KR101045669B1 - Method for producing porous organic thin film and porous organic thin film produced thereby - Google Patents

Abstract

It provides a method for producing a porous organic thin film and a porous organic thin film produced thereby. Preparing a substrate having a functional group capable of bonding an amino group to the porous organic thin film, coating a first monomer having 2 to 4 amino groups on the substrate to react with the functional group, and removing the unreacted first monomer And coating a second monomer having 2 to 4 isocyanate groups or 2 to 4 acyl chloride groups on the coated first monomer to react with the first monomer, and removing the unreacted second monomer. At least one of the first monomer and the second monomer may be a compound represented by Formula 1 below.

<Formula 1>

Wherein R is all amino groups, all isocyanate groups or all acylchloride groups, and X is a carbon atom or a silicon atom.

Description

Method for fabricating porous organic thin film and porous organic thin film fabricated by the same

The present invention relates to a method for manufacturing an organic thin film and an organic thin film prepared therein, and more particularly, to a method for manufacturing a porous organic thin film and a porous organic thin film produced thereby.

Nanoporous materials are known to exhibit inherent physical, chemical, biological and material properties of nanomaterials, and have a large surface area. They are new materials that can be applied to new fields such as energy, environment, catalysts, and tissue engineering. It is recognized. In particular, nanoporous polymers are generally low in density, exhibit high microporosity by organic molecular networks, and applications to filters, catalysts, and various reservoirs have been studied. Accordingly, various methods for the preparation of the porous polymer structure have been studied, but until now, most of the organic materials synthesized do not have constant pores or show low mechanical strength, and their workability is low, and thus they are limited in their practical application. Therefore, a porous organic structure having a constant pore size and a large specific surface area and having excellent chemical resistance, heat resistance, durability and processability for various applications will be required.

The technical problem to be solved by the present invention is to provide a method for producing a porous organic thin film using a molecular lamination method.

Another technical problem to be solved by the present invention is to provide a porous organic thin film having excellent chemical resistance, heat resistance and durability.

One aspect of the present invention to achieve the above technical problem provides a method for producing a porous organic thin film. The method includes (a) preparing a substrate having a functional group bondable to an amino group, (b) coating a first monomer having 2 to 4 amino groups on the substrate and reacting the functional group with an unreacted first Removing the monomer and (c) coating a second monomer having 2 to 4 isocyanate groups or 2 to 4 acyl chloride groups on the coated first monomer to react with the first monomer, and an unreacted second Removing monomers,

At least one of the first monomer and the second monomer is a compound represented by one of Formulas 1 to 3 below.

<Formula 1>

Wherein R is all amino groups, all isocyanate groups or all acylchloride groups, and X is a carbon atom or a silicon atom.

<Formula 2>

Wherein R is all amino groups, all isocyanate groups or all acylchloride groups.

<Formula 3>

Wherein R is all amino groups, all isocyanate groups or all acylchloride groups, and n is 0 or 1.

In order to solve the above technical problem, another aspect of the present invention provides a method for manufacturing a porous organic thin film. The method comprises the steps of (a) preparing a substrate having an amino group, (b) coating a first monomer having 2 to 4 isocyanate groups or 2 to 4 acyl chloride groups on the substrate to react with the amino group, Removing unreacted first monomer and (c) coating a second monomer having 2 to 4 amino groups on the coated first monomer to react with the first monomer, and removing unreacted second monomer. Steps,

At least one of the first monomer or the second monomer is a compound represented by any one of Formulas 1 to 3.

Another aspect of the present invention to achieve the above technical problem provides a porous organic thin film prepared by the method for producing a porous organic thin film.

As described above, according to the present invention, a monomer having an amino group and a monomer having an isocyanate group or an acyl chloride group are alternately laminated in a molecular unit to polymerize and crosslink, and the nanoporous organic material controlled to a constant thickness by controlling the number of stacking times. A thin film can be formed. In addition, the prepared organic thin film may have excellent chemical resistance, heat resistance and durability by the introduction of a monomer having a tetrahedral structure.

However, the effects of the present invention are not limited to the above-mentioned effects, and other effects not mentioned will be clearly understood by those skilled in the art from the following description.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments disclosed herein are provided so that the disclosure can be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. In the drawings, the thicknesses of layers and regions may be exaggerated for clarity. In addition, where a layer is said to be "on" another layer or substrate, it may be formed directly on the other layer or substrate, or a third layer may be interposed therebetween. Throughout the specification "coating" and "lamination" are used interchangeably.

According to an embodiment of the present invention, a method of manufacturing a porous organic thin film includes (a) preparing a substrate having a functional group bondable to an amino group, and (b) a first monomer having 2 to 4 amino groups on the substrate. Reacting with the functional group to remove the unreacted first monomer and (c) coating the second monomer having 2 to 4 isocyanate groups or 2 to 4 acyl chloride groups on the coated first monomer. Reacting with the first monomer to remove the unreacted second monomer,

At least one of the first monomer or the second monomer may be a compound represented by one of Formulas 1 to 3 below.

<Formula 1>

(Wherein R is all amino groups, all isocyanate groups or all acylchloride groups, and X is a carbon atom or a silicon atom.)

<Formula 2>

(Wherein R is all amino groups, all isocyanate groups or all acylchloride groups)

<Formula 3>

(Wherein R is all amino groups, all isocyanate groups or all acylchloride groups, and n is 0 or 1)

In addition, after performing the step (c), it may further comprise the step of reacting with the second monomer by coating the first monomer on the coated second monomer.

According to another embodiment of the present invention, the method for preparing a porous organic thin film includes (a) preparing a substrate having an amino group, (b) 2 to 4 isocyanate groups or 2 to 4 acyl on the substrate. Coating a first monomer having a chloride group to react with the amino group, removing unreacted first monomer, and (c) coating a second monomer having 2 to 4 amino groups on the coated first monomer to Reacting with the first monomer and removing the unreacted second monomer,

At least one of the first monomer or the second monomer may be a compound represented by one of Formulas 1 to 3 below.

<Formula 1>

(Wherein R is all amino groups, all isocyanate groups or all acylchloride groups, and X is a carbon atom or a silicon atom.)

<Formula 2>

(Wherein R is all amino groups, all isocyanate groups or all acyl chloride groups)

<Formula 3>

(Wherein R is all amino groups, all isocyanate groups or all acylchloride groups, and n is 0 or 1)

In addition, after performing the step (c), it may further comprise the step of reacting with the second monomer by coating the first monomer on the coated second monomer.

That is, according to the present exemplary embodiments of the method of manufacturing the porous organic thin film, the first monomer having the amino group (or the first monomer having the isocyanate group or the acyl chloride group) and the second monomer having the isocyanate group or the acyl chloride group ( Or alternatively laminating the second monomer having an amino group) to induce polymerization and crosslinking reaction of an amino group and an isocyanate group or an amino group and an acyl chloride group at the contact interface thereof to form a polyurea or polyamide, Strong covalent bonds can form across organic molecular networks. In addition, the layer composed of each monomer may be formed as a monomolecular film by removing the unreacted monomer. Therefore, when sequentially and repeatedly coating each monomer, it is possible to prepare a porous organic thin film having a desired thickness by laminating monomolecular films of a predetermined size. In particular, at least one of the first monomer and the second monomer is to use a monomer of the tetrahedral structure represented by any one of the formulas (1) to (3), the monomer of the tetrahedral structure is a kind of crosslinking It is possible to form a three-dimensional network of organic molecules that form points and are connected around it. Therefore, the organic thin film three-dimensionally polymerized and crosslinked around the monomer represented by any one of Chemical Formulas 1 to 3 may form a large number of nanopores having a large specific surface area. have. In addition, it may have excellent chemical resistance, heat resistance and durability due to high crosslinking rate and strong covalent bonds.

FIG. 1 is a schematic diagram illustrating a method of preparing a porous organic thin film using tetra (4-isocyanatophenyl) methane (TIPM) as a first monomer and tetra (4-aminophenyl) methane (TAPM) as a second monomer. In the figure, the step of removing unreacted monomers is omitted.

Referring to FIG. 1, TIPM and TAPM may be sequentially and repeatedly coated on a substrate having an amino group to form a porous organic thin film in which a monomolecular film of a first monomer and a monomolecular film of a second monomer are alternately stacked. have. In addition, although FIG. 1 illustrates a polyurea thin film laminated in three layers, it will be apparent to those skilled in the art that polyurea thin films having various thicknesses can be formed by controlling the number of lamination.

The substrate having a functional group bondable to the amino group is a substrate coated with a monomer represented by the following formula (4) or (5), or a polymer substrate containing an isocyanate group, acyl chloride group, aldehyde group, epoxy group, glycidyloxy group or phthalic anhydride group. Can be.

<Formula 4>

Wherein X is an isocyanate group, acyl chloride group, aldehyde group, epoxy group, glycidyloxy group or phthalic anhydride group, and R ₁ to R ₃ are each independently H, Cl, methoxy group or ethoxy group ( At least one of R ₁ to R ₃ is Cl, a methoxy group or an ethoxy group, n is an integer of 1 to 10).

<Formula 5>

(Wherein, X is an isocyanate group, acyl chloride group, aldehyde group, epoxy group, glycidyloxy group or phthalic anhydride group, R ₁ and R ₃ are H, C1 to C5 alkyl group irrespective of each other, n is 1 to 1 Is an integer of 15)

In addition, the substrate provided with the amino group may be a substrate coated with a monomer represented by Formula 6 or 7 below, or may be a polymer substrate containing an amino group.

<Formula 6>

Wherein X is an amino group, R ₁ to R ₃ are each independently a H, Cl, methoxy group or an ethoxy group, provided that at least one of R ₁ to R ₃ is a Cl, methoxy or ethoxy group n is an integer from 1 to 10.

<Formula 7>

(Wherein, X is an amino group, R ₁ and R ₃ is an alkyl group of H or C1 to C5 irrespective of each other, n is an integer of 1 to 15.)

A functional group bondable to an amino group provided on the substrate or the amino group provides a reaction site with a first monomer having an amino group or a first monomer having an isocyanate group (or acyl chloride group), respectively, and is first coated on the substrate. It serves to provide the basis on which 1 monomer can be formed into a monomolecular film.

The substrate is not particularly limited, and may be an inorganic substrate such as quartz, silicon, gold, silver, or alumina, or an organic substrate such as cellulose, polyimide, polyethylene terephthalate, polystyrene, or polycarbonate. In addition, the substrate may use not only planar substrates but also various types of substrates such as patterned substrates, porous substrates, or particulate substrates. That is, by appropriately selecting and coating the monomer represented by the formula of any one of formulas (4) to (7) according to the type of the substrate and the first monomer, the surface of the substrate may be bonded to amino group bond or isocyanate group (or acyl chloride) bond. Because it can be functionalized, various substrates can be used to support organic thin films. On the other hand, when the material of the substrate itself is a polymer substrate containing a functional group or amino group bondable to the amino group, the coating process of the monomer represented by the formula (4) to (7) can be omitted.

The first monomer having 2 to 4 amino groups may be a C 1 to C 20 aliphatic compound substituted with 2 to 4 amino groups or a C 6 to C 30 aromatic compound substituted with 2 to 4 amino groups. The second monomer having 2 to 4 isocyanate groups (or 2 to 4 acyl chloride groups) is a C1 to C20 aliphatic compound substituted with 2 to 4 isocyanate groups (or 2 to 4 acyl chloride groups). Or a C 6 -C 30 aromatic compound substituted with 2 to 4 isocyanate groups (or 2 to 4 acyl chloride groups).

For example, the first monomer having 2 to 4 amino groups or the second monomer having 2 to 4 isocyanate groups (or 2 to 4 acyl chloride groups) may be any one selected from the group consisting of the following compounds: Can be. However, at least one of the first monomer having 2 to 4 amino groups and the second monomer having 2 to 4 isocyanate groups (or 2 to 4 acyl chloride groups) may be the same as described above. It should be a compound represented by either formula.

<Compound Group>

(n은 1~6의 정수),

,

,

,

,

,

,

,

,

(n은 0 또는 1)

(n is an integer from 1 to 6),

,

,

,

,

,

,

,

,

(n is 0 or 1)

(Wherein R is all amino groups, all isocyanate groups or all acylchloride groups)

In addition, the first monomer having 2 to 4 isocyanate groups (or 2 to 4 acyl chloride groups) may be a C1 to C20 aliphatic compound substituted with 2 to 4 isocyanate groups (or 2 to 4 acyl chloride groups). Or a C 6 -C 30 aromatic compound substituted with 2 to 4 isocyanate groups (or 2 to 4 acyl chloride groups). The second monomer having 2 to 4 amino groups may be a C1 to C20 aliphatic compound substituted with 2 to 4 amino groups or a C6 to C30 aromatic compound substituted with 2 to 4 amino groups.

For example, the first monomer having 2 to 4 isocyanate groups (or 2 to 4 acyl chloride groups) or the second monomer having 2 to 4 amino groups may be any one selected from the group consisting of the following compounds: Can be. However, at least one of the first monomer having 2 to 4 isocyanate groups (or 2 to 4 acyl chloride groups) and the second monomer having 2 to 4 amino groups may be the same as described above. It should be a compound represented by either formula.

<Compound Group>

(n은 1~6의 정수),

,

,

,

,

,

,

,

,

(n은 0 또는 1)

(n is an integer from 1 to 6),

,

,

,

,

,

,

,

,

(n is 0 or 1)

(Wherein R is all amino groups, all isocyanate groups or all acylchloride groups)

Coating and reacting the first monomer or the second monomer may be performed by, for example, supporting a substrate in an organic solution in which the first monomer is dissolved or an organic solution in which the second monomer is dissolved. That is, a film of each monomer may be formed on the substrate by reacting the substrate for coating the first monomer or the second monomer into a solution in which each monomer is dissolved for a predetermined time. The concentration of each organic solution may be 0.05 ~ 5 w / v%. In this case, in order to promote the reaction, the organic base may be added to the solution of the monomer (at 1/1000 to 1/20 times the monomer).

Meanwhile, after forming the porous organic thin film to a desired thickness, the step of modifying the surface of the thin film may be further performed, and by selectively etching the substrate on which the porous organic thin film is formed, separating only the porous organic thin film. It can also be done.

According to another embodiment of the present invention, a porous organic thin film is provided. The porous organic thin film is prepared by the method of manufacturing the porous organic thin film described above.

Hereinafter, preferred examples are provided to aid the understanding of the present invention. However, the following experimental examples are only for helping understanding of the present invention, and the present invention is not limited to the following experimental examples.

Preparation Example 1: Fabrication of Porous Organic Thin Film on Quartz Substrate

The clean quartz substrate was subjected to air plasma treatment, and then supported by 2 w / v% APTES (3-aminopropyltriethoxysilane) anhydrous toluene solution for 2 minutes to prepare a quartz substrate having amino groups. Tetra (4-isocyanatophenyl) methane as the first monomer and tetra (4-aminophenyl) methane as the second monomer were dissolved in anhydrous THF, respectively, and tetra (4-isocyanatophenyl) methane at a concentration of 0.2w / v%. A solution (5 mL) and a tetra (4-aminophenyl) methane solution (5 mL) at 0.2w / v% concentration were prepared.

The surface-amined quartz substrate was reacted by supporting it for 3 hours in a tetrala (4-isocyanatophenyl) methane solution being stirred under normal temperature and nitrogen atmosphere. After the reaction, unreacted tetra (4-isocyanatophenyl) methane adsorbed onto the quartz substrate coated with tetra (4-isocyanatophenyl) methane was washed three times with clean anhydrous THF. Subsequently, the substrate was supported by reacting with stirring tetra (4-aminophenyl) methane solution for 20 seconds, and then unreacted tetra (4-aminophenyl) methane was washed three times with clean anhydrous THF. Subsequently, the reaction was carried out by supporting the tetra (4-isocyanatophenyl) methane solution and the tetra (4-aminophenyl) methane solution for 20 seconds, and washing the unreacted monomer repeatedly to obtain a porous organic thin film. .

Hereinafter, throughout the specification of the present invention, a cycle means a number of times the first monomer and the second monomer are coated on the substrate, and one cycle means that the first monomer and the second monomer are on the substrate. It means that each coating once.

2a and 2b are graphs showing the UV absorbance of the porous organic thin film prepared according to Preparation Example 1

3 is a one-dimensional schematic graph in the q _z direction of the GISAXS image of the porous organic thin film prepared according to Preparation Example 1.

2A and 2B are based on polyurea thin films stacked in 5, 10, 15, and 25 cycles, and FIG. 3 is based on polyurea thin films stacked in 100 cycles.

2A and 2B, it can be seen that the absorbance of UV increases in proportion to the number of stacking of monomers. Referring to FIG. 3, q _z has a layer structure of 6.5 nm ^−1, that is, d = 0.96 nm. You can see that it is achieved.

Preparation Example 2 Fabrication of Porous Organic Material Thin Film on Silicon Substrate

Except for using a silicon substrate instead of a quartz substrate, a porous organic thin film was obtained by the same method as in Preparation Example 1.

4A to 4D are SEM images of the porous organic thin film prepared according to Preparation Example 2, and FIG. 4E is a graph showing the thickness of the porous organic thin film according to the number of lamination.

4A to 4E, it can be seen that the thickness of the porous organic thin film increases in proportion to the number of laminations.

5A to 5D are AFM height images (including height profile data) of the porous organic thin film manufactured according to Preparation Example 2, and are graphs showing the thickness of the porous organic thin film according to the number of laminations of FIG. 5E.

5A, 5A, 5C and 5D are based on porous organic thin films deposited in 5, 15, 18 and 30 cycles, respectively. 5A to 5D, the dark portion is the bottom portion of the silicon substrate and the bright portion is the portion where the polyurea thin film is formed.

5A to 5E, it can be seen that the thickness of the porous organic thin film increases in proportion to the number of laminations.

Preparation Example 3: Fabrication of Porous Organic Material Thin Film on Cellulose Substrate

A porous organic material thin film was obtained in the same manner as in Preparation Example 1, except that a cellulose substrate was used instead of a quartz substrate, and the amount of the organic solution in which each monomer was dissolved was 20 mL.

6A is an SEM image of the cellulose substrate used in Preparation Example 3, and FIG. 6B is an SEM image of the porous organic thin film prepared according to Preparation Example 3.

Preparation Example 4: Fabrication of Porous Organic Material Thin Film on Alumina Substrate

An alumina substrate was used instead of the quartz substrate, and the organic organic thin film was obtained by the same method as in Preparation Example 1, except that the amount of the organic solution in which each monomer was dissolved was 15 mL.

7A is an SEM image of the alumina substrate used in Preparation Example 4, and FIG. 7B is an SEM image of the porous organic thin film prepared according to Preparation Example 4.

Preparation Example 5 Fabrication of Porous Organic Pattern Thin Film on Patterned Silicon Substrate

2w / v% APTES (3-aminopropyltriethoxysilane) anhydrous toluene solution was spin-coated on PDMS (polydimethylsiloxane) having a line pattern of 5㎛ size. The APMS-coated PDMS was stamped on an air plasma-treated silicon substrate to prepare a silicon substrate having amino groups pre-patterned to a size of 5 μm. Tetra (4-isocyanatophenyl) methane as the first monomer and tetra (4-aminophenyl) methane as the second monomer were dissolved in anhydrous THF, respectively, and tetra (4-isocyanatophenyl) methane at a concentration of 0.2w / v%. A solution (5 mL) and a tetra (4-aminophenyl) methane solution (5 mL) at 0.2w / v% concentration were prepared.

The surface-amine-patterned silicon substrate was reacted by supporting it in a tetra (4-isocyanatophenyl) methane solution under stirring at room temperature and under nitrogen atmosphere for 3 hours. After the reaction, unreacted tetra (4-isocyanatophenyl) methane adsorbed onto tetra (4-isocyanatophenyl) methane coated silicon substrate was washed three times with clean anhydrous THF. Subsequently, the silicon substrate was supported by reacting with stirring tetra (4-aminophenyl) methane solution for 20 seconds, and then unreacted tetra (4-aminophenyl) methane was washed three times with clean anhydrous THF. Subsequently, the reaction was carried out by supporting the tetra (4-isocyanatophenyl) methane solution and the tetra (4-aminophenyl) methane solution for 20 seconds, and then washing the unreacted monomers on the patterned silicon substrate. A porous organic pattern thin film was obtained.

8 is an AFM height image (including height profile data) of the porous organic pattern thin film prepared according to Preparation Example 5.

Referring to FIG. 8, it can be seen that the patterned porous organic thin film may be formed by sequentially laminating the first monomer and the second monomer on the patterned silicon substrate.

Preparation Example 6 Fabrication of Porous Organic Pattern Thin Film on Patterned Polyimide Substrate

A porous organic pattern thin film was obtained by the same method as in Preparation Example 5 except that the line pattern was formed on the polyimide substrate instead of the silicon substrate in a size of 10 μm.

9 is an AFM height image (including height profile data) of the porous organic pattern thin film prepared according to Preparation Example 6.

Referring to FIG. 9, it can be seen that the patterned porous organic thin film can be formed by sequentially laminating the first monomer and the second monomer on the patterned polyimide substrate.

In the above, the present invention has been described in detail with reference to preferred embodiments, but the present invention is not limited to the above embodiments, and various modifications and changes by those skilled in the art within the spirit and scope of the present invention. You can change it.

FIG. 1 is a schematic diagram illustrating a method of preparing a porous organic thin film using tetra (4-isocyanatophenyl) methane (TIPM) as a first monomer and tetra (4-aminophenyl) methane (TAPM) as a second monomer.

2a and 2b is a graph showing the UV absorbance of the porous organic thin film prepared according to Preparation Example 1

3 is a one-dimensional schematic graph in the q _z direction of the GISAXS image of the porous organic thin film prepared according to Preparation Example 1.

4A to 4D are SEM images of the porous organic thin film prepared according to Preparation Example 2, and FIG. 4E is a graph showing the thickness of the porous organic thin film according to the number of lamination.

5A to 5D are AFM height images (including height profile data) of the porous organic thin film prepared according to Preparation Example 2, and FIG. 5E is a graph showing the thickness of the porous organic thin film according to the number of laminations.

6A is an SEM image of the cellulose substrate used in Preparation Example 3, and FIG. 6B is an SEM image of the porous organic thin film prepared according to Preparation Example 3. FIG.

FIG. 7A is an SEM image of the alumina substrate used in Preparation Example 4, and FIG. 7B is an SEM image of the porous organic thin film prepared according to Preparation Example 4. FIG.

8 is an AFM height image (including height profile data) of the porous organic pattern thin film prepared according to Preparation Example 5.

9 is an AFM height image (including height profile data) of a porous organic pattern thin film prepared according to Preparation Example 6.

Claims (17)

(a) preparing a substrate having a functional group bondable to an amino group; (b) coating the first monomer having 2 to 4 amino groups on the substrate to react with the functional group, and removing the unreacted first monomer; And (c) coating a second monomer having 2 to 4 isocyanate groups or 2 to 4 acyl chloride groups on the coated first monomer to react with the first monomer, and removing the unreacted second monomer. Include, At least one of the first monomer and the second monomer is a compound represented by one of the following Chemical Formulas 1 to 3 <Formula 1>

Wherein R is all amino groups, all isocyanate groups or all acylchloride groups, and X is a carbon atom or a silicon atom. <Formula 2>

Wherein R is all amino groups, all isocyanate groups or all acylchloride groups. <Formula 3>

Wherein R is all amino groups, all isocyanate groups or all acylchloride groups, and n is 0 or 1. The method of claim 1, wherein after performing step (c): And coating the first monomer on the coated second monomer to react with the second monomer and removing the unreacted first monomer. The method of claim 1, Method for producing a porous organic thin film is a substrate having a functional group capable of bonding to the amino group is a substrate coated with a monomer represented by the following formula (4) or (5): <Formula 4>

Wherein X is an isocyanate group, acyl chloride group, aldehyde group, epoxy group, glycidyloxy group or phthalic anhydride group, and R ₁ to R ₃ are independently of each other H, Cl, methoxy group or ethoxy group (where R is At least one of ₁ to R ₃ is Cl, a methoxy group or an ethoxy group), and n is an integer of 1 to 10. <Formula 5>

In the above formula, X is an isocyanate group, acyl chloride group, aldehyde group, epoxy group, glycidyloxy group or phthalic anhydride group, R ₁ and R ₃ are each independently H or C 1 -C 5 alkyl group, n is 1 to 15 Is an integer. The method of claim 1, The substrate provided with a functional group bondable to the amino group is a polymer organic thin film manufacturing method comprising an isocyanate group, acyl chloride group, aldehyde group, epoxy group, glycidyloxy group or phthalic anhydride group. The method of claim 1, The first monomer is a C1 to C20 aliphatic compound substituted with 2 to 4 amino groups or a C6 to C30 aromatic compound substituted with 2 to 4 amino groups, and the second monomer is 2 to 4 isocyanate groups or 2 to 4 amino groups. A method for producing a porous organic thin film, which is an aliphatic compound of C1 to C20 substituted with four acyl chloride groups or an aromatic compound of C6 to C30 substituted with 2 to 4 isocyanate groups or 2 to 4 acyl chloride groups. The method of claim 1, The first monomer or the second monomer is any one selected from the group consisting of the following compounds of the porous organic thin film manufacturing method.

(n is an integer from 1 to 6),

,

,

,

,

,

,

,

,

(n is 0 or 1) In the above formulas, R is all amino groups, all isocyanate groups or all acylchloride groups. The method of claim 1, Coating and reacting the first monomer or the second monomer is carried out by supporting the substrate in an organic solution in which the first monomer is dissolved or an organic solution in which the second monomer is dissolved. The method of claim 1, And selectively etching the substrate on which the porous organic thin film is formed. (a) preparing a substrate having an amino group; (b) coating the first monomer having 2 to 4 isocyanate groups or 2 to 4 acyl chloride groups on the substrate to react with the amino group, and removing the unreacted first monomer; And (c) coating a second monomer having 2 to 4 amino groups on the coated first monomer to react with the first monomer, and removing the unreacted second monomer, At least one of the first monomer and the second monomer is a compound represented by one of the following Chemical Formulas 1 to 3 <Formula 1>

Wherein R is all amino groups, all isocyanate groups or all acylchloride groups, and X is a carbon atom or a silicon atom. <Formula 2>

Wherein R is all amino groups, all isocyanate groups or all acylchloride groups. <Formula 3>

Wherein R is all amino groups, all isocyanate groups or all acylchloride groups, and n is 0 or 1. The method of claim 9, wherein after performing step (c): And coating the first monomer on the coated second monomer to react with the second monomer and removing the unreacted first monomer. 10. The method of claim 9, The substrate having an amino group is a method for producing a porous organic thin film which is a substrate coated with a monomer represented by the following formula (6) or (7): <Formula 6>

Wherein X is an amino group, and R ₁ to R ₃ are H, Cl, methoxy or ethoxy groups irrespective of each other, provided that at least one of R ₁ to R ₃ is Cl, methoxy or ethoxy and n is an integer of 1-10. <Formula 7>

Wherein X is an amino group, R ₁ and R ₃ are each independently an alkyl group of H or C 1 to C 5, and n is an integer from 1 to 15. 10. The method of claim 9, The substrate with an amino group is a porous organic thin film manufacturing method which is a polymer substrate containing an amino group. 10. The method of claim 9, The first monomer is an aliphatic compound of C1 to C20 substituted with 2 to 4 isocyanate groups or 2 to 4 acyl chloride groups or an aromatic compound of C6 to C30 substituted with 2 to 4 isocyanate groups or 2 to 4 acyl chloride groups And wherein the second monomer is a C1 to C20 aliphatic compound substituted with 2 to 4 amino groups or a C6 to C30 aromatic compound substituted with 2 to 4 amino groups. 10. The method of claim 9, The first monomer or the second monomer is a porous organic thin film manufacturing method which is any one selected from the group consisting of:

(n is an integer from 1 to 6),

,

,

,

,

,

,

,

,

(n is 0 or 1) In the above formulas, R is all amino groups, all isocyanate groups or all acylchloride groups. 10. The method of claim 9, Coating and reacting the first monomer or the second monomer is carried out by supporting the substrate in an organic solution in which the first monomer is dissolved or an organic solution in which the second monomer is dissolved. 10. The method of claim 9, And selectively etching the substrate on which the polyurea thin film is formed. A porous organic thin film prepared by the method of any one of claims 1 to 16.

Images