WO2013172554A1 - Polymer, preparation method thereof, and molded product comprising said polymer - Google Patents

Description

Polymer, its manufacturing method and molded article comprising the polymer

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

The diffusion of small molecules or ions through pores in hard organic materials is essentially a phenomenon based on subnano or nanotechnology. Membranes containing such organic materials can be used to selectively separate low molecules or ions easily, and this technique can be used in various fields such as chemical manufacturing, energy conversion, energy storage, organic batteries, fuel cells, and gas separation. It can be used for a variety of purposes.

Therefore, research on this is being actively conducted. However, as described above, it is not easy to selectively separate low-molecules or ions, and at the same time, development of a material having both heat resistance, chemical resistance, solubility in general solvents, and mechanical strength has not been applied to various applications. 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.

A polymer according to an aspect of the present invention includes a polyamic acid including 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 combinations thereof.

[Revision 17.06.2013 under Rule 91]
Formula 1

[Revision 17.06.2013 under Rule 91]
Formula 2

[Revision 17.06.2013 under Rule 91]
Formula 3

[Revision 17.06.2013 under Rule 91]
Formula 4

In 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 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 a substituted or unsubstituted tetravalent C 1 to C 30 aliphatic organic group Connected by

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 at each repeating unit and each independently is 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 in the range of 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.

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

[Revision 17.06.2013 under Rule 91]

[Revision 17.06.2013 under Rule 91]

Where

X ¹ to X ⁶ are the same or different from each other and each independently 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 , or C (═O) NH,

W ¹ and W ² are the same or different and are 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 from each other and are each independently hydrogen or a C1 to C5 alkyl group,

Z ² and Z ³ are the same or different from each other and independently of each other N or CR ³⁰³ (wherein R ³⁰³ is hydrogen or a C1 to C5 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,

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

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

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

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

[Revision 17.06.2013 under Rule 91]

Where

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

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

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

[Revision 17.06.2013 under Rule 91]

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

[Revision 17.06.2013 under Rule 91]

[Revision 17.06.2013 under Rule 91]

[Revision 17.06.2013 under Rule 91]

In the polymer, the molar ratio between each repeating unit in the copolymer of polyamic acid including the repeating units represented by Formula 1 and Formula 2 may be about 0.1: 9.9 to about 9.9: 0.1.

Meanwhile, in the polymer, the molar ratio between each repeating unit in the copolymer of the polyimide including the repeating units represented by 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 or a copolymer thereof including a repeating unit represented by any one of Formulas 5 to 8.

[Revision 17.06.2013 under Rule 91]
Formula 5

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Formula 6

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Formula 7

[Revision 17.06.2013 under Rule 91]
Formula 8

In Chemical Formulas 5 to 8,

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

Ar ^{1 ′} is the same or different from each other and each independently 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, wherein the aromatic ring group Exist 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,

Y '' is O or S.

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

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

[Revision 17.06.2013 under Rule 91]

[Revision 17.06.2013 under Rule 91]

Where

X ¹ to X ⁶ are the same or different from each other and each independently 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 , or C (═O) NH,

W ¹ and W ² are the same or different and are 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 from each other and are each independently hydrogen or a C1 to C5 alkyl group,

Z ² and Z ³ are the same or different from each other and independently of each other N or CR ³⁰³ (wherein R ³⁰³ is hydrogen or a C1 to C5 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, or a metal sulfonate group,

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

k64 to k66, k68, k71, k74, k75, k77, k78, k81, k83, k110 to k112, k115, k117, k118, k120 and k123 are integers from 0 to 3,

k67, k72, k73, k76, k79, k80, k82, k90, k98, k100, k101, k113, k114, k121 and k122 are integers from 0 to 2,

k70 is an integer of 0 or 1,

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

As described above, T in Ar ^{1 ′} is also the same as defined for T in Ar ¹ , and examples and specific examples are also the same as those defined in T in Ar ¹ .

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

[Revision 17.06.2013 under Rule 91]

[Revision 17.06.2013 under Rule 91]

[Revision 17.06.2013 under Rule 91]

[Revision 17.06.2013 under Rule 91]

Where

M is hydrogen or a metal, said metal being sodium, potassium, lithium, alloys thereof or a combination thereof.

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

According to another aspect of the present invention, there is provided a method of preparing a polymer, wherein a polyamic acid including a repeating unit represented by Formula 1 and Formula 2, a copolymer thereof, or a blend thereof is imidized to form a poly Obtaining a mead; And heat treating the polyimide.

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

Method for producing a polymer according to another embodiment of the present invention is a step of heat-treating a polyimide comprising a repeating unit represented by the formula (3) and formula (4), a copolymer thereof, or a blend thereof It includes.

Description of the heat treatment is as described above.

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

Description of the heat treatment is as described above.

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

The molded article may be a gas separation membrane.

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

The polymer according to the present invention is excellent in permeability and selectivity of low molecules, excellent in heat resistance, chemical resistance, solubility in solvents, and also excellent in 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.

Unless otherwise defined herein, a "hetero ring group" means a substitution containing 1 to 3 heteroatoms selected from the group consisting of O, S, N, P, Si, and combinations thereof in one ring, or Unsubstituted C2 to C30 cycloalkyl group, substituted or unsubstituted C2 to C30 cycloalkenyl group, substituted or unsubstituted C2 to C30 cycloalkynyl group, or substituted or unsubstituted C2 to C30 heteroaryl group. .

Unless otherwise defined herein, an "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 group. An alkynylene group, and specifically, 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, and Alicyclic organic 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, C3 to C15 cycloalkyl group, C3 to C15 cycloalkenyl group, C3 to C15 cycloalkynyl group, C3 to C15 cycloalkylene group, C3 to C15 cycloalkenylene group, or By C3 to C15 cycloalkynylene group, "aromatic organic group" means a C6 to C30 aryl group or a C6 to C30 arylene group, and specifically means a C6 to C16 aryl group or a C6 to C16 arylene group.

Unless otherwise defined herein, “combination” means mixed or copolymerized. In addition, "copolymerization" means block copolymerization to random copolymerization, and "copolymer" means block copolymer to random copolymerization.

In addition, in this specification, "*" means the part connected with the same or different atom or formula.

A polymer according to an embodiment of the present invention includes a polyamic acid including 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 combinations thereof.

[Formula 1]

[Revision 17.06.2013 under Rule 91]

[Formula 2]

[Revision 17.06.2013 under Rule 91]

[Formula 3]

[Revision 17.06.2013 under Rule 91]

[Formula 4]

[Revision 17.06.2013 under Rule 91]

In 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 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 a substituted or unsubstituted tetravalent C 1 to C 30 aliphatic organic group Connected by

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 at each repeating unit and each independently is OH, SH or NH ₂ ,

n is an integer satisfying 10 ≦ n ≦ 400.

The polyamic acid including the repeating units represented by Formulas 1 and 2 and the polyimide including the repeating units represented by Formulas 3 and 4 may be prepared according to a general method. For example, the polyamic acid may be prepared by reacting a tetraamine anhydride with a diamine including an OH, SH, or NH ₂ group present at an ortho position relative to an amine group. In addition, the polyimide can be prepared by thermal solution imidization or chemical imidization of the polyamic acid prepared as described above. The thermal solution imidization and chemical imidization will be described later.

The polyamic acid is imidized and thermally converted through a manufacturing process to be described later, and the polyimide is thermally converted through a manufacturing process to be described later, and has a high degree of free polybenzoxazole, polybenzothiazole, polypyrrolone or It can be converted into a polymer comprising a combination of these.

The polymer derived from the polyamic acid and the polymer derived from the polyimide include a rigid structure having excellent solubility in an organic solvent and a flexible structure, and at the same time, a rigid structure connected between the flexible structures. , Specifically, a rigid ladder structure. Accordingly, the polymer derived from the polyamic acid and the polymer derived from the polyimide include a repeating structure in which a rigid ladder structure is connected by a flexible hinge, and thus fine pores are formed while the refractive staircase is amorphously distributed. It may have, and also excellent mechanical strength and workability can be easily used to manufacture in the form of film, fiber, hollow fiber and the like.

The polymer derived from the polyamic acid and the polymer derived from the polyimide may have a free volume (FFV) of about 0.20 to about 0.35, and the d-spacing by XRD is about 520 pm to about It can be in the range of 850 pm. As a result, the polymer derived from the polyamic acid and the polymer derived from the polyimide can easily permeate or separate low molecules.

The polymer derived from the polyamic acid and the polymer derived from the polyimide may have a Brunauer-Emmett-Teller (BET) 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 permeate or selectively separate low molecules.

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

[Revision 17.06.2013 under Rule 91]

[Revision 17.06.2013 under Rule 91]

Where

X ¹ to X ⁶ are the same or different from each other and each independently 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 , or C (═O) NH,

W ¹ and W ² are the same or different and are 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 from each other and are each independently hydrogen or a C1 to C5 alkyl group,

Z ² and Z ³ are the same or different from each other and independently of each other N or CR ³⁰³ (wherein R ³⁰³ is hydrogen or a C1 to C5 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,

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

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

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

Examples of the T may be selected from those represented by the following formula, but are not limited thereto.

[Revision 17.06.2013 under Rule 91]

Where

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

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

Specifically, the example of T may be selected from those represented by the following formula, but is not limited thereto.

[Revision 17.06.2013 under Rule 91]

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

[Revision 17.06.2013 under Rule 91]

[Revision 17.06.2013 under Rule 91]

[Revision 17.06.2013 under Rule 91]

In Formulas 1 to 4, examples and specific examples of T are the same as those mentioned in Examples and specific examples of T described when describing Ar ¹ .

Molar ratio between each repeating unit in the copolymer of polyamic acid including the repeating units represented by Formula 1 and Formula 2; Alternatively, by controlling the molar ratio between the repeating units in the copolymer of the polyimide including the repeating units represented by Formulas 3 and 4, it is possible to control the physical properties of the prepared polymer.

The molar ratio between each repeating unit in the copolymer of polyamic acid including the repeating units represented by Formula 1 and Formula 2 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.

In addition, the molar ratio between each repeating unit in the copolymer of the polyimide including the repeating units represented by Formula 3 and Formula 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.

The copolymerization ratio affects the molecular structure and morphology of the prepared polymer, which is related to density, pore properties, heat resistance, tensile strength, shear force, and the like. When the molar ratio to the copolymerization ratio is within the above range, the prepared polymer may efficiently permeate or selectively separate low molecules, and may 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 a compound including a repeating unit represented by any one of Formulas 5 to 8 or a copolymer thereof, but is not limited thereto.

[Formula 5]

[Revision 17.06.2013 under Rule 91]

[Formula 6]

[Revision 17.06.2013 under Rule 91]

[Formula 7]

[Revision 17.06.2013 under Rule 91]

[Formula 8]

[Revision 17.06.2013 under Rule 91]

In Formulas 5 to 8, Ar ¹ , T and n are as described for Ar ¹ , T and n of Formulas 1 to 4, respectively,

Ar ^{1 ′} is the same or different from each other, and is each independently 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, and the aromatic The ring group is present 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,

Y '' is O or S.

In the above Chemical Formulas 5 to 8, examples of Ar ^1, and T, and specific examples of them are the same as each of the formulas (1) to the examples and mentioned specific examples of Ar ¹ and T in the formula (4).

In Formulas 5 to 8, an example of Ar ^{1 '} may be selected from those represented by the following formulas, but is not limited thereto.

[Revision 17.06.2013 under Rule 91]

[Revision 17.06.2013 under Rule 91]

Where

X ¹ to X ⁶ are the same or different from each other and each independently 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 , or C (═O) NH,

W ¹ and W ² are the same or different and are 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 from each other and are each independently hydrogen or a C1 to C5 alkyl group,

Z ² and Z ³ are the same or different from each other and independently of each other N or CR ³⁰³ (wherein R ³⁰³ is hydrogen or a C1 to C5 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 are each independently hydrogen, a substituted or unsubstituted C 1 to C 10 aliphatic organic group, or a metal sulfonate group,

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

k64 to k66, k68, k71, k74, k75, k77, k78, k81, k83, k110 to k112, k115, k117, k118, k120 and k123 are integers from 0 to 3,

k67, k72, k73, k76, k79, k80, k82, k90, k98, k100, k101, k113, k114, k121 and k122 are integers from 0 to 2,

k70 is an integer of 0 or 1,

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

Specifically, the example of Ar ^{1 '} may be selected from those represented by the following formula, but is not limited thereto.

[Revision 17.06.2013 under Rule 91]

[Revision 17.06.2013 under Rule 91]

[Revision 17.06.2013 under Rule 91]

[Revision 17.06.2013 under Rule 91]

Where

M is hydrogen or a metal, said metal being sodium, potassium, lithium, alloys thereof or a combination thereof.

Polymers derived from polyamic acid and polymers derived from polyimide according to an embodiment of the present invention may be prepared using polyamic acid or polyimide that is soluble in a general organic solvent, and the polymer may be easily formed without defects or cracks. Since it can be coated, it is possible to simplify the manufacturing process to reduce the process cost and to form a large area. In addition, the polymer can control the pore size or distribution by adjusting the manufacturing process conditions. As a result, the polymer may be widely applied to various applications such as gas permeation, gas separation, steam separation, water purification, adsorbent, heat resistant fiber, thin film manufacturing, and the like.

According to another embodiment of the present invention, the polymer may be derived from a combination of the polyamic acid and the polyimide, in which case the polymer may include a polymer derived from the polyamic acid and a polymer derived from the polyimide. have. Unless otherwise described below, the description of the polyamic acid, the polyimide, the polymer derived from the polyamic acid and the polymer derived from the polyimide is as described above.

The polymer including the polymer derived from the polyamic acid and the polymer derived from the polyimide may be a polymer having a weight ratio of about 0.1: 9.9 to about 9.9: 0.1 of the polymer: polyimide derived from the polyamic acid. 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 properties of the polymer derived from polyimide. It can also have good dimensional stability and long term stability.

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

Another embodiment of the present invention comprises the steps of imidating 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 it provides a method for producing a polymer comprising the step of heat-treating the polyimide. The polymer may include a compound including a repeating unit represented by any one of Formulas 5 to 8 or a copolymer thereof, but is not limited thereto.

In the method of preparing the polymer, the imidization may be performed by a thermal imidization process, but is not limited thereto.

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

The imidation condition is Ar, which is a functional group of the polyamic acid.^One, It can adjust suitably according to the kind of T and Y.

When the polyimide is heat-treated, it is rearranged through a heat conversion reaction to obtain a polymer having picopores. The polymer having picopores has a reduced density compared to the polyimide, increased free volume and increased interplanar distance as picopores are well connected to each other. As a result, the polymer having the picopores can efficiently permeate or selectively separate low molecules.

In addition, the polymer derived from the polyamic acid has a rigid structure, specifically rigid, which has excellent solubility in organic solvents and includes a flexible structure, and at the same time is connected between the flexible structures. By including one ladder structure, it can have fine pores, and can also have excellent workability and 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 ° C / min to 30 ° C / min to about 350 ° C to about 500 ° C, and at that temperature under an inert atmosphere for about 1 minute to about 12 hours. Specifically, the heat treatment may be performed at an elevated temperature rate of about 5 ° C./min to about 20 ° C./min to 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 may be performed at an elevated temperature rate of about 10 ° C./min to about 15 ° C./min to about 420 ° C. to about 450 ° C., and at that temperature for about 2 hours to about 5 hours under inert atmosphere. have. When the heat treatment is made within the above condition range, the heat conversion reaction may be sufficiently made.

Through such heat treatment, a polybenzoxazole, polybenzothiazole or polypyrrolone polymer including a repeating unit represented by Chemical Formulas 5 to 8 may be obtained. Preparation of such a polymer is carried out through the CO ₂ or H ₂ O removal reaction in the polyimide obtained by the imidization.

Another embodiment of the present invention is to prepare a polymer comprising the step of heat-treating a polyimide comprising a repeating unit represented by the formula (3) and formula (4), a copolymer thereof, or a blend thereof Provide a method. The polymer may include a compound including a repeating unit represented by any one of Formulas 5 to 8 or a copolymer thereof, but is not limited thereto.

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 including a repeating unit represented by the above formulas (1) and (2), for example, chemical imidation or thermal solution imidation.

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

The chemical imidization may be performed after _first protecting OH, SH and NH ₂ , which are functional groups present at the ortho position of the amine group in the polyamic acid. Specifically, a protecting group may be introduced into OH, SH, and NH ₂ , which are functional groups, and imidization may be performed to remove the protecting group. The protecting group may be trimethylchlorosilane ((CH ₃ ) ₃ SiCl), triethylchlorosilane ((C ₂ H ₅ ) ₃ SiCl), tributylchlorosilane ((C ₄ H ₉ ) ₃ SiCl), tribenzylchlorosilane Chlorosilanes such as ((C ₆ H ₅ ) ₃ SiCl), triethoxychlorosilane ((OC ₂ H ₅ ) ₃ SiCl), and hydrofuran, such as tetrahydrofurane (THF), may be used. As such, tertiary amines such as trimethylamine, triethylamine, tripropylamine, pyridine and the like can be used. Diluted hydrochloric acid, sulfuric acid, nitric acid, acetic acid, etc. may be used as the material for removing the protecting group. Chemical imidization using a protecting group as described above may increase the yield and molecular weight of the polymer according to an embodiment of the present invention.

The thermal solution imidization can be accomplished by running the reaction on the solution 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, the imidization of the polyamic acid can be sufficiently achieved.

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 the polyamic acid amine group. Specifically, a protecting group may be introduced into OH, SH, and NH ₂ , which are functional groups, and imidization may be performed to remove the protecting group. As the protecting group, chlorosilanes such as trimethylchlorosilane, triethylchlorosilane, tributylchlorosilane, tribenzylchlorosilane, triethoxychlorosilane, and hydrofuran, such as tetrahydrofuran, may be used. Tertiary amines such as triethylamine, tripropylamine, pyridine and the like can be used. Diluted hydrochloric acid, sulfuric acid, nitric acid, acetic acid, etc. may be used as a material for removing the protecting group.

In addition, the thermal solution imidization may be performed using an azeotrope made by further adding benzenes such as benzene, toluene, xylene, cresol, aliphatic organic solvents such as hexane, cyclohexane, and the like.

Thermal solution imidization made by introducing a protecting group and using an azeotrope as described above may increase the yield and molecular weight of the polymer according to one embodiment of the present invention.

The imidation condition is Ar, which is a functional group of the polyamic acid.^One, It can adjust suitably according to the kind of T and Y.

Another embodiment of the present invention is a polyamic acid including a repeating unit represented by Formula 1 and Formula 2, a copolymer thereof, or a polyamic acid including a blend thereof, and represented by Formula 3 and Formula 4 Imidizing a polyamic acid in a compound including a polyimide comprising a repeating unit, a copolymer thereof, or a combination of polyimides including a blend thereof to obtain a polyimide; And it provides a method for producing a polymer comprising the step of heat-treating the polyimide. The polymer may include a compound including a repeating unit represented by any one of Formulas 5 to 8 or a copolymer thereof, but is not limited thereto.

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

In the manufacturing process of the polymer, by adjusting the polymer design in consideration of the properties of Ar ₁ , T and Y in the chemical structure, it is possible to control the relevant properties such as pore size or distribution.

The polymer according to one embodiment of the present invention includes a rigid structure present in the polymer, so that it can withstand not only under mild conditions but also under 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 has excellent chemical stability, heat resistance, and mechanical properties.

At this time, the polymer comprising a repeating unit represented by Formula 5 to Formula 8 or copolymers thereof are designed to have an appropriate weight average molecular weight in the manufacturing step, specifically, the weight average molecular weight is about 10,000 g / mol to about 500,000 g / mol. If their weight average molecular weight is within the above range, the physical properties of the polymer can be maintained excellent.

The polymer according to an embodiment of the present invention is a polymer derived from polyamic acid or a polymer derived from polyimide, and has picopores. Since two or more picopores are connected to each other to form an hourglass shape, the picopores may have a high free volume to efficiently penetrate or selectively separate small molecules.

Yet another embodiment of the present invention provides an article including 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 article may include a structure in which a rigid ladder structure is repeated in the form of being connected by a flexible hinge, and thus may have micropores, specifically dumbbell-shaped micropores, which are formed while the refractive staircase is amorphous. . Therefore, the molded article can efficiently penetrate or selectively separate low-molecules, 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.

Hereinafter, the Example and comparative example of this description are described. However, the following examples are merely examples of the present disclosure, and the present disclosure is not limited by the following examples.

Example : Synthesis of Polymer and Preparation of Gas Separation Membrane Using the Same

Example 1

A polymer containing polybenzoxazole was prepared as shown in Scheme 1 below.

Scheme 1

[Revision 17.06.2013 under Rule 91]

100 g of bisphenol A is mixed with 4.5 g of methane sulfonic acid, and then reacted at 140 ° C. for 5 hours. Then, precipitated in 2 liters of distilled water to separate 3,3,3 ', 3'-tetramethyl-1,1'-spirobi (indan) -6,6'-diol (3,3,3' , 3'-tetramethyl-1,1'-spirobi (indane) -6,6'-diol) is prepared.

Subsequently, 3,3,3 ', 3'-tetramethyl-1,1'-spirobibi (Indan) -6,6'-diol prepared above was added to 360 ml of nitric acid and reacted for 5 hours to give 3,3, 3 ', 3'-tetramethyl-1,1'-spirobi (Indan) -5,5'-dinitro-6,6'-diol (3,3,3', 3'-tetramethyl-1,1 '-spirobi (indane) -5,5'-dinitro-6,6'-diol) was prepared.

Subsequently, the 3,3,3 ', 3'-tetramethyl-1,1'-spirobi (indan) -5,5'-dinitro-6,6'-diol prepared above with 2.5 g of Pd / C Put together 330ml of ethanol and reflux while stirring with 66ml of NH ₂ NH ₂ H ₂ O for 10 hours, 3,3,3 ', 3'-tetramethyl-1,1'-spirobi (Indan) -5 , 5'-diamino-6,6'-diol (3,3,3 ', 3'-tetramethyl-1,1'-spirobi (indane) -5,5'-diamino-6,6'-diol) 2.85 g was prepared.

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

Subsequently, 40 ml of pyridine and ortho-xylene were added thereto, followed by reaction for 6 hours while refluxing to obtain a yellow solution. Subsequently, the 6FDA-TSBIDD polyimide obtained by immersing it in distilled water and washing and drying was dissolved again in N-methylpyrrolidone (NMP) to 20% by weight.

Subsequently, 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 prepare a film. The thickness of the film thus prepared was 64 μm.

The polyimide film prepared above was placed in a muffle furnace and heated to 300 ° C. at a rate of 10 ° C./min per minute, and maintained at 300 ° C. for 30 minutes. Subsequently, a gas separation membrane was prepared by performing a heat treatment to be heated to 425 ° C. and maintained for 2 hours to obtain a transparent pale brown TSBIDD-based polybenzoxazole film.

The FTIR analysis, free volume, interplanar distance and BET surface area were measured for the polybenzoxazole film obtained 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 the gas permeability. The film density was measured by buoyancy method using a Sartorius LA 310S analytical balance according to Equation 1 below.

[Equation 1]

In Equation 1,

ρ _P is the density of the polymer,

ρ _W is the density of deionized water,

Wa is the weight of the polymer measured in air,

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

Free volume degrees (FFV, V _f ) were calculated according to the following equation (2) from the data.

[Equation 2]

[Revision 17.06.2013 under Rule 91]

In Equation 2,

V is the specific volume of the polymer,

Vw is the specific Van der Waals volume.

<Measurement between planes>

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

<BET surface area measurement>

The BET surface area was measured by Brunauer-Emmett-Teller using an isothermal curve of the relative pressure-nitrogen adsorption of materials measured at a temperature of 77K using a pore size and surface area analyzer (ASAP 2020, Micromeritics, USA). Calculated using the formula.

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

Example 2

Except that the heat treatment for 30 minutes at 450 ℃ was carried out in the same manner as in Example 1 to prepare a polymer containing a polybenzoxazole, to obtain a polybenzoxazole film. The FT-IR analysis revealed bands of 1,553 cm ^-1 , 1,480 cm ^-1 (C = N) and 1,058 cm ^-1 (CO), which are polybenzoxazole characteristic bands that were not present in polyhydroxyimide. In addition, the prepared polymer had a free volume of 0.26 and an interplanar distance of 619 pm. The BET surface area was 371 m ² / g.

Example 3

3.384 g of 3,3,3 ', 3'-tetramethyl-1,1'-spirobi (Indan) -5,5'-diamino-6,6'-diol (TSBIDD) prepared above was 3,3 N-methylpyrrolidinone (NMP) with 4.442 g of ', 4,4'-hexafluoropropylidene diphthalic dianhydride (3,3', 4,4'-hexafluoropropylidene diphthalic dianhydride, 6FDA) The solution was reacted for 4 hours in 31.3 g of a solution 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 prepare a film. The thickness of the film thus prepared was 126 mu m.

The polyimide film prepared above was placed in a muffle furnace and heated to 300 ° C. at a rate of 10 ° C./min per minute, and maintained at 300 ° C. for 30 minutes.

Subsequently, a gas separation membrane was prepared by performing a heat treatment to be heated to 425 ° C. and maintained for 2 hours to obtain a transparent pale brown TSBIDD-based polybenzoxazole film.

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

Example 4

A polymer containing polybenzoxazole was prepared as shown in Scheme 2 below.

Scheme 2

[Revision 17.06.2013 under Rule 91]

3.384 g of 3,3,3 ', 3'-tetramethyl-1,1'-spirobi (Indan) -5,5'-diamino-6,6'-diol (TSBIDD) prepared as above was pyromelli A light yellow solution was prepared by reacting with 2.181 g of tic dianhydride (PMDA) in 31.3 g of N-methylpyrrolidinone (NMP) solution for 4 hours.

Subsequently, 40 ml of pyridine and ortho-xylene were added thereto, followed by reaction under reflux for 6 hours to obtain a yellow solution. Subsequently, PMDA-TSBIDD polyimide obtained by immersing it in distilled water and washing and drying is dissolved again in N-methylpyrrolidone (NMP) to 20% by weight. Subsequently, the dissolved solution was cast on a glass plate and maintained at 100 ° C., 150 ° C., 200 ° C. and 250 ° C. for 1 hour in a vacuum oven to prepare a film to obtain a gas separation membrane. The thickness of the film thus prepared was 45 μm.

Heat treatment temperature: 1.5 hours at 450 ℃

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

Example 5

3.384 g of 3,3,3 ', 3'-tetramethyl-1,1'-spirobi (Indan) -5,5'-diamino-6,6'-diol (TSBIDD) prepared as above was pyromelli A light yellow solution was prepared by reacting with 2.181 g of tic dianhydride (PMDA) in 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 to prepare a film. The thickness of the film thus prepared was 52 μm.

The polyimide film prepared above was placed in a muffle furnace and heated to 300 ° C. at a rate of 10 ° C./min per minute, and maintained at 300 ° C. for 30 minutes.

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

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

Example 6

A polymer containing polybenzoxazole was prepared as shown in Scheme 3 below.

Scheme 3

[Revision 17.06.2013 under Rule 91]

3.384 g of 3,3,3 ', 3'-tetramethyl-1,1'-spirobi (Indan) -5,5'-diamino-6,6'-diol (TSBIDD) prepared above was 3,3 N-methylpyrrolidinone (NMP) solution with 2.942 g of ', 4,4'-biphenyl tetracarboxylic dianhydride (3,3', 4,4'-Biphenyltetracarboxylic Dianhydride, BP) 31.3 The reaction was carried out for 4 hours at g to prepare a pale yellow solution.

Subsequently, 40 ml of pyridine and ortho-xylene were added thereto, followed by reaction under reflux for 6 hours to obtain a yellow solution. Subsequently, the BPDA-TSBIDD polyimide obtained by immersion in distilled water, washed and dried is dissolved again in N-methylpyrrolidone (NMP) to 20% by weight. Subsequently, 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 prepare a film. The thickness of the film thus prepared was 61 μm.

The polyimide film prepared above was placed in a muffle furnace and heated to 300 ° C. at a rate of 10 ° C./min per minute, and maintained at 300 ° C. for 30 minutes.

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

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

Example 7

3.384 g of 3,3,3 ', 3'-tetramethyl-1,1'-spirobi (Indan) -5,5'-diamino-6,6'-diol (TSBIDD) prepared above was 3,3 N-methylpyrrolidinone (NMP) solution with 2.942 g of ', 4,4'-biphenyl tetracarboxylic dianhydride (3,3', 4,4'-Biphenyltetracarboxylic Dianhydride, BPDA) The reaction was carried out for 4 hours at g 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 prepare a film. The thickness of the film thus prepared was 93 μm.

The polyimide film prepared above was placed in a muffle furnace and heated to 300 ° C. at a rate of 10 ° C./min per minute, and maintained at 300 ° C. for 30 minutes.

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

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

Example 8

A polymer containing polybenzoxazole was prepared as shown in Scheme 4 below.

Scheme 4

[Revision 17.06.2013 under Rule 91]

3.384 g of 3,3,3 ', 3'-tetramethyl-1,1'-spirobi (Indan) -5,5'-diamino-6,6'-diol (TSBIDD) prepared as above was pyromelli With 1.09g of pyromelitic (PMDA) and 2.221g of 3,3 ', 4,4'-hexafluoropropylidene diphthalic dianhydride (3,3', 4,4'-hexafluoropropylidene diphthalic dianhydride, 6FDA) A light yellow solution was prepared by reacting N-methylpyrrolidinone (N-methylpyrrolidinone, NMP) solution for 3 hours in 31.3 g.

Subsequently, 40 ml of pyridine and ortho-xylene were added thereto, followed by reaction under reflux for 6 hours to obtain a yellow solution. Subsequently, the 6FDA / PMDA-TSBIDD polyimide obtained by immersing it in distilled water and washing and drying was dissolved again in N-methylpyrrolidone (NMP) to 20% by weight. Subsequently, 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 prepare a film. The thickness of the film thus prepared was 46 μm.

The polyimide film prepared above was placed in a muffle furnace and heated to 300 ° C. at a rate of 10 ° C./min per minute, and maintained at 300 ° C. for 30 minutes.

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

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

Comparative Example 1: Polymer Synthesis and Gas Separation Membrane Preparation Using the Same

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

Scheme 5

[Revision 17.06.2013 under Rule 91]

3,3,3 ', 3'-tetramethyl-1,1'-spirobisindane-5,5', 6,6'-tetrol (3,3,3 ', 3'-tetramethyl) in 500 ml flask -1,1'-spirobisindane-5,5 ', 6,6'-tetrol (TTSBI)) 10.213 g (30 mmol) and 1,4-dicyanotetrafluorobenzene (1,4-dicyanotetrafluorobenzene (DCTB)) 6.003 g (30 mmol) and 8.292 g (60 mmol) of potassium carbonate were vigorously stirred at room temperature for about 20 minutes under 200 ml of dimethylformamide (DMF).

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

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

A polymer solution having a concentration of 2 wt% was prepared using a chloroform solvent, purified using a 0.45 μm syringe filter, and then cast on a glass plate to volatilize the solvent 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 μm and the BET surface area was 850 m ² / g.

Comparative Example 2

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

Scheme 6

[Revision 17.06.2013 under Rule 91]

2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (bisAPAF, 3.663 g, 10 mmol) and NMP (15.06 mL) were placed in a 100 mL three neck flask with nitrogen gas and maintained at 0 ° C. Place in ice bath. In this order, a solution of propylene oxide (PO, 0.3 mL) and terephthaloyl chloride (TCL, 2.030 g, 10 mmol) mixed with NMP (8.35 mL) was placed in a flask and allowed to proceed for 2 hours.

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

The poly hydroxy amide precursor film flows argon gas, placed in a furnace that increases by 5 ° C. per minute, increases the temperature to 350 ° C. and is maintained for one hour. After slowly cooling the temperature inside the furnace, a polybenzoxazole film is obtained. The average thickness of the polymer film was 40 μm, the density was 1.39 g / cm ³ , and the interplanar distance was 719 pm.

Comparative Example 3

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

Scheme 7

[Revision 17.06.2013 under Rule 91]

2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (bisAPAF, 3.663 g, 10 mmol) and NMP (15.06 mL) were placed in a 100 mL three neck flask with nitrogen gas and maintained at 0 ° C. Place in ice bath. In this order, a solution of propylene oxide (PO, 0.3 mL) and para-phenylene (tedraloyl dichloride) (TPCL, 2.030 g, 10 mmol) mixed with NMP (8.35 mL) was added to the flask, followed by reaction for 2 hours. Allow this to proceed.

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

The poly hydroxyamide precursor film is placed in a furnace with flowing argon gas and increased by 5 ° C. per minute, increased in temperature to 350 ° C. and maintained for one hour. After slowly cooling the temperature inside the furnace, a polybenzoxazole film is obtained. The average thickness of the polymer film was 42 μm, the density was 1.32 g / cm ³ , and the interplanar distance was 758 pm.

Test Example 1: Mechanical Properties Evaluation

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

Table 1 Gas separation membrane Tensile Strength (MPa) Elongation at Break (%) 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 have elongation percent at break (unit:%) at the gas separation membranes prepared in Comparative Examples 1 to 3. Better than This is because the polymers included in the gas separation membranes prepared in Examples 1 to 8 have a benzoxazole structure and a ladder-type structure at the same time to have a rigidity and flexibility to increase tensile strength.

From the test results, the polymers included in the gas separation membranes prepared in Examples 1 to 8 have a benzoxazole structure and a ladder structure at the same time, such as long working time, acidic conditions and high humidity, high temperature, as well as mild conditions. It can be seen that it can withstand harsh conditions.

Test Example 2: Measurement of gas permeability and selectivity

The gas separation membranes prepared in Examples 1 to 8 and Comparative Examples 2 to 3 were subjected to the following tests in order to determine gas permeability and selectivity. 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 , and the upstream and downstream pressures were 33 atm and 0.002 atm, respectively. Measurements were made using a Baratron transducer with full scale.

All pure gas permeability measurements were performed 5 times or more at 27 ° C. The standard deviation for the mean value of permeability was within ± 2% and the reproducibility of the samples was excellent within ± 5%. The effective area of the gas separation membrane was 4.00 cm ² .

For pure gases, the rate of increase of the permeation pressure in the volume permeated at a fixed pressure or in a fixed collection volume can be measured. Injection pressurep                  _One Permeation pressure above this atmospheric pressurep                  ₂ Has a very small value (<2 Torr). Pressure on the permeate sidep                  ₂                  While measured while recording in large time, an approximation of the permeability of gas molecules through the polymer membrane can be obtained. Gas Permeability of A MoleculesP                  _A  Can be calculated according to the following equation from the rate at which the downstream pressure increases the fixed permeate volume at equilibrium.

[Equation 3]

In Equation 3,

V is the volume of the fixed downstream collector,

l is the film thickness,

A is just area,

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

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

TABLE 2 Gas separation membrane He permeability (Barrer) H ₂ Barrer CO ₂ Permeability (Barrer) O ₂ Barrer N ₂ Barrer CH ₄ Transmittance (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

TABLE 3 Gas separation membrane 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 Table 2 and Table 3, the gas separation membranes prepared in Examples 1 to 8 generally have excellent gas permeability compared to the gas separation membranes prepared in Comparative Examples 2 and 3. In addition, it can be seen that the gas separation membranes prepared in Examples 1 to 8 have a higher level of gas selectivity than the gas separation membranes prepared in Comparative Examples 2 and 3.

Thus, 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)

[Revision 17.06.2013 under Rule 91]
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]

[Formula 2] [Formula 3]

[Formula 4]

In 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 bonds, O, S, C (= 0), CH (OH), S (= 0) ₂ , Si (CH ₃ ) ₂ , (CH ₂ ) _p (where 1 ≦ _p ≦ 10) , (CF ₂ ) q, wherein 1 ≦ q ≦ 10, C (CH ₃ ) ₂ , C (CF ₃ ) ₂ , C (═O) NH or a substituted or unsubstituted tetravalent C 1 to C 30 aliphatic organic group Connected by 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 at each repeating unit and each independently is 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. [Revision 17.06.2013 under Rule 91]
The method of claim 1, Ar ¹ is a polymer selected from one represented by the following formula:

Where X ¹ to X ⁶ are the same or different from each other and each independently 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 , or C (═O) NH, W ¹ and W ² are the same or different and are 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 from each other and are each independently hydrogen or a C1 to C5 alkyl group, Z ² and Z ³ are the same or different from each other and independently of each other N or CR ³⁰³ (wherein R ³⁰³ is hydrogen or a C1 to C5 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, k4, k6, k7, k17, k18, k20, k22, k26 to k29, k31, k34 to k36, k38, k41, k44 to k46 and k55 to k58 are integers from 0 to 3, k30, k37, k42, k43, k47 and k48 are integers from 0 to 4, k32, k33, k39 and k40 are integers from 0 to 5. [Revision 17.06.2013 under Rule 91]
The method of claim 5, Wherein the T is selected from a polymer represented by the following formula:

Where R ²⁰⁰ to R ²³¹ are the same or different from each other and are each independently hydrogen, a substituted or unsubstituted C1 to C30 aliphatic organic group, a substituted or unsubstituted C3 to C30 alicyclic organic group, or a substituted or unsubstituted divalent C6 To C30 aromatic organic group, t1 to t12 are the same or different and are each independently an integer of 0 to 4; [Revision 17.06.2013 under Rule 91]
The method of claim 6, Wherein the T is selected from a polymer represented by the following formula:

[Revision 17.06.2013 under Rule 91]
The method of claim 5, Ar ¹ is a polymer selected from one represented by the following formula:

[Revision 17.06.2013 under Rule 91]
The method of claim 1, Wherein the T is selected from those represented by the following formula:

Where R ²⁰⁰ to R ²³¹ are the same or different from each other and are each independently hydrogen, a substituted or unsubstituted C1 to C30 aliphatic organic group, a substituted or unsubstituted C3 to C30 alicyclic organic group, or a substituted or unsubstituted divalent C6 To C30 aromatic organic group, t1 to t12 are the same or different and are each independently an integer of 0 to 4; [Revision 17.06.2013 under Rule 91]
The method of claim 9, Wherein the T is selected from a polymer represented by the following formula:

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. [Revision 17.06.2013 under Rule 91]
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: [Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

In Chemical Formulas 5 to 8, 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 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 a substituted or unsubstituted tetravalent C 1 to C 30 aliphatic organic group Connected by Ar ^{1 ′} is the same or different from each other and each independently 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, wherein the aromatic ring group Exist 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 '' is O or S, n is an integer satisfying 10 ≦ n ≦ 400. [Revision 17.06.2013 under Rule 91]
The method of claim 13, Ar ¹ is a polymer selected from one represented by the following formula:

Where X ¹ to X ⁶ are the same or different from each other and each independently 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 , or C (═O) NH, W ¹ and W ² are the same or different and are 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 from each other and are each independently hydrogen or a C1 to C5 alkyl group, Z ² and Z ³ are the same or different from each other and independently of each other N or CR ³⁰³ (wherein R ³⁰³ is hydrogen or a C1 to C5 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, k4, k6, k7, k17, k18, k20, k22, k26 to k29, k31, k34 to k36, k38, k41, k44 to k46 and k55 to k58 are integers from 0 to 3, k30, k37, k42, k43, k47 and k48 are integers of 0-4, and k32, k33, k39 and k40 are integers of 0-5. [Revision 17.06.2013 under Rule 91]
The method of claim 14, Wherein the T is selected from a polymer represented by the following formula:

Where R ²⁰⁰ to R ²³¹ are the same or different from each other and are each independently hydrogen, a substituted or unsubstituted C1 to C30 aliphatic organic group, a substituted or unsubstituted C3 to C30 alicyclic organic group, or a substituted or unsubstituted divalent C6 To C30 aromatic organic group, t1 to t12 are the same or different and are each independently an integer of 0 to 4; [Revision 17.06.2013 under Rule 91]
The method of claim 15, Wherein the T is selected from a polymer represented by the following formula:

[Revision 17.06.2013 under Rule 91]
The method of claim 14, Ar ¹ is a polymer selected from one represented by the following formula:

Where M is hydrogen or a metal, said metal being sodium, potassium, lithium, alloys thereof or a combination thereof. [Revision 17.06.2013 under Rule 91]
The method of claim 13, Ar ^{1 ′} is a polymer selected from one of the following formulas:

Where X ¹ to X ⁶ are the same or different from each other and each independently 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 , or C (═O) NH, W ¹ and W ² are the same or different and are 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 from each other and are each independently hydrogen or a C1 to C5 alkyl group, Z ² and Z ³ are the same or different from each other and independently of each other N or CR ³⁰³ (wherein R ³⁰³ is hydrogen or a C1 to C5 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 are each independently hydrogen, a substituted or unsubstituted C 1 to C 10 aliphatic organic group, or a metal sulfonate group, k63, k69, k84 to k88, k92 to k96, k102 to k109, k116 and k119 are integers from 0 to 4, k64 to k66, k68, k71, k74, k75, k77, k78, k81, k83, k110 to k112, k115, k117, k118, k120 and k123 are integers from 0 to 3, k67, k72, k73, k76, k79, k80, k82, k90, k98, k100, k101, k113, k114, k121 and k122 are integers from 0 to 2, k70 is an integer of 0 or 1, k89, k91, k97 and k99 are integers of 0-5. [Revision 17.06.2013 under Rule 91]
The method of claim 18, Ar ^{1 ′} is a polymer selected from one of the following formulas:

Where M is hydrogen or a metal, said metal being sodium, potassium, lithium, alloys thereof or a combination thereof. [Revision 17.06.2013 under Rule 91]
The method of claim 13, Wherein the T is selected from those represented by the following formula:

Where R ²⁰⁰ to R ²³¹ are the same or different from each other and are each independently hydrogen, a substituted or unsubstituted C1 to C30 aliphatic organic group, a substituted or unsubstituted C3 to C30 alicyclic organic group, or a substituted or unsubstituted divalent C6 To C30 aromatic organic group, t1 to t12 are the same or different and are each independently an integer of 0 to 4; [Revision 17.06.2013 under Rule 91]
The method of claim 20, Wherein the T is selected from those represented by the following formula:

The method of claim 1, The polymer is a polymer having a weight average molecular weight (Mw) of 10,000 g / mol to 500,000 g / mol. [Revision 17.06.2013 under Rule 91]
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 Method for producing a polymer comprising the step of heat-treating the polyimide: [Formula 1]

[Formula 2] In Chemical Formula 1 and Chemical Formula 2, 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 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 a substituted or unsubstituted tetravalent C 1 to C 30 aliphatic organic group Connected by 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 at each repeating unit and each independently is OH, SH or NH ₂ , n is an integer satisfying 10 ≦ n ≦ 400. The method of claim 23, wherein The heat treatment is a method of producing a polymer that is heated to 350 to 500 ℃ at a temperature increase rate of 1 to 30 ℃ / min, and performed for 1 minute to 12 hours at an inert atmosphere at that temperature. [Revision 17.06.2013 under Rule 91]
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: [Formula 3]

[Formula 4]

In Chemical Formulas 3 and 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 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 a substituted or unsubstituted tetravalent C 1 to C 30 aliphatic organic group Connected by 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 at each repeating unit and each independently is OH, SH or NH ₂ , n is an integer satisfying 10 ≦ n ≦ 400. The method of claim 25, The heat treatment is a method of producing a polymer that is heated to 350 to 500 ℃ at a temperature increase rate of 1 to 30 ℃ / min, and performed for 1 minute to 12 hours at an inert atmosphere at that temperature. [Revision 17.06.2013 under Rule 91]
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, Imidizing 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 Method for producing a polymer comprising: [Formula 1]

[Formula 2] [Formula 3]

[Formula 4]

In 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 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 a substituted or unsubstituted tetravalent C 1 to C 30 aliphatic organic group Connected by 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 at each repeating unit and each independently is OH, SH or NH ₂ , n is an integer satisfying 10 ≦ n ≦ 400. The method of claim 27, The heat treatment is a method of producing a polymer that is heated to 350 to 500 ℃ at a temperature increase rate of 1 to 30 ℃ / min, and performed for 1 minute to 12 hours at an inert atmosphere at that temperature. A molded article comprising the polymer according to any one of claims 1 to 28. The method of claim 29, The molded article is a gas separation membrane.