KR20130127197A - Polymer, method of preparing the same, and article including the polymer - Google Patents

Abstract

Provided are a polymer derived from a polyamic acid including repeating units represented by chemical formula 1 and chemical formula 2, copolymers thereof, or blends thereof; polyimide including repeating units represented by chemical formula 3 and chemical formula 4, copolymers thereof, or blends thereof; or combination thereof, a manufacturing method thereof, and articles including the polymer.

Description

TECHNICAL FIELD [0001] The present invention relates to a polymer, a method for producing the same, and a molded article comprising the polymer. BACKGROUND ART [0002]

The present invention relates to a polymer, a method for producing the same, and a molded article comprising the polymer.

The diffusion of small molecules or ions through pores in hard organic materials is a phenomenon based essentially on subnano or nanotechnology. Such a membrane containing an organic material can be used for selectively separating low molecular ions or ions easily, and this technique can be applied to various fields such as chemical manufacturing process, energy conversion, energy storage, organic battery, fuel cell, And can be used for various purposes.

Therefore, researches are actively being conducted. However, as described above, a material having both heat resistance, chemical resistance, solubility in general solvents and mechanical strength has not been developed at the same time while selectively separating low molecular weight or ion, and thus it has not been applied to various application fields. to be.

One embodiment of the present invention is to provide a polymer having excellent low-molecular permeability and selectivity, and excellent heat resistance, chemical resistance, and solubility in a solvent.

Another embodiment of the present invention is to provide a method for producing the polymer.

Another embodiment of the present invention is to provide a molded article comprising the polymer.

According to one aspect of the present invention, there is provided a polymer comprising: a polyamic acid including a polyamic acid, a copolymer thereof, or a blend thereof; A polyimide including repeating units represented by the following formulas (3) and (4), a copolymer thereof, or a blend thereof; Or a combination thereof.

In the above Chemical Formulas 1 to 4,

Ar ¹ is an aromatic ring group selected from the group consisting of a substituted or unsubstituted tetravalent C6 to C60 arylene group and a substituted or unsubstituted tetravalent C4 to C60 heterocyclic group which are the same or different from each other in each repeating unit, Said aromatic ring group being present alone; Two or more are joined to each other to form a condensed ring; Two or more single bond, O, S, C (= O), CH (OH), S (= O) 2, Si (CH 3) 2, (CH 2) p ( where, 1≤p≤10) , (CF _{2) q (where, 1≤q≤10), C (CH 3} ) 2, C (CF 3) 2, C (= O) NH or a substituted or unsubstituted tetravalent aliphatic organic groups C1 to C30 Lt; / RTI >

,

T represents a divalent C1 to C40 aliphatic organic group, a substituted or unsubstituted quaternary C3 to C40 alicyclic group, or a substituted or unsubstituted aliphatic group, A tetravalent C6 to C40 aromatic organic group,

Y is the same or different from each other in each repeating unit and is independently OH, SH or NH ₂ ,

n is an integer satisfying 10? n? 400.

The polymer derived from the polyamic acid or the polymer derived from the polyimide may have a free volume degree (FFV) of about 0.20 to about 0.35.

The polymer derived from the polyamic acid or the polymer derived from the polyimide may have an interplanar distance by XRD measurement ranging from about 520 pm to about 850 pm.

The polymer derived from the polyamic acid or the polymer derived from the polyimide may have a BET surface area of about 280 m ² / g to about 600 m ² / g.

The Ar ¹ may be selected from those represented by the following formulas.

Where

X ¹ to X ⁶ are the same or different, each independently O, S, C (= O ), CH (OH), S (= O) 2, Si (CH 3) 2, (CH 2) p ( where , and _{1≤p≤10), (CF 2) q} ( _{where, 1≤q≤10), C (CH 3} ) 2, C (CF 3) 2, or C (= O) NH,

W ¹ and W ² are the same or different and each independently O, S, or C (= O)

Z ¹ is O, S, CR ³⁰⁰ R ³⁰¹ or NR ³⁰² wherein R ³⁰⁰ , R ³⁰¹ and R ³⁰² are the same or different and are each independently hydrogen or a C 1 to C 5 alkyl group,

Z ² and Z ³ are the same or different and are each independently N or CR ³⁰³ (wherein R ³⁰³ is a hydrogen or a C 1 to C 5 alkyl group) but not CR ³⁰³ at the same time,

T is independently a substituted or unsubstituted quadrivalent C1 to C40 aliphatic organic group, a substituted or unsubstituted quadrivalent C3 to C40 alicyclic group group, or a substituted or unsubstituted quadrivalent C6 to C40 aromatic organic group,

R ¹ to R ⁶² are the same or different and are each independently hydrogen or a substituted or unsubstituted C1 to C10 aliphatic organic group,

k1 to k3, k8 to k14, k24, k25, k49 to k54 and k59 to k62 are integers of 0 to 2,

k5, k15, k16, k19, k21 and k23 are integers of 0 or 1,

and k55 to k58 are integers of from 0 to 3, and k4, k6, k7, k17, k18, k20, k22, k26 to k29, k31, k34 to k36, k38, k41, k44 to k46,

k30, k37, k42, k43, k47 and k48 are integers of 0 to 4,

k32, k33, k39, and k40 are integers of 0 to 5.

The above T may be selected from those represented by the following formulas.

Where

R ²⁰⁰ to R ²³¹ are the same or different and each independently represents hydrogen, a substituted or unsubstituted C1 to C30 aliphatic organic group, a substituted or unsubstituted C3 to C30 alicyclic group or a substituted or unsubstituted divalent C6 To C30 aromatic organic groups,

t1 to t12 are the same or different from each other and independently an integer of 0 to 4;

Specifically, T may be selected from those represented by the following formulas.

Specifically, Ar ¹ may be selected from those represented by the following formulas.

In the polymer, the molar ratio between the respective repeating units in the copolymer of the polyamic acid containing the repeating units represented by the formulas (1) and (2) may be about 0.1: 9.9 to about 9.9: 0.1.

On the other hand, in the polymer, the molar ratio between the respective repeating units in the polyimide copolymer containing the repeating units represented by the above formulas (3) and (4) may be about 0.1: 9.9 to about 9.9: 0.1.

The polymer derived from the polyamic acid and the polymer derived from the polyimide may include a compound containing a repeating unit represented by any of the following Chemical Formulas 5 to 8 or a copolymer thereof.

In the above Chemical Formulas 5 to 8,

Ar ¹ , T and n are as described in Ar ¹ , T and n in the above Chemical Formulas 1 to 16, respectively,

Ar ^{1 '} are the same or different and are each independently an aromatic ring group selected from substituted or unsubstituted divalent C6 to C60 arylene groups and substituted or unsubstituted divalent C4 to C60 heterocyclic groups, and the aromatic ring group is Either alone; Two or more are joined to each other to form a condensed ring; Two or more single bond, O, S, C (= O), CH (OH), S (= O) 2, Si (CH 3) 2, (CH 2) p ( where, 1≤p≤10) , (CF _{2) q (where, 1≤q≤10), C (CH 3} ) 2, C (CF 3) 2, C (= O) NH , or substituted or unsubstituted C1 to C30 aliphatic organic tetravalent Lt; / RTI >

Y " is O or S;

Examples of Ar ¹ and T, and descriptions of specific examples are as described above.

The Ar ^{1 '} may be selected from those represented by the following formulas.

Where

X ¹ to X ⁶ are the same or different, each independently O, S, C (= O ), CH (OH), S (= O) 2, Si (CH 3) 2, (CH 2) p ( where , and _{1≤p≤10), (CF 2) q} ( _{where, 1≤q≤10), C (CH 3} ) 2, C (CF 3) 2, or C (= O) NH,

W ¹ and W ² are the same or different and each independently O, S, or C (= O)

Z ¹ is O, S, CR ³⁰⁰ R ³⁰¹ or NR ³⁰² wherein R ³⁰⁰ , R ³⁰¹ and R ³⁰² are the same or different and are each independently hydrogen or a C 1 to C 5 alkyl group,

Z ² and Z ³ are the same or different and are each independently N or CR ³⁰³ (wherein R ³⁰³ is a hydrogen or a C 1 to C 5 alkyl group) but not CR ³⁰³ at the same time,

T is independently a substituted or unsubstituted quadrivalent C1 to C40 aliphatic organic group, a substituted or unsubstituted quadrivalent C3 to C40 alicyclic group group, or a substituted or unsubstituted quadrivalent C6 to C40 aromatic organic group,

R ¹ to R ⁶² are the same or different and are each independently hydrogen or a substituted or unsubstituted C1 to C10 aliphatic organic group or a metal sulfonate group,

k63, k69, k84 to k88, k92 to k96, k102 to k109, k116 and k119 are integers of 0 to 4,

k81, k115, k117, k118, k120, and k123 are integers of 0 to 3,

k100, k101, k113, k114, k121, and k122 are integers of 0 to 2,

k70 is an integer of 0 or 1,

k89, k91, k97, and k99 are integers of 0 to 5.

As described above, T in Ar ^{1 '} is as defined for T in Ar ¹ , and examples and specific examples thereof are also the same as those defined for T in Ar ¹ .

Specifically, Ar ^{1 '} may be selected from those represented by the following formulas.

Where

M is hydrogen or a metal, and the metal is sodium, potassium, lithium, an alloy thereof, or a combination thereof.

The polymer may have a weight average molecular weight (Mw) of from about 10,000 g / mol to about 500,000 g / mol.

A method for producing a polymer according to another embodiment of the present invention includes the steps of imidizing a polyamic acid containing a repeating unit represented by the above formulas (1) and (2), a copolymer thereof, or a blend thereof, Mead; And heat treating the polyimide.

The heat treatment may be performed at a temperature rising rate of about 1 占 폚 / min to about 30 占 폚 / min to a temperature of about 350 占 폚 to about 500 占 폚, and at that temperature for about 1 minute to about 12 hours under an inert atmosphere.

According to another embodiment of the present invention, there is provided a process for preparing a polymer, comprising the steps of: heat-treating a polyimide including the repeating units represented by the above formulas 3 and 4, a copolymer thereof, .

The above description of the heat treatment is as described above.

The method for producing a polymer according to another embodiment of the present invention includes a polyamic acid including the repeating units represented by the above formulas (1) and (2), a copolymer thereof or a polyamic acid including a blend thereof, Imidizing a polyamic acid in a compound comprising a polyimide including a repeating unit represented by Formula (3) and Formula (4), a copolymer thereof, or a blend of polyimides comprising a blend thereof to obtain a polyimide; And heat treating the polyimide.

The above description of the heat treatment is as described above.

Another aspect of the present invention provides a molded article comprising the polymer.

The molded article may be a gas separation membrane.

Other aspects of the present invention are included in the following detailed description.

The polymer according to the present invention has excellent low-molecular permeability and selectivity and is excellent in heat resistance, chemical resistance, solubility in solvents, and excellent mechanical strength.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Unless otherwise defined herein, the term "substituted" or "substituted" means that the hydrogen atom in the compound or functional group is a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C1 to C10 haloalkyl group, a C1 to C10 haloalkoxy group and a C6 group. To C20 is substituted with one or more substituents selected from the group consisting of aromatic organic groups.

As used herein, unless otherwise defined, a "heterocyclic group" refers to a substituted or unsubstituted heteroaryl group containing 1 to 3 heteroatoms selected from the group consisting of O, S, N, P, Si, Means a substituted or unsubstituted C2 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 cycloalkenyl group, a substituted or unsubstituted C2 to C30 cycloalkynyl group, or a substituted or unsubstituted C2 to C30 heteroaryl group .

Unless otherwise defined herein, the term "aliphatic organic group" means a C1 to C30 alkyl group, a C2 to C30 alkenyl group, a C2 to C30 alkynyl group, a C1 to C30 alkylene group, a C2 to C30 alkenylene group, or a C2 to C30 Means a C1 to C15 alkyl group, a C2 to C15 alkenyl group, a C2 to C15 alkynyl group, a C1 to C15 alkylene group, a C2 to C15 alkenylene group, or a C2 to C15 alkynylene group, Means a C3 to C30 cycloalkyl group, a C3 to C30 cycloalkenyl group, a C3 to C30 cycloalkynyl group, a C3 to C30 cycloalkylene group, a C3 to C30 cycloalkenylene group, or a C3 to C30 cycloalkynylene group. Specifically, a C3 to C15 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C3 to C15 cycloalkynyl group, a C3 to C15 cycloalkylene group, a C3 to C15 cycloalkenylene group, or Refers to a C3 to C15 cycloalkynylene group, and "aromatic organic group" means a C6 to C30 aryl group or a C6 to C30 arylene group, specifically a C6 to C16 aryl group or a C6 to C16 arylene group.

As used herein, unless otherwise defined, "combination" means mixing or copolymerization. "Copolymerization" means block copolymerization or random copolymerization, and "copolymer" means block copolymer or random copolymer.

In the present specification, "*" means the same or different atom or part connected to a chemical formula.

The polymer according to an embodiment of the present invention is a polyamic acid including a polyamic acid including a repeating unit represented by the following general formula (1) and a general formula (2), a copolymer thereof, or a blend thereof; A polyimide including repeating units represented by the following formulas (3) and (4), a copolymer thereof, or a blend thereof; Or a combination thereof.

[Formula 1]

(2)

(3)

[Formula 4]

In the above Chemical Formulas 1 to 4,

Ar ¹ is an aromatic ring group selected from the group consisting of a substituted or unsubstituted tetravalent C6 to C60 arylene group and a substituted or unsubstituted tetravalent C4 to C60 heterocyclic group which are the same or different from each other in each repeating unit, Said aromatic ring group being present alone; Two or more are joined to each other to form a condensed ring; Two or more single bond, O, S, C (= O), CH (OH), S (= O) 2, Si (CH 3) 2, (CH 2) p ( where, 1≤p≤10) , (CF _{2) q (where, 1≤q≤10), C (CH 3} ) 2, C (CF 3) 2, C (= O) NH or a substituted or unsubstituted tetravalent aliphatic organic groups C1 to C30 Lt; / RTI >

T represents a divalent C1 to C40 aliphatic organic group, a substituted or unsubstituted quaternary C3 to C40 alicyclic group, or a substituted or unsubstituted aliphatic group, A tetravalent C6 to C40 aromatic organic group,

Y is the same or different from each other in each repeating unit and is independently OH, SH or NH ₂ ,

n is an integer satisfying 10? n? 400.

The polyamic acid including the repeating units represented by the above formulas (1) and (2) and the polyimide including the repeating units represented by the above formulas (3) and (4) can be prepared by a general method. For example, the polyamic acid may be prepared by reacting a diamine containing an OH, SH, or NH ₂ group present in ortho position with respect to an amine group, and a tetracarboxylic acid anhydride. The polyimide may be prepared by subjecting the polyamic acid prepared as described above to thermal solution imidization or chemical imidization. The thermal solution imidization and the chemical imidization will be described later.

The polyamic acid is imidized and thermally converted through a production process to be described later, and the polyimide is thermally converted through a production process to be described later to obtain polybenzoxazole, polybenzothiazole, polypyrrolone or the like having high free volume Or a combination thereof.

The polymer derived from the polyamic acid and the polymer derived from the polyimide have excellent solubility in an organic solvent and include a flexible structure and at the same time a rigid structure ), And specifically includes an elongated ladder-like structure. Accordingly, the polymer derived from the polyamic acid and the polymer derived from the polyimide include a repeating structure in which the rigid ladder structure is connected to the flexible hinge, so that the refractory stairs are distributed in an amorphous form, And has excellent mechanical strength and processability. Therefore, it can be easily used in the form of films, fibers, hollow yarns, and the like.

The polymer derived from the polyamic acid and the polymer derived from the polyimide may have a free volume degree (FFV) of about 0.20 to about 0.35, and the d-spacing by XRD measurement is about 520 pm to about 850 < / RTI > As a result, the polymer derived from the polyamic acid and the polymer derived from the polyimide can easily transmit or separate low molecular weight molecules.

The polymer derived from the polyamic acid and the polymer derived from the polyimide may have a BET (Brunauer-Emmett-Teller) surface area of about 280 m ² / g to about 600 m ² / g. Therefore, the polymer derived from the polyamic acid and the polymer derived from the polyimide can efficiently transmit low molecular weight or can be selectively separated

In the above Chemical Formulas 1 to 4, examples of Ar ¹ may be selected from those represented by the following formulas, but are not limited thereto.

Where

X ¹ to X ⁶ are the same or different, each independently O, S, C (= O ), CH (OH), S (= O) 2, Si (CH 3) 2, (CH 2) p ( where , and _{1≤p≤10), (CF 2) q} ( _{where, 1≤q≤10), C (CH 3} ) 2, C (CF 3) 2, or C (= O) NH,

W ¹ and W ² are the same or different and each independently O, S, or C (= O)

Z ¹ is O, S, CR ³⁰⁰ R ³⁰¹ or NR ³⁰² wherein R ³⁰⁰ , R ³⁰¹ and R ³⁰² are the same or different and are each independently hydrogen or a C 1 to C 5 alkyl group,

Z ² and Z ³ are the same or different and are each independently N or CR ³⁰³ (wherein R ³⁰³ is a hydrogen or a C 1 to C 5 alkyl group) but not CR ³⁰³ at the same time,

T is independently a substituted or unsubstituted quadrivalent C1 to C40 aliphatic organic group, a substituted or unsubstituted quadrivalent C3 to C40 alicyclic group group, or a substituted or unsubstituted quadrivalent C6 to C40 aromatic organic group,

R ¹ to R ⁶² are the same or different and are each independently hydrogen or a substituted or unsubstituted C1 to C10 aliphatic organic group,

k1 to k3, k8 to k14, k24, k25, k49 to k54 and k59 to k62 are integers of 0 to 2,

k5, k15, k16, k19, k21 and k23 are integers of 0 or 1,

and k55 to k58 are integers of from 0 to 3, and k4, k6, k7, k17, k18, k20, k22, k26 to k29, k31, k34 to k36, k38, k41, k44 to k46,

k30, k37, k42, k43, k47 and k48 are integers of 0 to 4,

k32, k33, k39, and k40 are integers of 0 to 5.

The example of T may be selected from the following formulas, but is not limited thereto.

Where

R ²⁰⁰ to R ²³¹ are the same or different and each independently represents hydrogen, a substituted or unsubstituted C1 to C30 aliphatic organic group, a substituted or unsubstituted C3 to C30 alicyclic group or a substituted or unsubstituted divalent C6 To C30 aromatic organic groups,

t1 to t12 are the same or different from each other and independently an integer of 0 to 4;

Specifically, examples of T may be selected from the following formulas, but are not limited thereto.

In the above Chemical Formulas 1 to 4, specific examples of Ar ¹ may be selected from the following formulas, but are not limited thereto.

In the above Chemical Formulas 1 to 4, examples of T and specific examples thereof are the same as those mentioned for T and specific examples of T described above for Ar ¹ .

A molar ratio between repeating units in a copolymer of a polyamic acid containing repeating units represented by the above formulas (1) and (2); Or by controlling the molar ratio between the respective repeating units in the copolymer of polyimide including the repeating units represented by the above formulas (3) and (4), the physical properties of the prepared polymer can be controlled.

The molar ratio between the respective repeating units in the copolymer of the polyamic acid containing the repeating units represented by the above formulas (1) and (2) is about 0.1: 9.9 to about 9.9: 0.1, specifically about 2: 8 to about 8: , More specifically about 5: 5.

The molar ratio between the repeating units in the polyimide copolymer containing the repeating units represented by the above formulas (3) and (4) is about 0.1: 9.9 to about 9.9: 0.1, specifically about 2: 8 to about 8: 2, more specifically about 5: 5.

Such a copolymerization ratio affects the molecular structure and morphology of the prepared polymer. Such molecular structure arrangement and morphological change are related to density, pore characteristics, heat resistance, tensile strength, shear force, and the like. When the molar ratio or the copolymerization ratio is within the above range, the produced polymer can efficiently permeate low molecular weight or can be selectively separated, and can have excellent heat resistance, chemical resistance, mechanical strength and processability.

The polymer derived from the polyamic acid and the polymer derived from the polyimide may include, but are not limited to, a compound containing a repeating unit represented by any one of Chemical Formulas 5 to 8, or a copolymer thereof.

[Chemical Formula 5]

[Chemical Formula 6]

[Formula 7]

[Formula 8]

In the above Chemical Formulas 5 to 8, Ar ¹ , T and n are as described for Ar ¹ , T and n in the above Chemical Formulas 1 to 4, respectively,

Ar ^{1 '} are the same or different from each other, and each independently represents an aromatic ring group selected from a substituted or unsubstituted divalent C6 to C60 arylene group and a substituted or unsubstituted divalent C4 to C60 heterocyclic group, The ring group is present alone; Two or more are joined to each other to form a condensed ring; Two or more single bond, O, S, C (= O), CH (OH), S (= O) 2, Si (CH 3) 2, (CH 2) p ( where, 1≤p≤10) , (CF _{2) q (where, 1≤q≤10), C (CH 3} ) 2, C (CF 3) 2, C (= O) NH , or substituted or unsubstituted C1 to C30 aliphatic organic tetravalent Lt; / RTI >

Y " is O or S;

Examples of Ar ¹ and T in the above Chemical Formulas 5 to 8 and specific examples thereof are the same as those mentioned in the examples and specific examples of Ar ¹ and T in the above Chemical Formulas 1 to 4, respectively.

In the general formulas (5) to (8), examples of Ar ^{1 '} may be selected from the following formulas, but are not limited thereto.

Where

X ¹ to X ⁶ are the same or different, each independently O, S, C (= O ), CH (OH), S (= O) 2, Si (CH 3) 2, (CH 2) p ( where , and _{1≤p≤10), (CF 2) q} ( _{where, 1≤q≤10), C (CH 3} ) 2, C (CF 3) 2, or C (= O) NH,

W ¹ and W ² are the same or different and each independently O, S, or C (= O)

Z ¹ is O, S, CR ³⁰⁰ R ³⁰¹ or NR ³⁰² wherein R ³⁰⁰ , R ³⁰¹ and R ³⁰² are the same or different and are each independently hydrogen or a C 1 to C 5 alkyl group,

Z ² and Z ³ are the same or different and are each independently N or CR ³⁰³ (wherein R ³⁰³ is a hydrogen or a C 1 to C 5 alkyl group) but not CR ³⁰³ at the same time,

T is independently a substituted or unsubstituted quadrivalent C1 to C40 aliphatic organic group, a substituted or unsubstituted quadrivalent C3 to C40 alicyclic group group, or a substituted or unsubstituted quadrivalent C6 to C40 aromatic organic group,

R ⁶³ to R ¹²³ are the same or different and each independently represents hydrogen, a substituted or unsubstituted C1 to C10 aliphatic organic group, or a metal sulfonate group,

k63, k69, k84 to k88, k92 to k96, k102 to k109, k116 and k119 are integers of 0 to 4,

k81, k115, k117, k118, k120, and k123 are integers of 0 to 3,

k100, k101, k113, k114, k121, and k122 are integers of 0 to 2,

k70 is an integer of 0 or 1,

k89, k91, k97, and k99 are integers of 0 to 5.

Specifically, examples of Ar ^{1 '} may be selected from the following formulas, but are not limited thereto.

Where

M is hydrogen or a metal, and the metal is sodium, potassium, lithium, an alloy thereof, or a combination thereof.

The polymer derived from polyamic acid and the polymer derived from polyimide according to an embodiment of the present invention can be produced using polyamic acid or polyimide soluble in general organic solvent and the polymer can be easily produced without defects or cracks It is possible to simplify the manufacturing process, reduce the process cost, and can be formed in a large area. Further, the polymer can control pore size or distribution by controlling the manufacturing process conditions. As a result, the polymer can be widely applied to a variety of applications such as gas permeation, gas separation, steam separation, water purification, adsorbent, heat resistant fiber, and thin film manufacturing fields.

According to another embodiment of the present invention, the polymer may be derived from a combination of the polyamic acid and the polyimide, wherein the polymer may comprise a polymer derived from the polyamic acid and a polymer derived from the polyimide have. Unless otherwise described below, the polyamic acid, the polyimide, the polymer derived from the polyamic acid, and the polymer derived from the polyimide are as described above.

The polymer comprising the polyamic acid and the polymer derived from the polyimide is obtained by mixing a polymer derived from a polyamic acid and a polyimide derived polymer at a weight ratio of about 0.1: 9.9 to about 9.9: 0.1, 8: 2 to about 2: 8 by weight, more specifically about 5: 5 by weight. Such a polymer may have both the properties of the polymer derived from the polyamic acid described above and the characteristics of the polymer derived from the polyimide. And can have excellent dimensional stability and long-term stability.

The polymer derived from the polyamic acid and the polymer derived from the polyimide may have a weight average molecular weight (Mw) of about 10,000 g / mol to about 500,000 g / mol, respectively. In this case, the polymer derived from the polyamic acid and the polymer derived from the polyimide can be easily synthesized, and can have excellent mechanical strength and dimensional stability.

According to another embodiment of the present invention, there is provided a process for producing a polyimide, comprising: imidizing a polyamic acid containing a repeating unit represented by the above general formulas (1) and (2), a copolymer thereof or a blend thereof to obtain a polyimide; And heat treating the polyimide. The present invention also provides a method for producing a polymer. The polymer may include, but is not limited to, a compound containing a repeating unit represented by any one of formulas (5) to (8), or a copolymer thereof.

In the method for producing a polymer, the imidization may be performed by a thermal imidization process, but the present invention is not limited thereto.

The thermal imidization may be performed under an inert atmosphere at about 150 ° C to about 300 ° C for about 30 minutes to about 2 hours. If the temperature of the imidization is less than the above range, the imidization of the precursor polyamic acid is insignificant. On the contrary, even if the imidization temperature exceeds the above range, there is no significant increase in the effect.

The conditions for the imidization are that the functional groups of the polyamic acid, Ar ¹ , T and Y depending on the kind of the material.

When the polyimide is heat-treated, it is rearranged through thermal conversion reaction to obtain a polymer having picopores. The polymer having picopores has a reduced density as compared with the polyimide, an increased free volume and an increased interplanar distance as the picopores are connected to each other. As a result, the polymer having picopores can efficiently transmit low molecular weight or can be selectively separated.

In addition, the polymer derived from the polyamic acid has a rigid structure which is excellent in solubility in an organic solvent and includes a flexible structure and at the same time is connected via the flexible structure, By including a ladder-like structure, it is possible to have micropores, to have excellent processability, and to improve mechanical strength such as tensile strength, expansion rate and the like.

The heat treatment may be performed at a temperature rising rate of about 1 占 폚 / min to 30 占 폚 / min to about 350 占 폚 to about 500 占 폚, and at that temperature for about 1 minute to about 12 hours under an inert atmosphere. Specifically, the heat treatment may be performed at a temperature rising rate of about 5 ° C / min to about 20 ° C / min to a temperature of about 350 ° C to about 450 ° C, and at that temperature for about 1 hour to about 6 hours under an inert atmosphere . More specifically, the heat treatment can be performed at an elevated temperature rate of about 10 [deg.] C / min to about 15 [deg.] C / min to a temperature of about 420 [deg.] C to about 450 [deg.] C and for about 2 hours to about 5 hours have. When the heat treatment is performed within the above-mentioned range, the thermal conversion reaction can be sufficiently performed.

Through such heat treatment, polybenzoxazole, polybenzothiazole or polypyrrolone polymer containing the repeating units represented by the above formulas (5) to (8) can be obtained. The production of such a polymer is carried out through the removal of CO ₂ or H ₂ O in the polyimide obtained by the imidization.

Another embodiment of the present invention is a process for preparing a polymer comprising heat-treating a polyimide including the repeating units represented by the above-mentioned formulas (3) and (4), a copolymer thereof, or a blend thereof ≪ / RTI > The polymer may include, but is not limited to, a compound containing a repeating unit represented by any one of formulas (5) to (8), or a copolymer thereof.

Unless otherwise described below, the description of the heat treatment, the heat conversion and the rearrangement is as described above.

The polyimide can be obtained by imidizing a polyamic acid containing the repeating units represented by the above formulas (1) and (2), for example, by chemical imidization or thermal solution imidization.

The chemical imidization may be carried out by carrying out the reaction at about 20 ° C to about 180 ° C for about 4 hours to about 24 hours. At this time, acetic anhydride may be added to remove pyridine and generated water as a catalyst. If the temperature of the chemical imidization is within the above range, imidization of the polyamic acid can be sufficiently performed.

The chemical imidization may first be performed after protecting the functional groups OH, SH, and NH ₂ present at the ortho position of the amine group in the polyamic acid. Specifically, the protecting group may be removed by introducing a protecting group into the functional groups OH, SH and NH ₂ , proceeding to imidization, and then removing the protecting group. Examples of the protecting group include trimethylchlorosilane ((CH ₃ ) ₃ SiCl), triethylchlorosilane ((C ₂ H ₅ ) ₃ SiCl), tributylchlorosilane ((C ₄ H ₉ ) ₃ SiCl), tribenzylchlorosilane Such as chlorosilane and tetrahydrofuran (THF), such as ((C ₆ H ₅ ) ₃ SiCl), triethoxychlorosilane ((OC ₂ H ₅ ) ₃ SiCl) and the like, Tertiary amines such as trimethylamine, triethylamine, tripropylamine, pyridine and the like can be used. As the material for removing the protecting group, diluted hydrochloric acid, sulfuric acid, nitric acid, acetic acid, etc. may be used. As described above, chemical imidization using a protecting group can increase the yield and molecular weight of the polymer according to one embodiment of the present invention.

The thermal solution imidization may be carried out by allowing the reaction to proceed in a solution state at about 100 ° C to about 180 ° C for about 2 hours to about 30 hours. If the temperature of the thermal solution imidization is within the above range, imidization of the polyamic acid can be sufficiently performed.

The thermal solution imidization may be performed after _first protecting OH, SH, and NH ₂ , which are functional groups present at the ortho position of a polyamine, with a polyamine acid. Specifically, the protecting group may be removed by introducing a protecting group into the functional groups OH, SH and NH ₂ , proceeding to imidization, and then removing the protecting group. As the protecting group, there may be used, for example, a chlorosilane such as trimethylchlorosilane, triethylchlorosilane, tributylchlorosilane, tribenzylchlorosilane, triethoxychlorosilane or the like, or hydrofuran such as tetrahydrofuran, , Tertiary amines such as triethylamine, tripropylamine, pyridine and the like can be used. Examples of the material for removing the protecting group include diluted hydrochloric acid, sulfuric acid, nitric acid, acetic acid, and the like.

The thermal solution imidization may be performed using an azeotropic mixture prepared by further adding benzene, toluene, xylene, cresol or the like, or aliphatic organic solvents such as hexane or cyclohexane.

The thermal solution imidization by introducing a protecting group and using an azeotropic mixture as described above can increase the yield and molecular weight of the polymer according to one embodiment of the present invention.

The conditions for the imidization are that the functional groups of the polyamic acid, Ar ¹ , T and Y depending on the kind of the material.

Another embodiment of the present invention is a polyamic acid comprising a repeating unit represented by the above formulas (1) and (2), a copolymer thereof, or a polyamic acid including a blend thereof, Imidizing a polyamic acid in a compound comprising a polyimide including a repeating unit having a repeating unit represented by the following general formula (1), a copolymer thereof, or a blend thereof, to obtain a polyimide; And heat treating the polyimide. The present invention also provides a method for producing a polymer. The polymer may include, but is not limited to, a compound containing a repeating unit represented by any one of formulas (5) to (8), or a copolymer thereof.

Unless otherwise described below, the imidization, the heat treatment, the heat conversion, and the rearrangement are as described above.

In the process of preparing the polymer, related characteristics such as pore size and distribution can be controlled by controlling the polymer design in consideration of the characteristics of Ar ₁ , T and Y in the chemical structure.

The polymer according to an embodiment of the present invention includes a rigid structure existing in a polymer, so that it can withstand not only mild conditions but also long working hours, acidic conditions and harsh conditions such as high humidity and high temperature. That is, the polymer according to one embodiment of the present invention is excellent in chemical stability, heat resistance, and mechanical properties.

The polymer having repeating units represented by the above formulas (5) to (8) or a copolymer thereof is designed to have an appropriate weight average molecular weight in the preparation stage. Specifically, the polymer has a weight average molecular weight of about 10,000 g / mol to about 500,000 g / mol. When the weight average molecular weight thereof is within the above range, the physical properties of the polymer can be maintained to be excellent.

A polymer according to an embodiment of the present invention is a polymer derived from a polyamic acid or a polymer derived from a polyimide, and has a picopore. The picopores are formed in an hourglass shape by connecting two or more of the picopores. Thus, the picopores can efficiently transmit or selectively separate small molecules due to high free volume.

Another embodiment of the present invention provides a molded article comprising the polymer. The molded article may be a sheet, a film, a powder, a film or a fiber, but is not limited thereto.

The molded product may have a structure in which a rigid ladder structure is connected in a flexible hinge structure to the inside of the molded article so that the refractable stairs may have micropores formed by amorphous distribution, specifically dumbbell-shaped micropores . Therefore, the molded article can efficiently transmit or selectively separate low molecular weight materials, and is excellent in heat resistance, surface hardness and dimensional stability, and thus can be used in various technical fields requiring the above performance. Specifically, the molded article may be used as a gas separation membrane.

Examples and comparative examples of the present invention will be described below. However, the following examples are only examples of the present invention, and the present invention is not limited by the following examples.

Example : Synthesis of Polymer and Preparation of Gas Separation Membrane Using It

Example  One

Polymers containing polybenzoxazole were prepared as shown in Reaction Scheme 1 below.

[Reaction Scheme 1]

100 g of bisphenol A was mixed with 4.5 g of methane sulfonic acid and reacted at 140 ° C for 5 hours. Subsequently, precipitation and separation were carried out in 2 liters of distilled water to obtain 3,3,3 ', 3'-tetramethyl-1,1'-spirobi (indan) -6,6'-diol (3,3,3' , 3'-tetramethyl-1,1'-spirobi (indane) -6,6'-diol.

Then, the prepared 3,3,3 ', 3'-tetramethyl-1,1'-spirobi (indan) -6,6'-diol was added to 360 ml of nitric acid and reacted for 5 hours, 3'-tetramethyl-1,1'-spirobi (indane) -5,5'-dinitro-6,6'-diol (3,3,3 ' -spirobi (indane) -5,5'-dinitro-6,6'-diol.

Subsequently, the above-prepared 3,3,3 ', 3'-tetramethyl-1,1'-spirobi (indan) -5,5'-dinitro-6,6'-diol was mixed with 2.5 g of Pd / And the mixture was stirred with 66 ml of NH ₂ NH ₂ H ₂ O for 10 hours while refluxing it in 330 ml of ethanol to obtain 3,3,3 ', 3'-tetramethyl-1,1'-spirobi (indane) -5 , 3'-tetramethyl-1,1'-spirobi (indane) -5,5'-diamino-6,6'-diol (3,3,3 ' 2.85 g.

3.384 g of the above-prepared 3,3,3 ', 3'-tetramethyl-1,1'-spirobi (indane) -5,5'-diamino-6,6'-diol (TSBIDD) N-methylpyrrolidinone (NMP) together with 4.442 g of 4,4'-hexafluoropropylidene diphthalic dianhydride (6FDA) (3,3 ', 4,4'-hexafluoropropylidene diphthalic dianhydride, The solution was reacted at 31.3 g for 4 hours to prepare a pale yellow solution.

Then, 40 ml of pyridine and ortho-xylene were added thereto, and the mixture was reacted for 6 hours while refluxing to obtain a yellow solution. Subsequently, it is immersed in distilled water, washed and dried, and then the resulting 6FDA-TSBIDD polyimide is dissolved again in N-methylpyrrolidone (NMP) to 20 wt%.

Then, the dissolved solution was cast on a glass plate and kept at 100 ° C, 150 ° C, 200 ° C, and 250 ° C for 1 hour in a vacuum oven to produce a film. The thickness of the film thus prepared was 64 占 퐉.

The polyimide film prepared above was put into a muffle furnace, heated to 300 캜 at a rate of 10 캜 / min, and maintained at 300 캜 for 30 minutes. Subsequently, heat treatment was performed by heating to 425 DEG C and holding for 2 hours to obtain a transparent light brown TSBIDD-based polybenzoxazole film, thereby preparing a gas separation membrane.

FTIR analysis, free volume degree, interplanar distance and BET surface area were measured for the obtained polybenzoxazole film according to the following method.

< FTIR  Analysis>

Fourier transform infrared (FTIR) spectra were measured using an infrared microspectrometer (IlluminatIR, SensIR Technologies, Danbury, CT, USA).

< Free volume  Measurement>

The density of the polymer is related to the free volume and affects gas permeability. The density of the membrane was measured by the buoyancy method using a Sartorius LA 310S analytical balance according to the following equation (1).

[Equation 1]

In the above equation (1)

ρ _P is the density of the polymer,

ρ _W is the density of the deionized water,

Wa Is the weight of the polymer measured in air,

Ww Is the weight of the polymer measured in deionized water.

The free volume diagrams (FFV, V _f ) were calculated from the above data according to the following equation (2).

&Quot; (2) &quot;

In Equation (2)

V is the specific volume of the polymer,

Vw is a specific Van der Waals volume.

<Measurement of interplanar distance>

The interplanar distance was calculated according to the Bragg's equation from the results of the X-ray diffraction pattern.

< BET  Surface area measurement>

The BET surface area was determined by the Brunauer-Emmett-Teller method using a pore size and surface area analyzer (ASAP 2020, Micromeritics, USA) And calculated using the formula.

FTIR analysis showed that polybenzoxazole characteristic bands of 1,553 cm ^-1 , 1,480 cm ^-1 (C = N) and 1,058 cm ^-1 (CO) were not present in the polyhydroxyimide. The free volume of the prepared polymer was 0.26 and the interplanar distance was 642 pm. The BET surface area was 446 m ² / g.

Example  2

The polybenzoxazole-containing polymer was prepared in the same manner as in Example 1 except that the polybenzoxazole film was heat-treated at 450 ° C for 30 minutes, and polybenzoxazole film was obtained. FT-IR analysis showed that polybenzoxazole characteristic bands of 1,553 cm ^-1 , 1,480 cm ^-1 (C = N) and 1,058 cm ^-1 (CO) were not present in the polyhydroxyimide. The free volume of the prepared polymer was 0.26 and the interplanar distance was 619 pm. The BET surface area was 371 m ² / g.

Example  3

3.384 g of the above-prepared 3,3,3 ', 3'-tetramethyl-1,1'-spirobi (indane) -5,5'-diamino-6,6'-diol (TSBIDD) N-methylpyrrolidinone (NMP) together with 4.442 g of 4,4'-hexafluoropropylidene diphthalic dianhydride (6FDA) (3,3 ', 4,4'-hexafluoropropylidene diphthalic dianhydride, The solution was reacted at 31.3 g for 4 hours to prepare a pale yellow solution.

The prepared solution was cast on a glass plate and kept at 100 ° C, 150 ° C, 200 ° C, and 250 ° C for 1 hour in a vacuum oven to produce a film. The thickness of the film thus prepared was 126 탆.

The polyimide film prepared above was put into a muffle furnace, heated to 300 캜 at a rate of 10 캜 / min, and maintained at 300 캜 for 30 minutes.

Subsequently, heat treatment was performed by heating to 425 DEG C and holding for 2 hours to obtain a transparent light brown TSBIDD-based polybenzoxazole film, thereby preparing a gas separation membrane.

FT-IR analysis showed that polybenzoxazole characteristic bands of 1,553 cm ^-1 , 1,480 cm ^-1 (C = N) and 1,058 cm ^-1 (CO) were not present in the polyhydroxyimide. The free volume of the prepared polymer was 0.26 and the interplanar distance was 634 pm. The BET surface area was 431 m ² / g.

Example  4

Polymers containing polybenzoxazole were prepared as shown in Reaction Scheme 2 below.

[Reaction Scheme 2]

3.384 g of the above-prepared 3,3,3 ', 3'-tetramethyl-1,1'-spirobi (indane) -5,5'-diamino-6,6'-diol (TSBIDD) A pale yellow solution was prepared by reacting 2.181 g of pyromelitic (PMDA) with 31.3 g of N-methylpyrrolidinone (NMP) solution for 4 hours.

Then, 40 ml of pyridine and ortho-xylene were added thereto, and the mixture was reacted for 6 hours while refluxing to obtain a yellow solution. Subsequently, it is immersed in distilled water, followed by washing and drying, and the resultant PMDA-TSBIDD polyimide is dissolved again in N-methylpyrrolidone (NMP) in an amount of 20% by weight. Subsequently, the dissolved solution was cast on a glass plate and kept in a vacuum oven at 100 ° C, 150 ° C, 200 ° C, and 250 ° C for 1 hour, respectively, to obtain a gas separation membrane. The thickness of the film thus prepared was 45 탆.

Heat treatment temperature: 450 캜 for 1.5 hours

FT-IR analysis showed that polybenzoxazole characteristic bands of 1,553 cm ^-1 , 1,480 cm ^-1 (C = N) and 1,058 cm ^-1 (CO) were not present in the polyhydroxyimide. The free volume of the prepared polymer was 0.21 and the interplanar distance was 525 pm. The BET surface area was 282.5 m ² / g.

Example  5

3.384 g of the above-prepared 3,3,3 ', 3'-tetramethyl-1,1'-spirobi (indane) -5,5'-diamino-6,6'-diol (TSBIDD) A pale yellow solution was prepared by reacting 2.181 g of pyromelitic (PMDA) with 31.3 g of N-methylpyrrolidinone (NMP) solution for 4 hours.

The prepared solution was cast on a glass plate and kept in a vacuum oven at 100 ° C, 150 ° C, 200 ° C and 250 ° C for 1 hour, respectively, to produce a film. The thickness of the film thus prepared was 52 탆.

The polyimide film prepared above was put into a muffle furnace, heated to 300 캜 at a rate of 10 캜 / min, and maintained at 300 캜 for 30 minutes.

Subsequently, heat treatment was performed by heating to 450 DEG C and holding for 1.5 hours to prepare a transparent pale brown TSBIDD-based polybenzoxazole film.

FT-IR analysis showed that polybenzoxazole characteristic bands of 1,553 cm ^-1 , 1,480 cm ^-1 (C = N) and 1,058 cm ^-1 (CO) were not present in the polyhydroxyimide. The free volume of the prepared polymer was 0.22 and the interplanar distance was 544 pm.

Example  6

Polymers containing polybenzoxazole were prepared as shown in Reaction Scheme 3 below.

Scheme 3

3.384 g of the above-prepared 3,3,3 ', 3'-tetramethyl-1,1'-spirobi (indane) -5,5'-diamino-6,6'-diol (TSBIDD) N-methylpyrrolidinone (NMP) solution 31.3 (trade name, manufactured by Tosoh Corporation) along with 2.942 g of 4,4'-biphenyltetracarboxylic acid dianhydride (3,3 ', 4,4'- g for 4 hours to prepare a pale yellow solution.

Then, 40 ml of pyridine and ortho-xylene were added thereto, and the mixture was reacted for 6 hours while refluxing to obtain a yellow solution. Subsequently, it is immersed in distilled water, washed and dried, and then the resulting BPDA-TSBIDD polyimide is dissolved again in N-methylpyrrolidone (NMP) to a concentration of 20% by weight. Then, the dissolved solution was cast on a glass plate and kept at 100 ° C, 150 ° C, 200 ° C, and 250 ° C for 1 hour in a vacuum oven to produce a film. The thickness of the film thus prepared was 61 mu m.

The polyimide film prepared above was put into a muffle furnace, heated to 300 캜 at a rate of 10 캜 / min, and maintained at 300 캜 for 30 minutes.

Subsequently, heat treatment was performed by heating to 500 DEG C and holding for 15 minutes to prepare a transparent pale brown TSBIDD-based polybenzoxazole film.

FT-IR analysis showed that polybenzoxazole characteristic bands of 1,553 cm ^-1 , 1,480 cm ^-1 (C = N) and 1,058 cm ^-1 (CO) were not present in the polyhydroxyimide. The prepared polymer had a free volume of 0.18 and interplanar distance of 526 pm. The BET surface area was 306 m ² / g.

Example  7

3.384 g of the above-prepared 3,3,3 ', 3'-tetramethyl-1,1'-spirobi (indane) -5,5'-diamino-6,6'-diol (TSBIDD) N-methylpyrrolidinone (NMP) solution 31.3 (trade name, manufactured by Tosoh Corporation) along with 2.942 g of 4,4'-biphenyltetracarboxylic dianhydride (BPDA) g for 4 hours to prepare a pale yellow solution.

The prepared solution was cast on a glass plate and kept at 100 ° C, 150 ° C, 200 ° C, and 250 ° C for 1 hour in a vacuum oven to produce a film. The thickness of the film thus prepared was 93 탆.

The polyimide film prepared above was put into a muffle furnace, heated to 300 캜 at a rate of 10 캜 / min, and maintained at 300 캜 for 30 minutes.

Subsequently, heat treatment was performed by heating to 500 DEG C and holding for 15 minutes to prepare a transparent pale brown TSBIDD-based polybenzoxazole film.

FT-IR analysis showed that polybenzoxazole characteristic bands of 1,553 cm ^-1 , 1,480 cm ^-1 (C = N) and 1,058 cm ^-1 (CO) were not present in the polyhydroxyimide. The free volume of the prepared polymer was 0.25 and the interplanar distance was 565 pm.

Example  8

Polymers containing polybenzoxazole were prepared as shown in Reaction Scheme 4 below.

[Reaction Scheme 4]

3.384 g of the above-prepared 3,3,3 ', 3'-tetramethyl-1,1'-spirobi (indane) -5,5'-diamino-6,6'-diol (TSBIDD) 1.09 g of pyromelitic (PMDA) and 2.221 g of 3,3 ', 4,4'-hexafluoropropylidene diphthalic dianhydride (6FDA) (3,3', 4,4'-hexafluoropropylidene diphthalic dianhydride, And reacted with 31.3 g of N-methylpyrrolidinone (NMP) solution for 4 hours to prepare a pale yellow solution.

Then, 40 ml of pyridine and ortho-xylene were added thereto, and the mixture was reacted for 6 hours while refluxing to obtain a yellow solution. Subsequently, it is immersed in distilled water, washed and dried, and then the obtained 6FDA / PMDA-TSBIDD polyimide is dissolved again in N-methylpyrrolidone (NMP) to 20 wt%. Then, the dissolved solution was cast on a glass plate and kept at 100 ° C, 150 ° C, 200 ° C, and 250 ° C for 1 hour in a vacuum oven to produce a film. The thickness of the film thus prepared was 46 mu m.

The polyimide film prepared above was put into a muffle furnace, heated to 300 캜 at a rate of 10 캜 / min, and maintained at 300 캜 for 30 minutes.

Subsequently, heat treatment was performed by heating to 450 DEG C and holding for 1 hour to prepare a transparent pale brown TSBIDD-based polybenzoxazole film.

FT-IR analysis showed that polybenzoxazole characteristic bands of 1,553 cm ^-1 , 1,480 cm ^-1 (C = N) and 1,058 cm ^-1 (CO) were not present in the polyhydroxyimide. The interplanar distance of the prepared polymer was 831 pm. The BET surface area was 434 m ² / g.

Comparative Example  1: Synthesis of Polymer and Preparation of Gas Membrane Using It

A porous polymer having a trapezoidal structure was prepared as shown in Reaction Scheme 5 below.

[Reaction Scheme 5]

A 500 ml flask was charged with 3,3,3 ', 3'-tetramethyl-1,1'-spirobisinden-5,5', 6,6'-tetrol (3,3,3 ' 10.113 g (30 mmol) of 1,4-dicyanotetrafluorobenzene (DCTB), 1,1'-spirobisindane-5,5 ', 6,6'-tetrol (TTSBI) 6.003 g (30 mmol) of potassium carbonate and 8.292 g (60 mmol) of potassium carbonate were stirred vigorously in a dimethylformamide (DMF) 200 ml solvent at room temperature for about 20 minutes.

The reaction flask was placed in an oil bath, heated to 55 ° C, and maintained for about 23 hours. The stirring speed is 810 rpm.

The reaction flask is cooled and poured into 300 ml of water to obtain an unpurified polymer. The polymer is dissolved again in chloroform, and the polymer is again immersed in methanol and dried to obtain a PIM-1 polymer.

A 2 wt% polymer solution was prepared using chloroform solvent, purified using 0.45 ㎛ syringe filter, cast on a glass plate, and solvent evaporated slowly at room temperature for one day to obtain a polymer film. The PIM-1 polymer film is dried in an oven at 70 ° C to completely remove the solvent. The average thickness was 53 탆, and the BET surface area was 850 m ² / g.

Comparative Example  2

A porous polymer containing polybenzoxazole was prepared as shown in Reaction Scheme 6 below.

[Reaction Scheme 6]

(3-amino-4-hydroxyphenyl) hexafluoropropane (bisAPAF, 3.663 g, 10 mmol) and NMP (15.06 mL) were placed in a 100 mL three-necked flask with flowing nitrogen gas, I put it in the ice bath. A solution of propylene oxide (PO, 0.3 mL) and terephthaloyl chloride (TCL, 2.030 g, 10 mmol) in NMP (8.35 mL) was added to the flask in this order and the reaction was allowed to proceed for 2 hours.

Stirring at room temperature for 12 hours gives a viscous polyhydroxyamide solution. The solution is poured onto a glass plate and cast in a vacuum oven at 100 ° C for 1 hour and at 200 ° C for 10 hours to remove the solvent. After cooling slowly, a polyhydroxyamide precursor film is obtained.

The polyhydroxyamide precursor film is heated in an argon gas flow increasing to 5O &lt; 0 &gt; C / min to 350 &lt; 0 &gt; C and maintained for one hour. The temperature inside the furnace is slowly cooled to obtain a polybenzoxazole film. The average thickness of the polymer film was 40 탆, the density was 1.39 g / cm ³ , and the interplanar spacing was 719 pm.

Comparative Example  3

A porous polymer containing polybenzoxazole was prepared as shown in Reaction Scheme 7 below.

[Reaction Scheme 7]

(3-amino-4-hydroxyphenyl) hexafluoropropane (bisAPAF, 3.663 g, 10 mmol) and NMP (15.06 mL) were placed in a 100 mL three-necked flask with flowing nitrogen gas, I put it in the ice bath. A solution of propylene oxide (PO, 0.3 mL) and para-phenylene (tetraloyl dichloride) (TPCL, 2.030 g, 10 mmol) in NMP (8.35 mL) was placed in a flask and reacted for 2 hours .

Stirring at room temperature for 12 hours gives a viscous polyhydroxyamide solution. The solution is poured onto a glass plate and cast in a vacuum oven at 100 ° C for 1 hour and at 200 ° C for 10 hours to remove the solvent. After cooling slowly, a polyhydroxyamide precursor film is obtained.

The polyhydroxyamide precursor film is heated in an argon gas flow increasing to 5O &lt; 0 &gt; C / min to 350 &lt; 0 &gt; C and maintained for one hour. The temperature inside the furnace is slowly cooled to obtain a polybenzoxazole film. The average thickness of the polymer film was 42 탆, the density was 1.32 g / cm ³ , and the interplanar spacing was 758 pm.

Test Example  1: mechanical properties evaluation

Mechanical properties of the gas separation membranes were measured at 25 占 폚 using AGS-J 500N (shimadzu) using the films prepared in Examples 1 to 9 and Comparative Examples 1 to 3 as gas separation membranes. Four specimens were tested for each sample. The standard deviation for the mean was ± 10%. The results are shown in Table 1 below.

Gas separator The tensile strength
(MPa) Elongation at break point
(%) Example 1 83 20 Example 2 88 18 Example 3 84 23 Example 4 90 20 Example 5 85 19 Example 6 92 17 Example 7 88 17 Example 8 86 18 Comparative Example 1 45 7 Comparative Example 2 80 6 Comparative Example 3 75 8

As shown in Table 1, the gas separation membranes prepared in Examples 1 to 8 generally had elongation percent at break (unit:%) at the breaking point of the gas separation membranes prepared in Comparative Examples 1 to 3 . This is because the polymers included in the gas separation membranes prepared in Examples 1 to 8 have the characteristics of simultaneously including the benzoxazole structure and the ladder structure simultaneously and the flexibility that can increase the tensile strength at the same time.

From the above test results, the polymers included in the gas separation membranes prepared in Examples 1 to 8 have both a benzoxazole structure and a ladder-like structure, so that they can be used not only in mild conditions but also in long working times, acidic conditions, It can be confirmed that it can withstand under severe conditions.

Test Example  2: gas permeability ( permeability ) And selectivity ( selectivity ) Measure

The gas separation membranes prepared in Examples 1 to 8 and Comparative Examples 2 to 3 were tested for gas permeability and selectivity in the following manner. The results are shown in Tables 2 and 3 below.

Gas permeability and selectivity were measured using a high-vacuum time-lag apparatus, the downstream volume was adjusted to 30 cm ³ , the upstream and downstream pressures were 33 atm and 0.002 atm And measured using a full scale Baratron transducer.

All pure gas permeability measurements were carried out more than 5 times at 27 ° C. The standard deviation of the mean value of the transmittance was within ± 2%, and the reproducibility of the samples was within ± 5%. The effective area of the gas separation membrane was 4.00 cm ² .

For pure gases, the rate of increase in permeate pressure can be measured at a fixed volume or at a fixed collection volume. Injection pressure p ₁ The permeation pressure p ₂ has a very small value (<2 Torr). When the pressure on the transmitting surface is p ₂ An approximate value of the permeability of gas molecules through the polymer membrane can be obtained while being measured while being recorded in large time. The gas permeability P _A of the molecule _A can be calculated from the rate at which the downstream pressure increases the fixed permeation volume in the equilibrium state according to the following equation (3).

&Quot; (3) &quot;

In Equation (3)

V is the volume of the fixed downstream collector,

l is the film thickness,

A is the membrane area,

p ₁ and p ₂ are the pressures in the upstream and downstream, respectively,

R , T, and t are the gas constant, temperature, and time, respectively.

Gas separator He
Permeability
(Barrer) H ₂
Permeability
(Barrer) CO ₂
Permeability
(Barrer) O ₂
Permeability
(Barrer) N ₂
Permeability
(Barrer) CH ₄
Permeability
(Barrer) Example 1 318 428 675 120 30 34 Example 2 325 512 731 132 34 37 Example 3 428 668 843 189 45 40 Example 4 121 180 185 34 8 9 Example 5 134 226 216 38 8 11 Example 6 128 216 146 32 6 7 Example 7 136 208 144 27 6 7 Example 8 215 350 362 69 15 14 Comparative Example 2 82 85 50 11 2 2 Comparative Example 3 70 60 23 6 One One

Gas separator CO _{2 /} H ₂
Selectivity O ₂ / N ₂
Selectivity CO ₂ / CH ₄
Selectivity CO ₂ / N ₂
Selectivity Example 1 1.6 3.9 20.1 22.2 Example 2 1.4 3.9 20.0 21.6 Example 3 1.3 4.2 21.1 18.8 Example 4 1.0 4.1 20.5 23.7 Example 5 1.1 4.4 20.0 25.6 Example 6 0.7 4.6 21.7 22.6 Example 7 0.7 4.9 21.2 25.2 Example 8 1.0 4.7 25.0 24.8 Comparative Example 2 0.6 4.8 24.7 22.0 Comparative Example 3 0.4 4.6 16.4 23.0

As shown in Tables 2 and 3, the gas separation membranes prepared in Examples 1 to 8 have superior gas permeability compared to the gas separation membranes prepared in Comparative Examples 2 and 3. In addition, it can be confirmed that the gas separation membranes prepared in Examples 1 to 8 have better gas selectivity than the gas separation membranes prepared in Comparative Examples 2 and 3.

As a result, it can be seen that the gas separation membranes prepared in Examples 1 to 8 can efficiently separate a larger amount of gas than the gas separation membranes prepared in Comparative Examples 2 and 3.

Although specific embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications and changes can be made within the scope of the claims and the detailed description of the invention and the accompanying drawings. Naturally, it belongs to the scope of the invention.

Claims (30)

A polyamic acid comprising a repeating unit represented by Formula 1 and Formula 2, a copolymer thereof, or a blend thereof;
A polyimide comprising a repeating unit represented by Formulas 3 and 4, a copolymer thereof, or a blend thereof; or
Polymers derived from combinations of these:
[Formula 1]

(2)

(3)

[Chemical Formula 4]

In the above Chemical Formulas 1 to 4,
Ar ¹ is the same as or different from each other at each repeating unit, and each independently an aromatic ring group selected from a substituted or unsubstituted tetravalent C6 to C60 arylene group and a substituted or unsubstituted tetravalent C4 to C60 heterocyclic group, The aromatic ring groups are present alone; Two or more are joined to each other to form a condensed ring; Two or more single bond, O, S, C (= O), CH (OH), S (= O) 2, Si (CH 3) 2, (CH 2) p ( where, 1≤p≤10) , (CF ₂₎ q _{(where, 1≤q≤10), C (CH 3} ) 2, C (CF 3) 2, C (= O) NH or a substituted or unsubstituted tetravalent aliphatic organic groups C1 to C30 Lt; / RTI &gt;
T is the same or different at each repeating unit and is each independently a substituted or unsubstituted tetravalent C1 to C40 aliphatic organic group, a substituted or unsubstituted tetravalent C3 to C40 alicyclic organic group, or a substituted or unsubstituted group Tetravalent C6 to C40 aromatic organic group,
Y is the same or different from each other in each repeating unit and is independently OH, SH or NH ₂ ,
n is an integer satisfying 10? n? 400. The method of claim 1,
The polymer derived from the polyamic acid or the polyimide has a free volume (FFV) of 0.20 to 0.35. The method of claim 1,
The polymer derived from the polyamic acid or the polyimide has an interplanar distance by XRD measurement in the range of 520 pm to 850 pm. The method of claim 1,
The polymer derived from the polyamic acid or the polyimide has a BET surface area of 280 m ² / g to 600 m ² / g. The method of claim 1,
Wherein Ar &lt; ¹ &gt; is selected from the group consisting of the following formulas:

In this formula,
X ¹ to X ⁶ are the same or different, each independently O, S, C (= O ), CH (OH), S (= O) 2, Si (CH 3) 2, (CH 2) p ( where , and _{1≤p≤10), (CF 2) q} ( _{where, 1≤q≤10), C (CH 3} ) 2, C (CF 3) 2, or C (= O) NH,
W ¹ and W ² are the same or different and each independently O, S, or C (= O)
Z ¹ is O, S, CR ³⁰⁰ R ³⁰¹ or NR ³⁰² wherein R ³⁰⁰ , R ³⁰¹ and R ³⁰² are the same or different and are each independently hydrogen or a C 1 to C 5 alkyl group,
Z ² and Z ³ are the same or different and are each independently N or CR ³⁰³ (wherein R ³⁰³ is a hydrogen or a C 1 to C 5 alkyl group) but not CR ³⁰³ at the same time,
T is each independently a substituted or unsubstituted tetravalent C1 to C40 aliphatic organic group, a substituted or unsubstituted tetravalent C3 to C40 alicyclic organic group, or a substituted or unsubstituted tetravalent C6 to C40 aromatic organic group,
R ¹ to R ⁶² are the same or different and are each independently hydrogen or a substituted or unsubstituted C1 to C10 aliphatic organic group,
k1 to k3, k8 to k14, k24, k25, k49 to k54 and k59 to k62 are integers of 0 to 2,
k5, k15, k16, k19, k21 and k23 are integers of 0 or 1,
and k55 to k58 are integers of from 0 to 3, and k4, k6, k7, k17, k18, k20, k22, k26 to k29, k31, k34 to k36, k38, k41, k44 to k46,
k30, k37, k42, k43, k47 and k48 are integers of 0 to 4,
k32, k33, k39, and k40 are integers of 0 to 5. The method of claim 5,
Wherein T is selected from the group consisting of the following formulas:

In this formula,
R ²⁰⁰ to R ²³¹ are the same or different and each independently represents hydrogen, a substituted or unsubstituted C1 to C30 aliphatic organic group, a substituted or unsubstituted C3 to C30 alicyclic group or a substituted or unsubstituted divalent C6 To C30 aromatic organic groups,
t1 to t12 are the same or different and are each independently an integer of 0 to 4; The method according to claim 6,
Wherein T is selected from the group consisting of the following formulas:

. The method of claim 5,
Wherein Ar &lt; ¹ &gt; is selected from the group consisting of the following formulas:

. The method of claim 1,
Wherein T is selected from the group consisting of the following formulas:

In this formula,
R ²⁰⁰ to R ²³¹ are the same or different and each independently represents hydrogen, a substituted or unsubstituted C1 to C30 aliphatic organic group, a substituted or unsubstituted C3 to C30 alicyclic group or a substituted or unsubstituted divalent C6 To C30 aromatic organic groups,
t1 to t12 are the same or different and are each independently an integer of 0 to 4; 10. The method of claim 9,
Wherein T is selected from the group consisting of the following formulas:

. The method of claim 1,
The polymer ratio of the molar ratio between each repeating unit in the copolymer of the polyamic acid comprising a repeating unit represented by Formula 1 and Formula 2 is 0.1: 9.9 to 9.9: 0.1. The method of claim 1,
The polymer ratio of the molar ratio between each repeating unit in the copolymer of the polyimide containing the repeating units represented by the formula (3) and formula (4) is 0.1: 9.9 to 9.9: 0.1. The method of claim 1,
The polymer derived from the polyamic acid, the polymer derived from the polyimide, or the polymer derived from a combination of the polyamic acid and the polyimide may include a compound including a repeating unit represented by any one of the following Formulas 5 to 8 or A polymer comprising a copolymer of:
[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

In the above Chemical Formulas 5 to 8,
Ar ¹ is an aromatic ring group selected from the group consisting of a substituted or unsubstituted tetravalent C6 to C60 arylene group and a substituted or unsubstituted tetravalent C4 to C60 heterocyclic group which are the same or different from each other in each repeating unit, Said aromatic ring group being present alone; Two or more are joined to each other to form a condensed ring; Or at least two aromatic groups are a single bond, O, S, C (= O), CH (OH), S (= O) 2, Si (CH 3) 2, (CH 2) p ( where, 1≤p≤10) , (CF _{2) q (where, 1≤q≤10), C (CH 3} ) 2, C (CF 3) 2, C (= O) NH or a substituted or unsubstituted tetravalent aliphatic organic groups C1 to C30 Lt; / RTI &gt;
Ar ^{1 '} are the same or different and are each independently an aromatic ring group selected from substituted or unsubstituted divalent C6 to C60 arylene groups and substituted or unsubstituted divalent C4 to C60 heterocyclic groups, and the aromatic ring group is Either alone; Two or more are joined to each other to form a condensed ring; Two or more single bonds, O, S, C (= 0), CH (OH), S (= 0) ₂ , Si (CH ₃ ) ₂ , (CH ₂ ) _p (where 1 ≦ _p ≦ 10) , (CF ₂ ) _q where 1 ≦ _q ≦ 10, C (CH ₃ ) ₂ , C (CF ₃ ) ₂ , C (═O) NH or substituted or unsubstituted tetravalent C 1 to C 30 aliphatic organic Connected by groups,
T is the same or different at each repeating unit and is each independently a substituted or unsubstituted tetravalent C1 to C40 aliphatic organic group, a substituted or unsubstituted tetravalent C3 to C40 alicyclic organic group, or a substituted or unsubstituted group Tetravalent C6 to C40 aromatic organic group,
Y &quot; is O or S,
n is an integer satisfying 10? n? 400. The method of claim 13,
Wherein Ar &lt; ¹ &gt; is selected from the group consisting of the following formulas:

In this formula,
X ¹ to X ⁶ are the same or different, each independently O, S, C (= O ), CH (OH), S (= O) 2, Si (CH 3) 2, (CH 2) p ( where , and _{1≤p≤10), (CF 2) q} ( _{where, 1≤q≤10), C (CH 3} ) 2, C (CF 3) 2, or C (= O) NH,
W ¹ and W ² are the same or different and each independently O, S, or C (= O)
Z ¹ is O, S, CR ³⁰⁰ R ³⁰¹ or NR ³⁰² wherein R ³⁰⁰ , R ³⁰¹ and R ³⁰² are the same or different and are each independently hydrogen or a C 1 to C 5 alkyl group,
Z ² and Z ³ are the same or different and are each independently N or CR ³⁰³ (wherein R ³⁰³ is a hydrogen or a C 1 to C 5 alkyl group) but not CR ³⁰³ at the same time,
T is each independently a substituted or unsubstituted tetravalent C1 to C40 aliphatic organic group, a substituted or unsubstituted tetravalent C3 to C40 alicyclic organic group, or a substituted or unsubstituted tetravalent C6 to C40 aromatic organic group,
R ¹ to R ⁶² are the same or different and are each independently hydrogen or a substituted or unsubstituted C1 to C10 aliphatic organic group,
k1 to k3, k8 to k14, k24, k25, k49 to k54 and k59 to k62 are integers of 0 to 2,
k5, k15, k16, k19, k21 and k23 are integers of 0 or 1,
and k55 to k58 are integers of from 0 to 3, and k4, k6, k7, k17, k18, k20, k22, k26 to k29, k31, k34 to k36, k38, k41, k44 to k46,
k32, k33, k39, and k40 are integers of 0 to 5, and k30, k37, k42, k43, k47, and k48 are integers of 0 to 4. 15. The method of claim 14,
Wherein T is selected from the group consisting of the following formulas:

In this formula,
R ²⁰⁰ to R ²³¹ are the same or different and each independently represents hydrogen, a substituted or unsubstituted C1 to C30 aliphatic organic group, a substituted or unsubstituted C3 to C30 alicyclic group or a substituted or unsubstituted divalent C6 To C30 aromatic organic groups,
t1 to t12 are the same or different and are each independently an integer of 0 to 4; 16. The method of claim 15,
Wherein T is selected from the group consisting of the following formulas:

. 15. The method of claim 14,
Wherein Ar &lt; ¹ &gt; is selected from the group consisting of the following formulas:

In this formula,
M is hydrogen or a metal, and the metal is sodium, potassium, lithium, an alloy thereof, or a combination thereof. The method of claim 13,
Wherein Ar &lt; ¹ &gt; is selected from the group consisting of the following formulas:

In this formula,
X ¹ to X ⁶ are the same or different, each independently O, S, C (= O ), CH (OH), S (= O) 2, Si (CH 3) 2, (CH 2) p ( where , and _{1≤p≤10), (CF 2) q} ( _{where, 1≤q≤10), C (CH 3} ) 2, C (CF 3) 2, or C (= O) NH,
W ¹ and W ² are the same or different and each independently O, S, or C (= O)
Z ¹ is O, S, CR ³⁰⁰ R ³⁰¹ or NR ³⁰² wherein R ³⁰⁰ , R ³⁰¹ and R ³⁰² are the same or different and are each independently hydrogen or a C 1 to C 5 alkyl group,
Z ² and Z ³ are the same or different and are each independently N or CR ³⁰³ (wherein R ³⁰³ is a hydrogen or a C 1 to C 5 alkyl group) but not CR ³⁰³ at the same time,
T is each independently a substituted or unsubstituted tetravalent C1 to C40 aliphatic organic group, a substituted or unsubstituted tetravalent C3 to C40 alicyclic organic group, or a substituted or unsubstituted tetravalent C6 to C40 aromatic organic group,
R ⁶³ to R ¹²³ are the same or different and each independently represents hydrogen, a substituted or unsubstituted C1 to C10 aliphatic organic group, or a metal sulfonate group,
k63, k69, k84 to k88, k92 to k96, k102 to k109, k116 and k119 are integers of 0 to 4,
k81, k115, k117, k118, k120, and k123 are integers of 0 to 3,
k100, k101, k113, k114, k121, and k122 are integers of 0 to 2,
k70 is an integer of 0 or 1,
k89, k91, k97, and k99 are integers of 0 to 5. 19. The method of claim 18,
Wherein Ar &lt; ¹ &gt; is selected from the group consisting of the following formulas:

In this formula,
M is hydrogen or a metal, and the metal is sodium, potassium, lithium, an alloy thereof, or a combination thereof. The method of claim 13,
Wherein T is selected from the group consisting of the following formulas:

In this formula,
R ²⁰⁰ to R ²³¹ are the same or different and each independently represents hydrogen, a substituted or unsubstituted C1 to C30 aliphatic organic group, a substituted or unsubstituted C3 to C30 alicyclic group or a substituted or unsubstituted divalent C6 To C30 aromatic organic groups,
t1 to t12 are the same or different and are each independently an integer of 0 to 4; 21. The method of claim 20,
Wherein T is selected from the group consisting of the following formulas:

. The method of claim 1,
Wherein the polymer has a weight average molecular weight (Mw) of 10,000 g / mol to 500,000 g / mol. Imidizing a polyamic acid comprising a repeating unit represented by Formula 1 and Formula 2, a copolymer thereof, or a blend thereof to obtain a polyimide; And
And heat-treating the polyimide.
[Formula 1]

(2)

In the above formulas (1) and (2)
Ar ¹ is an aromatic ring group selected from the group consisting of a substituted or unsubstituted tetravalent C6 to C60 arylene group and a substituted or unsubstituted tetravalent C4 to C60 heterocyclic group which are the same or different from each other in each repeating unit, Said aromatic ring group being present alone; Two or more are joined to each other to form a condensed ring; Or at least two aromatic groups are a single bond, O, S, C (= O), CH (OH), S (= O) 2, Si (CH 3) 2, (CH 2) p ( where, 1≤p≤10) , (CF _{2) q (where, 1≤q≤10), C (CH 3} ) 2, C (CF 3) 2, C (= O) NH or a substituted or unsubstituted tetravalent aliphatic organic groups C1 to C30 Lt; / RTI &gt;
T is the same or different at each repeating unit and is each independently a substituted or unsubstituted tetravalent C1 to C40 aliphatic organic group, a substituted or unsubstituted tetravalent C3 to C40 alicyclic organic group, or a substituted or unsubstituted group Tetravalent C6 to C40 aromatic organic group,
Y is the same or different from each other in each repeating unit and is independently OH, SH or NH ₂ ,
n is an integer satisfying 10? n? 400. 24. The method of claim 23,
Wherein the heat treatment is carried out at a temperature raising rate of 1 to 30 占 폚 / min to 350 to 500 占 폚, and at that temperature for 1 to 12 hours under an inert atmosphere. A method for preparing a polymer comprising the step of heat-treating a polyimide comprising a repeating unit represented by the following formulas (3) and (4), copolymers thereof, or blends thereof:
(3)

[Chemical Formula 4]

In the above formulas (3) and (4)
Ar ¹ is an aromatic ring group selected from the group consisting of a substituted or unsubstituted tetravalent C6 to C60 arylene group and a substituted or unsubstituted tetravalent C4 to C60 heterocyclic group which are the same or different from each other in each repeating unit, Said aromatic ring group being present alone; Two or more are joined to each other to form a condensed ring; Or at least two aromatic groups are a single bond, O, S, C (= O), CH (OH), S (= O) 2, Si (CH 3) 2, (CH 2) p ( where, 1≤p≤10) , (CF _{2) q (where, 1≤q≤10), C (CH 3} ) 2, C (CF 3) 2, C (= O) NH or a substituted or unsubstituted tetravalent aliphatic organic groups C1 to C30 Lt; / RTI &gt;
T is the same or different at each repeating unit and is each independently a substituted or unsubstituted tetravalent C1 to C40 aliphatic organic group, a substituted or unsubstituted tetravalent C3 to C40 alicyclic organic group, or a substituted or unsubstituted group Tetravalent C6 to C40 aromatic organic group,
Y is the same or different from each other in each repeating unit and is independently OH, SH or NH ₂ ,
n is an integer satisfying 10? n? 400. 26. The method of claim 25,
Wherein the heat treatment is carried out at a temperature raising rate of 1 to 30 占 폚 / min to 350 to 500 占 폚, and at that temperature for 1 to 12 hours under an inert atmosphere. A polyamic acid comprising a repeating unit represented by the following Chemical Formulas 1 and 2, a copolymer thereof, or a polyamic acid including a blend thereof, and a polyimide comprising a repeating unit represented by the following Chemical Formulas 3 and 4, Imidating a polyamic acid in a compound comprising a combination of polyimides comprising these copolymers or blends thereof to obtain a polyimide; And
Heat-treating the polyimide
: &Lt; RTI ID = 0.0 &gt;
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

In the above Chemical Formulas 1 to 4,
Ar ¹ is an aromatic ring group selected from the group consisting of a substituted or unsubstituted tetravalent C6 to C60 arylene group and a substituted or unsubstituted tetravalent C4 to C60 heterocyclic group which are the same or different from each other in each repeating unit, Said aromatic ring group being present alone; Two or more are joined to each other to form a condensed ring; Or at least two aromatic groups are a single bond, O, S, C (= O), CH (OH), S (= O) 2, Si (CH 3) 2, (CH 2) p ( where, 1≤p≤10) , (CF _{2) q (where, 1≤q≤10), C (CH 3} ) 2, C (CF 3) 2, C (= O) NH or a substituted or unsubstituted tetravalent aliphatic organic groups C1 to C30 Lt; / RTI &gt;
T is the same or different at each repeating unit and is each independently a substituted or unsubstituted tetravalent C1 to C40 aliphatic organic group, a substituted or unsubstituted tetravalent C3 to C40 alicyclic organic group, or a substituted or unsubstituted group Tetravalent C6 to C40 aromatic organic group,
Y is the same or different from each other in each repeating unit and is independently OH, SH or NH ₂ ,
n is an integer satisfying 10? n? 400. 28. The method of claim 27,
Wherein the heat treatment is carried out at a temperature raising rate of 1 to 30 占 폚 / min to 350 to 500 占 폚, and at that temperature for 1 to 12 hours under an inert atmosphere. A molded article comprising the polymer according to any one of claims 1 to 28. 30. The method of claim 29,
The molded article is a gas separation membrane.