not functional. Therefore, it is an urgent task to develop a membrane having a good structural arrangement of pores and having functionality.

The technical problem to be achieved by the present invention is to provide a novel porous polymer that can be thinned by solving the above problems, and does not require harsh conditions of high temperature and high pressure, and a method of manufacturing the same.

Another technical problem to be achieved by the present invention is to provide a use of the porous polymer.

1 is a view showing a process for preparing a porous polymer from a liquid crystal material having a columnar structure and a process in which the porous polymer is applied according to the present invention,

2 is a view showing the results of X-ray diffraction analysis of the compound prepared according to Synthesis Example 1 of the present invention,

3 is a view showing a solid nuclear magnetic resonance spectrum before and after the sonication treatment of the polymer prepared according to Synthesis Example 2 of the present invention to a mixed solution of aqueous hydrochloric acid and methanol,

4 is a view showing the results of X-ray diffraction analysis of the porous polymer prepared according to Synthesis Example 3 of the present invention,

5 is a view showing the results of X-ray diffraction analysis of the porous polymer Ag is inserted into the pores according to Example 1 of the present invention,

6 is a view showing the results of X-ray diffraction analysis of the polymer obtained in Example 2 of the present invention.

In order to achieve the first technical problem, the present invention provides a template molecule, which is 2,5,8-trialkyl-4,7-dihydro-1H-diimidazo [4 ', 5': 3,4: 4 ', 5': 5,6] obtained by hydrogen bonding between benzo [d] imidazole and 3,4,5-tris (11'-acryloylalkyloxy) benzoic acid of the following structural formula which is a polymerizable monomer Polymerizing the liquid crystal material of Formula 1, which is a binder and has a columnar structure, to obtain a corresponding polymer in the liquid crystal phase, and immersing the resulting polymer in a mixture of an organic solvent and an acid solution, 2, 5,8-trialkyl-4,7-dihydro-1H-diimidazo [4 ', 5': 3,4: 4 ', 5': 5,6] obtained by removing benzo [d] imidazole It provides a porous polymer, characterized in that. <Formula 1> Wherein R ₁ , R ₂ and R ₃ are each independently selected from the group consisting of hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkylhydroxy group having 1 to 5 carbon atoms and an alken group having 1 to 5 carbon atoms, S ₁ , S ₂ and S ₃ are independently represented by the formula (2), <Formula 2> Wherein A ₁ , A ₂ and A ₃ are each independently an alkyl group having 8 to 30 carbon atoms. The porous polymer is obtained by immersing a polymerization product in a mixture of an organic solvent and an acid solution to remove template molecules in the polymer. .

The second technical problem of the present invention is (a) 2,5,8-trialkyl-4,7-dihydro-1H-diimidazo [4 ', 5': 3,4: 4 ' , 5 ': 5,6] Benzo [d] imidazole and 3,4,5-tris (11'-acryloylalkyloxy) benzoic acid of the following structural formula which is a polymerizable monomer are made to react, and hydrogen bond between them Obtaining a liquid crystal material of Formula 1 having a columnar structure through; (b) Obtaining a polymer for maintaining the structure of the liquid crystal phase by polymerizing the liquid crystal material of the columnar structure; And (c) immersing the polymer in a mixture of an organic solvent and an acid solution, 2,5,8-trialkyl-4,7-dihydro-1H-diimidazo [4 ', 5': 3, which is a template molecule in the polymer. , 4: 4 ', 5': 5,6] By the method for producing a porous polymer, characterized in that it comprises the step of removing benzo [d] imidazole. <Formula 1> Wherein R ₁ , R ₂ and R ₃ are each independently selected from the group consisting of hydrogen, an alkyl group of 1 to 5 carbon atoms, an alkylhydroxy group of 1 to 5 carbon atoms, and an alken group of 1 to 5 carbon atoms, S ₁ , S ₂ and S ₃ are independently represented by the formula (2), <Formula 2> In the above formula, A ₁ , A ₂ and A ₃ are alkyl groups having 8 to 30 carbon atoms irrespective of each other.

The third technical task of the present invention is to use a porous polymer in a functional membrane that recognizes a specific molecule or by coordinating a metal in the pores to form a nanocomposite as a catalyst or a method for the synthesis of semiconductor materials .

1 illustrates a process for preparing a porous polymer from a liquid crystal material having a columnar structure and a process in which the porous polymer is applied according to the present invention. Referring to this, the porous polymer (III) of the present invention has a columnar structure, in particular a hexagonal structure, through a hydrogen bond of a template molecule having a reaction site capable of hydrogen bonding, and a monomer capable of effectively interacting with these template molecules and polymerizing monomers. It can obtain through the process of obtaining the liquid crystal substance (I) which has a starting structure, superposing | polymerizing this liquid crystal substance (I), and removing a template molecule from the polymer (II) obtained by this polymerization. At this time, the porous polymer (III) can be used as a functional membrane for recognizing and separating specific molecules such as template molecules, and compound (IV) is obtained by inserting a metal into the pores formed in the porous polymer (III). (IV) can be used for synthesis of catalysts or semiconductor materials in various reactions.

Hereinafter, a specific example of the above-described porous polymer formation process will be described.

Template molecules include 2,5,8-trialkyl-4,7-dihydro-1H-diimidazo [4 ', 5': 3,4: 4 ', 5' having a discotic structure: 5,6] benzo [d] imidazole is used, and 3,4,5-tris (11'-acryloylalkyloxy) benzoic acid is used as a ligand capable of polymerizing with the template molecule.

Referring to Scheme 1 below, 3,4,5-tris (11'-acryloylalkyloxy) benzoic acid is dissolved in an organic solvent, and then 2,5,8-trialkyl-4,7-dihydro is added thereto. -1H-Diimidazo [4 ', 5': 3,4: 4 ', 5': 5,6] By adding benzo [d] imidazole and stirring at room temperature, the liquid crystal material represented by Chemical Formula 1 can be obtained. have. Herein, the organic solvent is 3,4,5-tris (11'-acryloylalkyloxy) benzoic acid and 2,5,8-trialkyl-4,7-dihydro-1H-diimidazo [4 ', 5': 3,4: 4 ', 5': 5,6] It is preferable to use a solvent which does not interfere with the hydrogen bonding between benzo [d] imidazole. Specifically, chloroform, methylene chloride or the like is used. .

Wherein R ₁ , R ₂ and R ₃ are each independently selected from the group consisting of hydrogen, an alkyl group of 1 to 5 carbon atoms, an alkylhydroxy group of 1 to 5 carbon atoms, and an alken group of 1 to 5 carbon atoms, and A ₁ , A ₂ and A ₃ are alkylene groups having 8 to 30 carbon atoms irrespective of each other.

The liquid crystal material of Chemical Formula 1 is a material formed by hydrogen bonding between the two compounds, and has a hexagonal columnar structure. In R ₁ , R _2, and R ₃ of Formula 1, examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, propyl group, butyl group, and pentyl group, and examples of the alkyl hydroxyl group having 1 to 5 carbon atoms include There are a methylhydroxy group, an ethyl hydroxy group, a propyl hydroxy group, a butyl hydroxy group, a pentyl hydroxy group, and an alkene group having 2 to 5 carbon atoms includes an ethylene group, a propylene group, a butylene group or a pentylene group. Examples of the alkyl group having 8 to 30 carbon atoms in A ₁ , A ₂ and A ₃ of Chemical Formula 2 include octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradacyl group, pentadecyl group, Hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosanyl group, heneicosanyl group, docosanyl group, tricosanyl group, tetracosanyl group, pentacosanyl group, hexacosanyl group, heptacosanyl group , Octacosanyl group, nonacosanyl group, triacontanyl group, and the like.

In particular, it is preferable that R <_1> , R <_2> and R <_3> is a butyl group or a pentyl group, and A <_1> , A <_2> and A <_3> are a decyl group or an undecyl group.

<Formula 1>

Wherein R ₁ , R ₂ and R ₃ are each independently selected from the group consisting of hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkyl hydroxy group having 1 to 5 carbon atoms, and an alken group having 1 to 5 carbon atoms,

S ₁ , S ₂ and S ₃ are independently represented by Formula 2,

<Formula 2>

In the above formula, A ₁ , A ₂ and A ₃ are alkyl groups having 8 to 30 carbon atoms irrespective of each other.

Thereafter, the liquid crystal material of Formula 1 is irradiated with light or heat to perform a polymerization reaction. At this time, it is preferable to use light of 400 nm or less, in particular, light of 365 nm or X-rays. When the polymerization reaction is carried out as described above, polymerization occurs around the acrylate group region in the polymerizable monomer, thereby obtaining a polymer having a liquid crystal structure. At this time, the template molecules are not polymerized and are constantly arranged in the polymer by hydrogen bonding.

Then, the desired porous polymer is completed when the process of removing the template molecules not participating in the polymerization reaction from the polymer obtained according to the above process. At this time, a method of removing the template molecules from the polymer is a method of immersing the polymer in a mixture of an organic solvent and an acid solution. Here, methanol, ethanol, propanol, etc. are used as an organic solvent, hydrochloric acid aqueous solution, nitric acid aqueous solution, etc. are used as an acid solution, The density | concentration of this acid solution is 1-4M. The mixing volume of the organic solvent and the acid solution is preferably 1: 1 to 10: 1. As such, when the template molecule is removed from the polymer, it is possible to obtain a porous polymer in which the pores are constantly arranged.

Hereinafter, the present invention will be described in detail with reference to the following Synthesis Examples and Examples, but the present invention is not limited to the following Synthesis Examples and Examples.

Synthesis Example 1. 2,5,8-Tripentyl-4,7-dihydro-1H-diimidazo [4 ', 5': 3,4: 4 ', 5': 5,6] Benzo [d] Experimental example for preparing a liquid crystal material which is a hydrogen bonding compound of imidazole and 3,4,5-tris (11'-acryloyl undecyloxy) benzoic acid

2,5,8-tripentyl-4,7-dihydro-1H-diimidazo [4 ', 5': 3,4: 4 ', 5': 5,6] benzo [d] imidazole 33.1 mg And 205 mg of 3,4,5-tris (11'-acryloyl undecyloxy) benzoic acid were dissolved in chloroform. Thereafter, the reaction mixture was stirred for 30 minutes, and then evaporated to remove the solvent to obtain a yellow liquid crystal material.

¹ H-NMR (CDCl ₃ , 500 MHz): δ 0.91 (d, 7H), 1.21-1.46 (m, 194H), 3.21 (d, 4H), 4.01 (d, 20H), 4.10 (t, 18H), 5.77 (d, 8H), 6.08 (m, 8H), 6.36 (d, 8H), 7.37 (s, 6H).

¹³ C-NMR (CDCl ₃ , 125 MHz): δ 14.41, 22.78, 26.49, 29.02, 29.68, 29.79, 29.95, 30.02, 30.76, 38.01, 39.48, 65.12, 69.51, 73.87, 108.83, 120.98, 126.93, 129.03, 130.87 , 142.59, 153.12, 166.76, 170.81, 171.80.

IR (KBr): ν 3036, 2925, 2854, 1729, 1686, 1636, 1585, 1467, 1428, 1407, 1384, 1328, 1295, 1271, 1191, 1117, 1059, 985, 967, 810.

The structure of the liquid crystal material prepared according to Synthesis Example 1 was confirmed by X-ray diffraction. X-ray diffraction analysis results are shown in FIG. 2. Referring to this, it was found that the liquid crystal material of Synthesis Example 1 was a liquid crystal phase compound having a hexagonal columnar structure, and the distance between the pillars was 38.7 Å. At this time, the liquid crystal material of Synthesis Example 1 was already polymerized by X-rays irradiated for X-ray diffraction experiment.

Synthesis Example 2. 2,5,8-Tripentyl-4,7-dihydro-1H-diimidazo [4 ', 5': 3,4: 4 ', 5': 5,6] Benzo [d] Experimental example of polymerization of liquid crystal substance which is a hydrogen bond compound of imidazole and 3,4,5-tris (11'-acryloyl undecyloxy) benzoic acid

2,5,8-tripentyl-4,7-dihydro-1H-diimidazo [4 ', 5': 3,4: 4 ', 5': 5,6] benzo prepared according to Synthesis Example 1 The liquid crystal material between 33.1 mg of [d] imidazole and 3,4,5-tris (11'-acryloyl undecyloxy) benzoic acid was dissolved in chloroform and then placed in a sealed glass tube with one end portion. Subsequently, the inside of the glass tube was depressurized to gradually remove the solvent to uniformly solidify the liquid crystal material on the glass base wall. Thereafter, the other end portion of the glass tube was sealed by heat treatment to completely block the inside of the glass tube from the outside.

The glass tube was placed in a thermostat controlled at 30 ° C. and subjected to polymerization by irradiation of 365 nm light for 3 hours. After the polymerization was completed, the reaction product was washed with chloroform to obtain a pure polymer.

¹³ C NMR (125 MHz): δ 4.87, 11.90, 24.23, 27.44, 38.05, 62.12, 66.75, 70.56, 105.92, 118.22, 127.49, 139.97, 150.33, 168.26, 171.95.

IR (KBr): ν 2929, 2853, 1728, 1686, 1637, 1584, 1500, 1466, 1428, 1407, 1376, 1329, 1295, 1262, 1190, 1111, 1060, 809, 774, 722.

Synthesis Example 3 2,5,8-Tripentyl-4,7-dihydro-1H-diimida [4 ', 5': 3,4: 4 ', 5': 5,6] Benzo [d] Experimental Example of Preparing a Porous Polymer by Removing a Template Molecule from a Polymer Formed from Polymerization of a Liquid Crystal Material of Imidazole and 3,4,5-Tris (11'-acryloyl undecyloxy) benzoic Acid

The polymer obtained according to Synthesis Example 2 was added to a 10: 1 mixed solution of methanol and 3M HCl aqueous solution and sonicated for 400 minutes. The mixture was then filtered and the solid obtained was washed with methanol and water. Thereafter, the obtained solid was dried in vacuo to give 2,5,8-tripentyl-4,7-dihydro-1H-diimidazo [4 ', 5': 3,4: 4 ', 5': 5,6]. It was possible to obtain a porous polymer from which a column made of benzo [d] imidazole was removed.

¹³ C NMR (125 MHz): δ 12.26, 27.28, 38.18, 62.12, 66.43, 105.45, 127.16, 140.53, 150.40, 171.60.

3 shows a solid nuclear magnetic resonance spectrum of the polymer (a) containing the template molecule and the polymer (b) from which the template molecule is removed. Referring to this, 2,5,8-tripentyl-4,7-dihydro-1H-diimazo [4 ', 5': 3,4: 4 ', 5': 5,6] benzo [4] appears at 118 ppm. d] The benzene carbon peak of imidazole disappeared after the sonication treatment under hydrochloric acid and methanol mixed solution. The carbon peak of the imidazole was also reduced, but it was found that the position of the benzoic acid present in the polymer overlaps with the benzene carbon so that it is not completely removed. Taken together, 2,5,8-tripentyl-4,7-dihydro-1H-diimazo [4 ', 5': 3,4: 4 ', 5': 5,6] benzo [ d] The template molecule consisting of imidazole disappeared completely and turned into a porous polymer.

Figure 4 shows the X-ray diffraction analysis of the porous polymer. Referring to this, the porous polymer showed a diffraction pattern similar to that of FIG. 2, and it was confirmed that the porous polymer had a hexagonal columnar structure even after the template molecules were removed.

Example 1 Experimental Example of Inserting Ag Metal into Pores of Porous Polymer of Synthesis Example 3

The porous polymer obtained in Synthesis Example 3 was placed in an aqueous 1M NaOH solution and left for 24 hours. Subsequently, the resultant was washed with distilled water and then immersed in 0.1M AgNO ₃ aqueous solution and left for 24 hours in the dark. Thereafter, the result was transferred to a bright place and stored for 1 hour.

X-ray diffraction experiment of the Ag-inserted polymer was performed according to the above-described procedure, and the X-ray diffraction analysis results thus obtained are shown in FIG. 5.

Referring to FIG. 5, although the Ag metal particles were inserted, it was found that the polymer had a hexagonal columnar structure. Since the Ag metal particles were spaced about 3.8 nm from each other, they were uniformly arranged in the polymer. It could be seen that.

Example 2 Experimental Example of Reinserting the Template Polymer into the Porous Polymer of Synthesis Example 3

The porous polymer obtained from Synthesis Example 3 was treated with 2,5,8-tripentyl-4,7-dihydro-1H-diimazo [4 ', 5': 3,4: 4 ', 5': 5,6] benzo. It was immersed in the mixed solvent of chloroform and methanol in which [d] imidazole was melt | dissolved. At this time, the mixing volume ratio of chloroform and methanol was adjusted to 10: 1.

After leaving the resultant for 24 hours, the porous polymer was taken out and washed with chloroform and methanol solvent to remove foreign substances present on the surface of the polymer. '

The solid nuclear magnetic spectrum of the polymer obtained according to the above-described procedure was investigated, and the results are shown in FIG. 6. Referring to this, 2,5,8-tripentyl-4,7-dihydro-1H-diimazo [4 ', 5': 3,4: 4 ', 5': 5,6] benzo [ d] When the imidazole was reinserted, it was confirmed that it remembered the shape of the molecules forming the original column.

Through these experimental examples it can be seen that the porous polymer obtained in Example 1 can be used as a selective permeable membrane that selectively adsorbs only the template polymer inserted into the pores.

In the porous polymer of the present invention, since pores of a predetermined size are regularly arranged, when the metal is included in the pores, the metal particles of a predetermined size may be uniformly arranged. In addition, the liquid crystal material before the polymerization has the advantage that it is possible to spin-coating and polymerize the resulting product it is easy to make a polymer thin film. Such polymer thin films can be used as industrially valuable porous materials or membranes, and in particular, can be applied as functional membranes that can recognize and separate only specific materials according to template molecules. In addition, the porous polymer of the present invention can be used as a template molecule in the synthesis of a polymer having different physical properties, and a compound obtained by inserting a metal into the pores of the porous polymer can be used as a catalyst. In addition, unlike the conventional method for producing a porous material, the porous polymer of the present invention can be easily produced without undergoing harsh conditions of high temperature and high pressure.

Although the present invention has been described with reference to the synthesis examples and examples, this is merely illustrative, and those skilled in the art to which the present invention pertains that various modifications and equivalent other embodiments are possible. Will understand. Therefore, the true technical protection scope of the present invention will be defined by the technical spirit of the appended claims.

Claims (9)

2,5,8-trialkyl-4,7-dihydro-1H-diimidazo [4 ', 5': 3,4: 4 ', 5': 5,6] benzo, which is a template molecule [d] a binder obtained by hydrogen bonding between imidazole and 3,4,5-tris (11'-acryloylalkyloxy) benzoic acid of the following structural formula which is a polymerizable monomer, and has a columnar structure Polymerizing the liquid crystal material of Chemical Formula 1 to obtain a corresponding polymer in the liquid crystal phase, and immersing the resulting polymer in a mixture of an organic solvent and an acid solution, 2,5,8-trialkyl-4,7- as a template molecule in the polymer. Dihydro-1H-diimidazo [4 ', 5': 3,4: 4 ', 5': 5,6] A porous polymer obtained by removing benzo [d] imidazole. <Formula 1> Wherein R ₁ , R ₂ and R ₃ are each independently selected from the group consisting of hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkylhydroxy group having 1 to 5 carbon atoms, and an alken group having 1 to 5 carbon atoms, S ₁ , S ₂ and S ₃ are independently represented by Formula 2, <Formula 2> In the above formula, A ₁ , A ₂ and A ₃ are alkyl groups having 8 to 30 carbon atoms irrespective of each other. delete delete (a) 2,5,8-trialkyl-4,7-dihydro-1H-diimidazo [4 ', 5': 3,4: 4 ', 5': 5,6 of the structural formula ] A chemical formula having a columnar structure through hydrogen bonding between benzo [d] imidazole and 3,4,5-tris (11'-acryloylalkyloxy) benzoic acid of the following structural formula which is a polymerizable monomer Obtaining a liquid crystal substance of 1; (b) polymerizing the columnar liquid crystal material to obtain a polymer that retains the structure of the liquid crystal phase as it is; And (c) immersing the polymer in a mixture of an organic solvent and an acid solution, 2,5,8-trialkyl-4,7-dihydro-1H-diimidazo [4 ', 5': 3, 4: 4 ', 5': 5,6] A method for producing a porous polymer, comprising the step of removing benzo [d] imidazole. <Formula 1> Wherein R ₁ , R ₂ and R ₃ are each independently selected from the group consisting of hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkyl hydroxy group having 1 to 5 carbon atoms, and an alken group having 1 to 5 carbon atoms, S ₁ , S ₂ and S ₃ are independently represented by Formula 2, <Formula 2> In the above formula, A ₁ , A ₂ and A ₃ are alkyl groups having 8 to 30 carbon atoms irrespective of each other. delete The method according to claim 4, wherein methanol is used as the organic solvent in step (c), an aqueous hydrochloric acid solution is used as the acid solution, and the acid solution has a concentration of 1 to 4 M, Method for producing a porous polymer, characterized in that the mixing volume ratio of the organic solvent and the acid solution is 1: 1 to 10: 1. The porous polymer of claim 1, wherein the porous polymer is used in a functional membrane that recognizes a specific molecule or by coordinating metal in pores to form nanocomposites to form a catalyst and a semiconductor. The method of claim 1, wherein the organic solvent used to remove the template molecules in the polymer is selected from the group consisting of methanol, ethanol and propanol, the acid solution is a porous hydrochloric acid or nitric acid solution of 1 to 4M concentration, characterized in that Polymer. The porous polymer of claim 1, wherein the mixing volume ratio of the organic solvent and the acid solution is 1: 1 to 10: 1.