Polymer for forming separation membrane, and separation membrane comprising same

Abstract

This polymer for forming a separation membrane comprises a first repeating unit and a second repeating unit, wherein the first repeating unit comprises a structure represented by chemical formula 1, and the second repeating unit comprises an ionic cross-linking bond. The separation membrane includes a support layer and a selective layer, which is formed on the support layer and includes a polymer for forming the separation membrane. A gas separation membrane providing high carbon dioxide permeability and selectivity can be formed using the polymer for forming the separation membrane.

Description

Polymer for forming a separation membrane and a separation membrane containing the same

[0001] The embodiments of the present application relate to a polymer for forming a separation membrane and a separation membrane comprising the same.

[0002] Recently, eco-friendly technologies based on low carbon and carbon neutrality are being developed. In particular, technologies for capturing and separating greenhouse gases such as carbon dioxide are being developed. For example, carbon dioxide can be selectively captured by permeating it through polymer membranes.

[0003] Polymers containing polyethylene oxide units can be used as polymers with high carbon dioxide affinity. However, polyethylene oxide-based polymers have excellent mechanical properties but low permeability when their molecular weight is high, and excellent permeability but low strength when their molecular weight is low, resulting in a trade-off between permeability and mechanical properties. Furthermore, the high flowability of the polyethylene oxide-based polymer can cause clogging of the pores of the porous support, which can consequently reduce gas permeability.

[0004] Therefore, it is necessary to design a membrane that provides enhanced gas permeability and selectivity while ensuring mechanical properties.

[0005] One objective of the present disclosure is to provide a polymer for forming a separation membrane having improved gas permeability selectivity and mechanical properties.

[0006] One objective of the present disclosure is to provide a separation membrane having improved gas permeability selectivity and mechanical properties.

[0007] A polymer for forming a separation membrane is a polymer for forming a separation membrane comprising a first repeating unit and a second repeating unit, wherein the first repeating unit comprises a structure represented by the following chemical formula 1, and the second repeating unit comprises an ionic crosslink.

[0008] [Chemical Formula 1]

[0009]

[0010] In Chemical Formula 1, R 1 and R 2 Each is independently hydrogen or a C1-C10 alkyl group, and n is an integer from 1 to 50.

[0011] In some embodiments, the second repeating unit may include ionic cross-linking by nitrogen (N).

[0012] In some embodiments, the second repeating unit is represented by the following chemical formula 2.

[0013] [Chemical Formula 2]

[0014]

[0015] In Chemical Formula 2, R 3 is hydrogen or a C1-C10 alkyl group, L is a direct bond, COO, CONH, or a C1-C10 alkylene group, m is an integer from 1 to 3, and R 4 is a substituent containing nitrogen that has formed an ionic cross-link.

[0016] In some embodiments, the above chemical formula 2 is represented by the following chemical formula 2-1.

[0017] [Chemical Formula 2-1]

[0018]

[0019] In Chemical Formula 2-1, R 5 is hydrogen or a C1-C10 alkyl group, X is O or NH, L1 is a direct bond or a C1-C10 alkylene group, and R 6 is a substituent containing nitrogen that has formed an ionic cross-link.

[0020] In some embodiments, the ionic crosslinking is the R 4 Ionic cross-linking between nitrogen contained in and a halogen compound or the above R 4 It is an ionic cross-linking between the nitrogen contained in and sulfonate compounds.

[0021] In some embodiments, the halogen compound includes F, Cl, Br, or I.

[0022] In some embodiments, the sulfonate compound comprises a substituted or unsubstituted aryl sulfonate, a substituted or unsubstituted alkyl sulfonate, or a cyclic sulfonate.

[0023] In some embodiments, the second repeating unit is represented by any one of the following chemical formulas 2-1-1 to 2-1-3.

[0024] [Chemical Formula 2-1-1]

[0025]

[0026] [Chemical Formula 2-1-2]

[0027]

[0028] [Chemical Formula 2-1-3]

[0029]

[0030] In chemical formulas 2-1-1 to 2-1-3, R 7 to R 12 is each independently hydrogen or a C1-C10 alkyl group, X is O or NH, Y is C or N, and L 11 and L 12 Each is independently a direct bond or a C1-C10 alkylene group, L2 to L4 are each independently O, a substituted or unsubstituted alkylene group, a substituted or unsubstituted ether group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted cycloalkylene group or a substituted or unsubstituted arylene group, n1 to n3 are each independently integers from 1 to 10, M is a halogen group or a sulfonate group, and ring A is a heterocyclic ring or a hydrocarbon ring.

[0031] In some embodiments, L1 is O, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C2-C80 ether group, a substituted or unsubstituted C1-C10 alkenylene group, a substituted or unsubstituted C1-C10 cycloalkylene group or a substituted or unsubstituted C6-C20 arylene group.

[0032] In some embodiments, the ring A is represented by any one of the following chemical formulas.

[0033]

[0034] In the chemical formula, R 13 is hydrogen or a C1-C10 alkyl group, and *- represents the bonding part of the above chemical formula 2-1-2.

[0035] In some embodiments, the content of the first repeating unit in the total weight of the first repeating unit and the second repeating unit is 60% to 95% by weight.

[0036] In some embodiments, the content of the second repeating unit in the total weight of the first repeating unit and the second repeating unit is 5% to 40% by weight.

[0037] The separator is a separator comprising a support layer; and a selective layer, wherein the selective layer comprises the polymer for forming the separator described above.

[0038] In some embodiments, the separation membrane has a permeability of carbon dioxide gas (CO2) of 550 GPU or more.

[0039] The polymer for forming a separation membrane according to the embodiments of the present disclosure described above comprises a first repeating unit and a second repeating unit, and by including the first repeating unit, it has a high affinity for carbon dioxide, thereby improving permeability and selectivity. In addition, the polymer for forming a separation membrane can realize a separation membrane having excellent mechanical properties by including ionic cross-linking by the second repeating unit.

[0040] Separation membranes comprising the polymer of the present disclosure can be applied to various functional membrane structures, such as ion exchange membranes, electrolyte separation membranes, and gas separation membranes. According to exemplary embodiments, the separation membranes of the present disclosure can be applied to eco-friendly technology fields to prevent climate change by suppressing air pollution and greenhouse gas emissions.

[0041] FIG. 1 is a schematic cross-sectional view showing a separation membrane according to exemplary embodiments.

[0042] FIGS. 2a to 2d are images showing the freestanding membranes of Examples 4, 5, 7, and 8, respectively.

[0043] Figures 3a and 3b show the FT-IR spectra of the polymers for forming separation membranes according to Example 4, Example 5 and Comparative Example 7.

[0044] The embodiments disclosed herein provide a polymer for forming a separation membrane comprising a first repeating unit comprising a structure represented by Formula 1 and a second repeating unit comprising an ionic crosslink. The embodiments disclosed herein provide a separation membrane comprising said polymer.

[0045] Exemplary embodiments will be described in more detail with reference to experimental examples and drawings. However, since the drawings and embodiments attached to this specification serve to further enhance understanding of the technical concept of the present invention, the present invention should not be interpreted as being limited only to the matters described in such drawings and embodiments.

[0046] Polymer for membrane formation

[0047] In this application, "Ca to Cb" is used to refer to substituents having a to b carbon atoms.

[0048] A polymer for forming a separation membrane according to the embodiments of the present disclosure (hereinafter referred to as a polymer) is a polymer for forming a separation membrane comprising a first repeating unit and a second repeating unit, wherein the first repeating unit comprises a structure represented by the following chemical formula 1, and the second repeating unit comprises an ionic crosslink.

[0049] [Chemical Formula 1]

[0050]

[0051] In Chemical Formula 1, R 1 and R 2 Each is independently hydrogen or a C1-C10 alkyl group, and n is an integer from 1 to 50.

[0052] The first repeating unit comprising the structure represented by Chemical Formula 1 has a high affinity for carbon dioxide. Therefore, when a polymer comprising the structure represented by Chemical Formula 1 is applied to a separation membrane, the permeability and selectivity of carbon dioxide can be improved.

[0053] In addition, the polymer can suppress excessive flowability of the polymer and improve the coating properties and mechanical strength of the polymer by including the second repeating unit containing ionic crosslinking.

[0054] In some embodiments, R 1 and R 2 Each can independently be hydrogen or a C1-C10 straight-chain or branched-chain alkyl group.

[0055] In one embodiment, R 1 and R 2 Each can independently be hydrogen or an unsubstituted C1-C10 straight-chain alkyl group.

[0056] In some embodiments, R 1 and R 2 Each can be hydrogen or a methyl group (-CH3).

[0057] In some embodiments, n may be an integer from 1 to 50.

[0058] In some embodiments, n may be an integer of 1 to 40, 2 to 40, 1 to 30, or 2 to 30.

[0059] The first repeating unit comprising the structure represented by Chemical Formula 1 above has a high affinity for gases such as carbon dioxide and can further accelerate gas separation properties. For example, the alkylene oxide unit included in the structure represented by Chemical Formula 1 above can have a high affinity for carbon dioxide through dipole-quadrupole interaction or electron donor-acceptance interaction with carbon dioxide.

[0060] The first repeating unit may be derived from a monomer containing a polyalkylene oxide unit. In some embodiments, the first repeating unit may be derived from a (meth)acrylate-based monomer containing a polyalkylene oxide unit.

[0061] In some embodiments, the first repeating unit comprising a structure represented by Chemical Formula 1 may be derived from a monomer represented by Chemical Formula 1-1 below.

[0062] [Chemical Formula 1-1]

[0063]

[0064] In Chemical Formula 1-1, R 21 and R 22 Each is independently hydrogen or a C1-C10 alkyl group, and n is an integer from 10 to 50.

[0065] In some embodiments, R 21 and R 22 Each can independently be hydrogen or a C1-C10 straight-chain or branched-chain alkyl group.

[0066] In some embodiments, R 21and R 22 Each can independently be hydrogen or a C1-C10 straight-chain alkyl group.

[0067] In some embodiments, R 21 and R 22 Each can be hydrogen or a methyl group (-CH3).

[0068] In some embodiments, R 21 It can be a methyl group (-CH3).

[0069] In some embodiments, R 22 It can be hydrogen.

[0070] In chemical formula 1-1, n can be an integer from 1 to 50.

[0071] In some embodiments, n may be an integer of 1 to 40, 2 to 40, 1 to 30, or 2 to 30.

[0072] In some embodiments, the number average molecular weight (Mn) of the monomer represented by Chemical Formula 1-1 may be 100 to 1,000.

[0073] In one embodiment, the number average molecular weight of the second monomer may be 200 to 1,000. In one embodiment, the number average molecular weight of the second monomer may be 150 to 950. Additionally, the number average molecular weight of the second monomer may be 100 to 200, or 300 to 1,000. In one embodiment, the number average molecular weight of the second monomer may be 150 to 200, or 300 to 1,000. Within the number average molecular weight range, the selectivity of the separation membrane can be further enhanced while ensuring the coating properties of the polymer.

[0074] In some embodiments, the second repeating unit includes ionic crosslinking by nitrogen (N).

[0075] The above "ionic crosslinking by nitrogen" may refer to ionic crosslinking by a substituent containing a nitrogen atom. For example, the above "ionic crosslinking by nitrogen" may refer to ionic crosslinking by a substituent containing a nitrogen cation.

[0076] As used in this specification, the term "ionic crosslinking" may also be referred to as "ionic crosslinking" and may mean a synthesis reaction of a polymer by ionic bonding.

[0077] In some embodiments, the second repeating unit may be represented by the following chemical formula 2.

[0078] [Chemical Formula 2]

[0079]

[0080] In Chemical Formula 2, R 3 is hydrogen or a C1-C10 alkyl group, L is a direct bond, COO, CONH, or a C1-C10 alkylene group, m is an integer from 1 to 3, and R 4 is a substituent containing nitrogen that has formed an ionic cross-link.

[0081] In some embodiments, R 3 It can be hydrogen or a C1-C10 straight-chain or branched-chain alkyl group.

[0082] In some embodiments, R 3 It can be hydrogen or a C1-C10 straight-chain alkyl group.

[0083] In some embodiments, R 3 It can be hydrogen or a methyl group (-CH3).

[0084] In some embodiments, R 3 It can be hydrogen.

[0085] In some embodiments, R 3 It can be a methyl group (-CH3).

[0086] In some embodiments, L may be a direct bond, COO, CONH, or a C1-C8 alkylene group.

[0087] In some embodiments, L may be a direct bond, COO, CONH, or a C1-C6 alkylene group.

[0088] In some embodiments, L may be a direct bond, COO, CONH, or a C1-C5 alkylene group.

[0089] In some embodiments, L may be a direct bond, COO, CONH, or a C1-C4 alkylene group.

[0090] In some embodiments, L may be a direct bond, COO, CONH, a methylene group, an ethylene group, or a propylene group.

[0091] In some embodiments, L may be a direct bond.

[0092] In some embodiments, L may be COO.

[0093] In some embodiments, L may be CONH.

[0094] In some embodiments, L may be a methylene group.

[0095] In some embodiments, L may be an ethylene group.

[0096] In some embodiments, L may be a propylene group.

[0097] In some embodiments, m can be 1 to 3, 2, or 1.

[0098] In some embodiments, R 4is an amine group (-NH2) containing nitrogen with ionic crosslinking, an alkylamine group containing nitrogen with C1-C10 ionic crosslinking, a piperazine group containing nitrogen with ionic crosslinking, an imidazole group containing nitrogen with ionic crosslinking, a pyridine group containing nitrogen with ionic crosslinking, or a triazole group containing nitrogen with ionic crosslinking.

[0099] In some embodiments, R 4 is an amine group (-NH2) containing nitrogen with ionic crosslinking, a dimethylamine group containing nitrogen with ionic crosslinking, a diethylamine group containing nitrogen with ionic crosslinking, a diisopropylamine group containing nitrogen with ionic crosslinking, a tert-butylamine group containing nitrogen with ionic crosslinking, a piperazine group containing nitrogen with ionic crosslinking, an imidazole group containing nitrogen with ionic crosslinking, a pyridine group containing nitrogen with ionic crosslinking, or a triazole group containing nitrogen with ionic crosslinking.

[0100] In some embodiments, Chemical Formula 2 may be represented by the following Chemical Formula 2-1.

[0101] [Chemical Formula 2-1]

[0102]

[0103] In Chemical Formula 2-1, R 5 is hydrogen or a C1-C10 alkyl group, X is O or NH, L1 is a direct bond or a C1-C10 alkylene group, and R 6 is a substituent containing nitrogen that has formed an ionic cross-link.

[0104] In some embodiments, R 5 It can be hydrogen or a C1-C10 straight-chain or branched-chain alkyl group.

[0105] In some embodiments, R5 It can be hydrogen or a C1-C10 straight-chain alkyl group.

[0106] In some embodiments, R 5 It can be hydrogen or a methyl group (-CH3).

[0107] In some embodiments, R 5 It can be hydrogen.

[0108] In some embodiments, R 5 It can be a methyl group (-CH3).

[0109] In some embodiments, X is O.

[0110] In some embodiments, X is NH.

[0111] In some embodiments, L1 is a direct bond, an ethylene group, or a propylene group.

[0112] In some embodiments, R 6 is an amine group (-NH2) containing nitrogen with ionic crosslinking, an alkylamine group containing nitrogen with C1-C10 ionic crosslinking, a piperazine group containing nitrogen with ionic crosslinking, an imidazole group containing nitrogen with ionic crosslinking, a pyridine group containing nitrogen with ionic crosslinking, or a triazole group containing nitrogen with ionic crosslinking.

[0113] In some embodiments, R 6is an amine group (-NH2) containing nitrogen with ionic crosslinking, a dimethylamine group containing nitrogen with ionic crosslinking, a diethylamine group containing nitrogen with ionic crosslinking, a diisopropylamine group containing nitrogen with ionic crosslinking, a tert-butylamine group containing nitrogen with ionic crosslinking, a piperazine group containing nitrogen with ionic crosslinking, an imidazole group containing nitrogen with ionic crosslinking, a pyridine group containing nitrogen with ionic crosslinking, or a triazole group containing nitrogen with ionic crosslinking.

[0114] In some embodiments, the ionic crosslinking is R 4 Ionic cross-linking between nitrogen contained in and halogen compounds or R 4 It is an ionic cross-linking between the nitrogen contained in and sulfonate compounds.

[0115] In some embodiments, the ionic crosslinking is R 6 The ionic cross-linking of nitrogen contained in and halogen groups contained in halogen compounds or R 6 It is an ionic cross-linking between the nitrogen contained in and the sulfonate group contained in sulfonate compounds.

[0116] In some embodiments, the ionic crosslinking is R 4 N included in + Ionic cross-linking of and halogen anions or R 4 N included in + It is an ionic cross-linking of sulfonate ions.

[0117] In some embodiments, the halogen compound comprises F, Cl, Br, or I.

[0118] In some embodiments, the halogen group is F, Cl, Br, or I.

[0119] In some embodiments, the halogen anion is F- , Cl - , Br - or I - am.

[0120] In some embodiments, the sulfonate compound comprises a substituted or unsubstituted aryl sulfonate, a substituted or unsubstituted alkyl sulfonate, or a cyclic sulfonate. In some embodiments, the sulfonate compound comprises a tosyl group, a mesyl group, a triflate group, or a cyclic sulfonate.

[0121] In some embodiments, the sulfonate compound containing the cyclic sulfonate may include 1,3-propane sultone.

[0122] In some embodiments, the sulfonate compound containing the cyclic sulfonate may have the following structure.

[0123]

[0124] In some embodiments, the tosyl group may mean -O-SO2-C6H6-CH3.

[0125] In some embodiments, the mesyl group may mean -O-SO2-CH3.

[0126] In some embodiments, the triflate group may mean -O-SO2-CF3.

[0127] In some embodiments, the second repeating unit is represented by any one of the following chemical formulas 2-1-1 to 2-1-3.

[0128] [Chemical Formula 2-1-1]

[0129]

[0130] [Chemical Formula 2-1-2]

[0131]

[0132] [Chemical Formula 2-1-3]

[0133]

[0134] In chemical formulas 2-1-1 to 2-1-3, R 7 to R 12 is each independently hydrogen or a C1-C10 alkyl group, X is O or NH, Y is C or N, and L 11 and L 12 Each is independently a direct bond or a C1-C10 alkylene group, L2 to L4 are each independently O, a substituted or unsubstituted alkylene group, a substituted or unsubstituted ether group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted cycloalkylene group or a substituted or unsubstituted arylene group, n1 to n3 are each independently integers from 1 to 10, M is a halogen group or a sulfonate group, and ring A is a heterocyclic ring or a hydrocarbon ring.

[0135] In some embodiments, R 7 to R 12 Each is independently hydrogen or a C1-C10 straight-chain alkyl group.

[0136] In some embodiments, R 7 to R 12 Each can independently be hydrogen or a methyl group (-CH3).

[0137] In some embodiments, R 7 to R 12 It can be hydrogen.

[0138] In some embodiments, R 7 to R 12 It can be a methyl group (-CH3).

[0139] In some embodiments, X is O or NH.

[0140] In some embodiments, X is O.

[0141] In some embodiments, X is NH.

[0142] In some embodiments, Y is C or N.

[0143] In some embodiments, Y is C.

[0144] In some embodiments, Y is N.

[0145] In some embodiments, L 11 and L 12 Each is independently a direct bond or a C1-C10 alkylene group.

[0146] In some embodiments, L 11 and L 12 Each is independently a direct bond, an ethylene group, or a propylene group.

[0147] In some embodiments, L2 to L4 are each independently O, a substituted or unsubstituted alkylene group, a substituted or unsubstituted ether group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted cycloalkylene group or a substituted or unsubstituted arylene group.

[0148] As used in this specification, the term “substituted or unsubstituted” may mean that it is substituted or unsubstituted with a substituent such as a halogen (e.g., fluorine (F)), an amino group, a hydroxyl group, a nitro group, an amide group, a cyano group, a cyanate group, an isocyano group, an isocyanate group, a sulfinyl group, a sulfonyl group, a sulfanyl group, a carboxyl group, a phosphine oxide group, a phosphine sulfide group, a silyl group, an oxy group, a carbonyl group, an alkoxy group, an ester group, an alkyl group, a cycloalkyl group, an aryl group, etc. For example, “substituted alkyl group” may mean that a substituent is further bonded to a carbon atom of an alkyl group by substituting at least one of the hydrogen atoms of the alkyl group with the substituent described above.

[0149] In some embodiments, the alkyl group may have 1 to 10, 1 to 9, 1 to 8, 1 to 7, 1 to 6, or 1 to 5 carbon atoms.

[0150] In some embodiments, the alkoxy group may have 1 to 10, 1 to 9, 1 to 8, 1 to 7, 1 to 6, or 1 to 5 carbon atoms.

[0151] In some embodiments, L2 to L4 are each independently O, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C2-C80 ether group, a substituted or unsubstituted C2-C20 alkenylene group, a substituted or unsubstituted C3-C20 cycloalkylene group or a substituted or unsubstituted C6-C20 arylene group.

[0152] In some embodiments, L2 to L4 are each independently O, a substituted or unsubstituted C1-C10 alkylene group, a substituted or unsubstituted C4-C80 ether group, a substituted or unsubstituted C2-C10 alkenylene group, a substituted or unsubstituted C3-C10 cycloalkylene group or a substituted or unsubstituted C6-C10 arylene group.

[0153] In some embodiments, L2 to L4 are each independently O, a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted propylene group, a substituted or unsubstituted butylene group, a substituted or unsubstituted pentylene group, a substituted or unsubstituted hexylene group, a substituted or unsubstituted decylene group, a substituted or unsubstituted dodecylene group, a substituted or unsubstituted cyclohexylene group, a substituted or unsubstituted ethenylene group or a substituted or unsubstituted phenylene group.

[0154] In some embodiments, the substituted or unsubstituted ether group is -L 101 -OL 102 -OL 103 It can be displayed as -, and L 101 to L 103is a substituted or unsubstituted alkylene group.

[0155] In some embodiments, L 101 to L 103 is a substituted or unsubstituted methylene group or a substituted or unsubstituted ethylene group.

[0156] In some embodiments, L 101 to L 103 It is a methylene group or an ethylene group.

[0157] In some embodiments, n1 to n3 are each independently integers from 1 to 10.

[0158] In some embodiments, n1 to n3 are each independently integers of 1 to 9, 1 to 8, 1 to 7, 1 to 6, 1 to 5, 1 to 4, and 1 to 3.

[0159] In some embodiments, M is a halogen group, for example, F, Cl, Br, or I.

[0160] In some embodiments, M is Br.

[0161] In some embodiments, M is a sulfonate group, for example, a tosyl group, a mesyl group, or a triflate group.

[0162] In some embodiments, ring A is a C1-C10 heterocyclic ring or a C1-C10 hydrocarbon ring.

[0163] The above heterocyclic group or hydrocarbon group can be substituted with the substituents described above.

[0164] In some embodiments, the ring A may be a piperazine group, an imidazole group, a pyridine group, or a triazole group.

[0165] In some embodiments, the ring A may be represented by any one of the following chemical formulas.

[0166]

[0167] Among the above chemical formulas, R 13 is hydrogen or a C1-C10 alkyl group, and *- represents the bonding part of the above chemical formula 2-1-2.

[0168] In some embodiments, the R 13 is hydrogen or a C1-C10 alkyl group.

[0169] In some embodiments, the R 13 is hydrogen.

[0170] In some embodiments, the content of the first repeating unit in the total weight of the first repeating unit and the second repeating unit is 60% to 95% by weight.

[0171] In some embodiments, the content of the second repeating unit in the total weight of the first repeating unit and the second repeating unit is 5% to 40% by weight.

[0172] When the content of the first repeating unit and the second repeating unit in the polymer satisfies the aforementioned ranges, sufficient mechanical stability and coating reliability of the separation membrane can be easily secured without impairing gas permeation selectivity.

[0173] The weight ratio or content of the first repeating unit and the second repeating unit may be substantially the same as the weight ratio or content of the first monomer and the second monomer used in polymer formation.

[0174] In some embodiments, the polymer for forming a separation membrane comprising the first repeating unit and the second repeating unit may be represented by any one of the following chemical formulas 3-1-1 to 3-1-3.

[0175] [Chemical Formula 3-1-1]

[0176]

[0177] [Chemical Formula 3-1-2]

[0178]

[0179] [Chemical Formula 3-1-3]

[0180]

[0181] In Chemical Formulas 3-1-1 to 3-1-3, R 1 and R 2 ≡ is each independently hydrogen or a C1-C10 alkyl group, n is an integer from 1 to 50, and R 7 to R 12 is each independently hydrogen or a C1-C10 alkyl group, X is O or NH, Y is C or N, and L 11 and L 12 Each is independently a direct bond or a C1-C10 alkylene group, L2 to L4 are each independently O, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted cycloalkylene group or a substituted or unsubstituted arylene group, n1 to n3 are each independently integers from 1 to 10, M is a halogen group or a sulfonate group, and ring A is a heterocyclic ring or a hydrocarbon ring.

[0182] In some embodiments, the substituents of Formulas 3-1-1 to 3-1-3 are the same as those defined in Formula 1 and Formulas 2-1-1 to 2-1-3 described above.

[0183] In some embodiments, the polymer for forming the separation membrane may be formed from a composition comprising the first monomer, the second monomer, and a crosslinking agent.

[0184] The first repeating unit is derived from the first monomer, and the second repeating unit may be derived from the second monomer and the crosslinking agent.

[0185] In some embodiments, the first monomer may refer to a monomer represented by the above-described chemical formula 1-1.

[0186] In some embodiments, the first monomer may be represented by the following chemical formula 4.

[0187] [Chemical Formula 4]

[0188]

[0189] In Chemical Formula 4, R a is hydrogen or a C1-C10 alkyl group, La is a direct bond, COO, CONH, or a C1-C10 alkylene group, a is an integer from 1 to 3, and R b is a nitrogen-containing substituent.

[0190] In some embodiments, R a It can be hydrogen or a C1-C10 straight-chain or branched-chain alkyl group.

[0191] In some embodiments, R a It can be hydrogen or a C1-C10 straight-chain alkyl group.

[0192] In some embodiments, R a It can be hydrogen or a methyl group (-CH3).

[0193] In some embodiments, R a It can be hydrogen.

[0194] In some embodiments, La may be a direct bond, COO, CONH, or a C1-C8 alkylene group.

[0195] In some embodiments, La may be a direct bond, COO, CONH, or a C1-C6 alkylene group.

[0196] In some embodiments, La may be a direct bond, COO, CONH, or a C1-C5 alkylene group.

[0197] In some embodiments, La may be a direct bond, COO, CONH, or a C1-C4 alkylene group.

[0198] In some embodiments, La may be a direct bond, COO, CONH, a methylene group, an ethylene group, or a propylene group.

[0199] In some embodiments, R b is an amine group (-NH2), a C1-C10 alkylamine group, a piperazine group, an imidazole group, a pyridine group, or a triazole group.

[0200] In some embodiments, R b is an amine group (-NH2), dimethylamine group, diethylamine group, diisopropylamine group, tert-butylamine group, piperazine group, imidazole group, pyridine group, or triazole group.

[0201] In some embodiments, the first monomer may be represented by the following chemical formula 5.

[0202] [Chemical Formula 5]

[0203]

[0204] In Chemical Formula 5, R a1 is hydrogen or a C1-C10 alkyl group, X1 is O or NH, and L a1 is a direct bond or a C1-C10 alkylene group, and R b1 is a substituent containing nitrogen.

[0205] In some embodiments, R a1 It can be hydrogen or a C1-C10 straight-chain or branched-chain alkyl group.

[0206] In some embodiments, R a1 It can be hydrogen or a C1-C10 straight-chain alkyl group.

[0207] In some embodiments, R a1 It can be hydrogen or a methyl group (-CH3).

[0208] In some embodiments, R a1 It can be hydrogen.

[0209] In some embodiments, R a1 It can be a methyl group (-CH3).

[0210] In some embodiments, X1 is O.

[0211] In some embodiments, X1 is NH.

[0212] In some embodiments, L a1 It is a direct bond, an ethylene group, or a propylene group.

[0213] In some embodiments, R b1 It is an amine group (-NH2), a C1-C10 alkylamine group, a piperazine group, an imidazole group, a pyridine group, or a triazole group.

[0214] In some embodiments, R b1 It is an amine group (-NH2), dimethylamine group, diethylamine group, diisopropylamine group, tert-butylamine group, piperazine group, imidazole group, pyridine group, or triazole group.

[0215] In some embodiments, the second monomer may be represented by any one of the following chemical formulas.

[0216]

[0217] In some embodiments, the crosslinking agent may be represented by the following chemical formula 5.

[0218] [Chemical Formula 6]

[0219]

[0220] In Chemical Formula 6, L6 is O, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted cycloalkylene group or a substituted or unsubstituted arylene group, and M1 and M2 are each independently a halogen group or a sulfonate group.

[0221] In some embodiments, L6 is O, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C2-C20 alkenylene group, a substituted or unsubstituted C3-C20 cycloalkylene group or a substituted or unsubstituted C6-C20 arylene group.

[0222] In some embodiments, L6 is O, a substituted or unsubstituted C1-C10 alkylene group, a substituted or unsubstituted C2-C10 alkenylene group, a substituted or unsubstituted C3-C10 cycloalkylene group or a substituted or unsubstituted C6-C10 arylene group.

[0223] In some embodiments, L6 is a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted propylene group, a substituted or unsubstituted butylene group, a substituted or unsubstituted pentylene group, a substituted or unsubstituted hexylene group, a substituted or unsubstituted decylene group, a substituted or unsubstituted dodecylene group, a substituted or unsubstituted cyclohexylene group, a substituted or unsubstituted ethenylene group or a substituted or unsubstituted phenylene group.

[0224] In some embodiments, M1 and M2 are each independently F, Cl, Br, or I.

[0225] In some embodiments, M1 and M2 are each independently a tosyl group or a mesyl group.

[0226] In some embodiments, the crosslinking agent may be represented by any one of the following chemical formulas.

[0227]

[0228] In the above chemical formula, M is the same as defined in the above chemical formulas 2-1-1 to 2-1-3.

[0229] In exemplary embodiments, the crosslinking agent may be used in an amount of 0.1 to 1 equivalent per 1 equivalent of amine group.

[0230] When the content of the crosslinking agent satisfies the aforementioned ranges, sufficient mechanical stability and coating reliability of the separation membrane can be easily secured without impairing gas permeability selectivity.

[0231] According to exemplary embodiments, the polymer can be prepared by copolymerizing the first monomer, the second monomer, and the crosslinking agent in the presence of an initiator.

[0232] The above initiator may be used in an amount of 0.01 to 1 part by weight, 0.03 to 0.5 parts by weight, or 0.05 to 0.1 parts by weight with respect to 100 parts by weight of the first monomer, the second monomer, and the crosslinking agent. Within the above range, appropriate radical polymerization of the first monomer, the second monomer, and the crosslinking agent can be induced.

[0233] The above initiator may include azobisisobutyronitrile (AIBN), ammonium persulfate and / or hydroperoxide, etc.

[0234] The copolymerization described above includes free radical polymerization and can be performed at 50°C to 100°C for 10 to 30 hours. In some embodiments, the copolymerization may be performed at 55°C to 80°C for 15 to 30 hours, or at 60°C to 70°C for 15 to 25 hours. Within the above condition range, appropriate molecular weight and mechanical properties of the polymer can be easily secured without impairing the gas permeability characteristics of the membrane.

[0235] Separator

[0236] In some embodiments, the separator comprises a support layer; and a selective layer, wherein the selective layer comprises the polymer for forming the separator described above.

[0237] FIG. 1 is a schematic cross-sectional view showing a separator according to exemplary embodiments.

[0238] Referring to FIG. 1, the separator (100) may include a support layer (110) and a selection layer (130). According to exemplary embodiments, a gutter layer (120) may be further formed between the support layer (110) and the selection layer (130).

[0239] The support layer (110) may be provided as a porous substrate layer. For example, the support layer (110) may include polysulfone, polyestersulfone, polymethyl methacrylate, polyethylene, polypropylene, polyoxymethylene, polyetheretherketone, polyethylene terephthalate, polyacrylonitrile, cellulose acetate, polyamide, polyimide, polyamideimide, polyetherimide, polyvinylidene fluoride, polyvinyl alcohol, polyarylate, etc. These may be included individually or in combination of two or more.

[0240] In some embodiments, the support layer (110) may comprise polysulfone, polyestersulfone, polyacrylonitrile and / or polyethylene. In one embodiment, the support layer (110) may comprise polyethylene terephthalate and polysulfone in terms of gas permeability.

[0241] In some embodiments, the thickness of the support layer may be 100 μm to 150 μm. For example, the thickness of the support layer may be 100 μm to 140 μm, 100 μm to 130 μm, or 100 μm to 120 μm. When the thickness of the support layer satisfies the aforementioned range, excellent gas permeability may be achieved.

[0242] The selective layer (130) may include a polymer for forming a separation membrane according to the embodiments of the present disclosure described above. According to exemplary embodiments, the polymer for forming a separation membrane may be dissolved in a solvent to prepare a coating solution. The coating solution may be coated onto a support layer (110), for example, through a bar-coating process, and then dried to form the selective layer (130).

[0243] In some embodiments, the thickness of the selective layer may be 10 nm to 300 nm or 100 nm to 300 nm. For example, the thickness of the selective layer may be 100 nm to 250 nm, 150 nm to 250 nm, or 200 nm to 250 nm. When the thickness of the selective layer satisfies the aforementioned ranges, excellent gas permeability may be achieved.

[0244] The above solvents may include water, methanol, ethanol, propanol, butanol, isopropanol, tetrahydrofuran, ethyl acetate, chloroform, dimethyl sulfoxide, dimethylformamide, N-methyl-2-pyrrolidone, etc. These may be used alone or in combination of two or more.

[0245] The gutter layer (120) can be provided as a surface treatment layer for the support layer (110). Through the gutter layer (120), the bonding or adhesion strength of the selection layer (130) to the support layer (110) can be further enhanced.

[0246] The gutter layer (120) may include a silane-based polymer. As a non-limiting example, the gutter layer (120) may include poly(1-trimethylsilyl-1-propine) or polydimethylsiloxane (PDMS). For example, a surface coating solution containing the silane-based polymer may be coated onto a support layer (110) via a bar-coating process and then dried to form the gutter layer (120).

[0247] In some embodiments, the thickness of the gutter layer may be 10 nm to 1000 nm or 200 nm to 400 nm. For example, the thickness of the gutter layer may be 10 nm to 300 nm, 250 nm to 400 nm, 250 nm to 350 nm, or 270 nm to 330 nm. When the thickness of the gutter layer satisfies the aforementioned ranges, excellent gas permeability may be achieved.

[0248] In this specification, room temperature may mean 20 to 30°C.

[0249] In some embodiments, the carbon dioxide gas (CO2) permeability of the separation membrane (100) is 550 GPU (Gas Permeation Unit) or more.

[0250] In some embodiments, the carbon dioxide gas (CO2) permeability of the membrane (100) may be 560 GPU to 2,000 GPU, 560 GPU to 1,900 GPU, 570 GPU to 1,800 GPU, 570 GPU to 1,700 GPU, or 570 GPU to 1,600 GPU.

[0251] In some embodiments, the nitrogen gas (N2) permeability of the membrane (100) may be 10 to 35 GPUs (Gas Permeation Units). In one embodiment, the nitrogen gas (N2) permeability of the membrane (100) may be 11 GPUs to 34 GPUs, or 12 GPUs to 33 GPUs.

[0252] In some embodiments, the selectivity ratio of the carbon dioxide gas (CO2) permeability to the nitrogen gas (N2) permeability of the separation membrane (100) is 40 or more.

[0253] According to exemplary embodiments, the selectivity ratio of carbon dioxide gas (CO2) permeability to nitrogen gas (N2) permeability of the membrane (100) may be 41 or higher, or 42 or higher. In some embodiments, the selectivity ratio of the membrane (100) may be 40 to 65, 40 to 63, 40 to 62, or 40 to 61.

[0254] Meanwhile, when an ionic crosslinking polymer containing polyimide (PI) is applied to the selective layer of a separation membrane, the affinity for carbon dioxide is not high compared to when the polymer for forming a separation membrane containing the first repeating unit according to the embodiment of the present specification is applied, and the thickness of the selective layer produced is thick, resulting in very low gas permeability performance of the separation membrane. On the other hand, the polymer for forming a separation membrane containing the first repeating unit according to the embodiment of the present specification has a relatively high affinity for carbon dioxide, so when the polymer for forming a separation membrane is applied to the selective layer of the separation membrane, the gas permeability performance is improved.

[0255] Hereinafter, experimental examples including specific embodiments and comparative examples are presented to aid in understanding the present disclosure; however, these embodiments are merely illustrative of the invention and are not intended to limit the appended claims. It is obvious to those skilled in the art that various changes and modifications to the embodiments are possible within the scope and spirit of the invention included in the present disclosure, and that such variations and modifications fall within the scope of the appended claims.

[0256] Preparation Example

[0257] The polymer of Example 1 was prepared according to the following reaction scheme.

[0258] [Reaction Equation]

[0259]

[0260] 8 g of POEM (poly(oxyethylene methacrylate)), number average molecular weight (Mn) 500, 2 g of the amine monomer N-[3-(Dimethylamino)propyl]methacrylamide, and 30 ml of dimethylacetamide (DMAc) were added to a 50 ml reactor vial, and N2 gas was bubbled for 1 hour while stirring. Subsequently, the mixture was heated to 60 ℃ under an N2 atmosphere, 10 mg of azobisisobutyronitrile (AIBN) dissolved in 1 g of dimethylacetamide (DMAc) was added dropwise, and the reaction was carried out by heating for 24 hours. After the reaction was completed, the mixture was cooled, and the cooled solution was added dropwise to 100 ml of diethyl ether to form a white precipitate, and the supernatant was removed. Hexane was added and stirred, the supernatant was removed, and the polymer was vacuum dried at 50 ℃ for 24 hours.

[0261]

[0262] A PTMSP (poly[1-(trimethylsilyl)-1-propyne]) solution diluted to a concentration of 1.0 wt% in heptane solvent was coated by a bar coating method onto the surface of a porous polysulfone support (composed of a polysulfone (Polysulfone, 10 kDa MWCO) with a thickness of approximately 40 μm on a porous polyethylene terephthalate (PET) nonwoven fabric with a thickness of approximately 70 μm) to form a gutter layer with a thickness of approximately 300 nm. Then, the obtained polymer was dissolved in an ethanol solvent to prepare a coating solution with a concentration of 1.0 wt% of the total weight of the solution.

[0263] Dibromododecane (DBD), a crosslinking agent, was added to the coating solution in an amount of 0.45 equivalents (eq) per 1 equivalent amine group and mixed. Then, the coating solution was coated onto a porous polysulfone support coated with PTMSP using a bar coating method. To facilitate crosslinking, a selective layer was prepared to a thickness of approximately 220 nm by drying at 50°C for about 16 hours, thereby producing the separator of Example 1.

[0264] Polymers and membranes were prepared in the same manner as in Example 1, except that the amine monomers and crosslinking agents applied in Examples 2 to 9, respectively, were those listed in Table 1 below, and the synthesis of the polymer was confirmed through the DSC analysis and FR-IR analysis below.

[0265] In addition, Comparative Examples 1 to 5 prepared polymers and separation membranes in the same manner as Example 1, except that the monomers and crosslinking agents listed in Table 1 below were used, respectively.

[0266] Comparative Examples 6 to 8 prepared polymers and separation membranes in the same manner as Example 1, except that no crosslinking agent was used.

[0267]

[0268] DSC analysis

[0269] The glass transition temperature (Tg) of the polymers in Examples 4 and 5 was measured by Differential Scanning Calorimetry (DSC).

[0270] The melting point (Tg) of the polymer before crosslinking was observed to be -60.16°C, and the glass transition temperature (Tg) of the polymers in Examples 4 and 5 increased to -54.95°C and -57.01°C, respectively. Accordingly, it can be predicted that the Tg value increases compared to before the addition of the crosslinking agent, the fluidity of the polymer decreases, and the mechanical properties are improved.

[0271]

[0272] FT-IR analysis

[0273] FT-IR Spectroscopy analysis was performed on the polymers according to Examples 4 and 5 and Comparative Example 7, and the results are shown in Figures 3a and 3b, and changes before and after ionic crosslinking were observed.

[0274] In Comparative Example 7, which does not include ionic cross-linking, 2765 cm -1 to 2825 cm -1N-CH2 and CH3 peaks were observed in the interval.

[0275] On the other hand, it was confirmed that the polymers according to Examples 4 and 5 contain ionic crosslinks and do not exhibit N-CH2, CH3 peaks like Comparative Example 7.

[0276]

[0277] Experimental Example

[0278] (1) Measurement of gas permeability and selectivity

[0279] The carbon dioxide permeability at room temperature was measured. Specifically, at room temperature, carbon dioxide gas (purity 99.995% or higher) at a constant pressure (1 bar, 2 bar, 5 bar, 10 bar, etc.) was injected into the upper part of the gas separation membrane using a pressure regulator to induce gas permeation due to the pressure difference between the upper and lower parts of the membrane (membrane area 11.34 cm²). At this time, the flow rate of the gas permeating through the membrane was measured using a mass flow meter to evaluate the carbon dioxide permeability of the membrane, and the results are listed in Table 1 below.

[0280] The permeability to nitrogen gas was evaluated by conducting the same procedure as the above carbon dioxide permeability measurement, except that nitrogen gas (99.999% purity) was used instead of carbon dioxide gas. The carbon dioxide selectivity was calculated as the ratio of carbon dioxide permeability to nitrogen permeability (CO2 / N2) and is listed in Table 1 below.

[0281] The measurement results are shown together in Table 1 below.

[0282]

[0283] Monomer (Content (g)) Crosslinking agent (Content (eq)) Permeability CO2 (GPU) N2 (GPU) Selectivity Example 1 POEM (8) N-[3-(Dimethylamino)propyl]methacrylamide (2) DBD (0.45) 979.7 1757.5 Example 2 POEM (8) N-[3-(Dimethylamino)propyl]methacrylamide (2) DBB (0.45) 854.5 14.16 0.6 Example 3 POEM (8) N-[3-(Dimethylamino)propyl]methacrylamide (2) DBDFH (0.45) 960.5 17.55 4.9 Example 4 POEM (8) 2-(Dimethylamino)ethyl methacrylate (2) DBD (0.45) 1508.13 1.24 8.3 Example 5 POEM(8) 2-(Dimethylamino)ethyl methacrylate(2) DBB(0.45) 1246.322.455.8 Example 6 POEM(8) 2-(Dimethylamino)ethyl methacrylate(2) DBDFH(0.45) 133725.851.8 Example 7 POEM(8) Vinyl imidazole(2) DBD(0.45) 917.421.742.3 Example 8 POEM(8) Vinyl imidazole(2) DBB(0.45) 575.211.152.1 Example 9 POEM(8) Vinyl imidazole(2) DBDFH(0.45) 813.91458.1 Comparative Example 1 POEM(8) Glycidyl methacrylate(2)PPG-diamine(0.45)143.79.215.6 Comparative Example 2 POEM(8)Glycidyl methacrylate(2)PEG-diamine(0.45)3872118.4 Comparative Example 3 POEM(8)Glycidyl methacrylate(2)AEP(0.45)47112.936.6 Comparative Example 4 POEM(8)Glycidyl methacrylate(2)TEPA(0.45)52714.137.3 Comparative Example 5 POEM(8)Glycidyl methacrylate(2)Jeffamine(0.45)28318.315.5 Comparative Example 6 POEM(8)N-[3-(Dimethylamino)propyl]methacrylamide (2)-11552057.8 Comparative Example 7 POEM(8)2-(Dimethylamino)ethyl methacrylate(2)-1319.828.745.9 Comparative Example 8 POEM(8)Vinyl imidazole(2)-1089.223.147.2.

[0284] The crosslinking agents listed in Table 1 are as follows.

[0285] -DBD: Dibromododacane

[0286] -DBB: Dibromobutane

[0287] -DBDFH (CAS No. 918-22-9): 1,6-Dibromododecafluorohexane

[0288] -PPG-diamine(Mn 2,000):

[0289]

[0290] -PEG-diamine(Mn 1,500):

[0291]

[0292] -AEP: Aminoethylpiperazine

[0293] -TEPA: Tetraethylenepentamine

[0294] -Jeffamine (CAS No. 65605-36-9) (Mw 1,900): Bis(2-aminopropyl) polypropylene glycol-block-polyethylene glycol-block-polypropylene glycol

[0295]

[0296] Referring to Table 1, overall improved carbon dioxide permeation selectivity was achieved in the separation membrane using the polymer of the examples.

[0297] In the separation membranes of Comparative Examples 1 to 5 using polymers that do not contain ionic crosslinking, significantly reduced permeation selectivity was provided compared to the examples.

[0298]

[0299] (2) Evaluation of mechanical properties

[0300] A first mixed solution was prepared in which the polymer was 10% by weight based on the total weight of the polymer and solvent (ethanol) of Examples 4, 5, 7, 8 and Comparative Examples 1 to 5 prepared according to the above-described preparation example. Additionally, a second mixed solution was prepared in which the crosslinking agent applied in the above-described preparation example was 10% by weight based on the total weight of the crosslinking agent and solvent (ethanol). 10g of the first mixed solution and the second mixed solution were mixed in an equivalent amount in a vial, poured into a trifluoroacetic acid (TFA) dish with a diameter of 5cm, and dried at 50°C until the solvent was removed. After removing the solvent, the mixture was dried at 80°C for 16 hours, cooled at room temperature for at least 1 hour, and then peeled off from the dish to produce a free-standing film, and its mechanical properties were evaluated as follows.

[0301] ○: A freestanding membrane is formed

[0302] X: Freestanding membrane not formed

[0303]

[0304] The evaluation results are shown in Table 2 below.

[0305] Mechanical Property Evaluation Example 4○ Example 5○ Example 7○ Example 8○ Comparative Example 1X Comparative Example 2X Comparative Example 3X Comparative Example 4X Comparative Example 5X

[0306] Referring to Table 2, freestanding membranes were formed in Examples 4, 5, 7, and 8. Specifically, FIG. 2a applied the polymer according to Example 4, FIG. 2b applied the polymer according to Example 5, FIG. 2c applied the polymer according to Example 7, and FIG. 2d applied the polymer according to Example 8. FIG. 2a to 2d confirm that freestanding membranes are formed well. This indicates that the mechanical properties of the separation membrane according to the examples are improved.

[0307] On the other hand, in comparative examples where polymers not containing ionic crosslinking were used, a freestanding film capable of evaluating mechanical properties was not substantially formed.

[0308] [Explanation of the symbol]

[0309] 100: Separator

[0310] 110: Support base

[0311] 120: Gutter layer

[0312] 130: Selection layer

Claims

1. A polymer for forming a separation membrane comprising a first repeating unit and a second repeating unit, A polymer for forming a separation membrane, wherein the first repeating unit comprises a structure represented by the following chemical formula 1, and the second repeating unit comprises an ionic crosslink: [Chemical Formula 1] (of Chemical Formula 1, R 1 and R 2 ≡ is each independently hydrogen or a C1-C10 alkyl group, and n is an integer from 1 to 50).

2. A polymer for forming a separation membrane according to claim 1, wherein the second repeating unit comprises ionic cross-linking by nitrogen (N).

3. The second repeating unit of Claim 1 is a polymer for forming a separation membrane, represented by the following chemical formula 2: [Chemical Formula 2] (of Chemical Formula 2, R 3 is hydrogen or a C1-C10 alkyl group, L is a direct bond, COO, CONH, or a C1-C10 alkylene group, m is an integer from 1 to 3, and R 4 is a substituent containing nitrogen that has formed an ionic cross-link).

4. The polymer for forming a separation membrane according to claim 3, wherein the chemical formula 2 is represented by the following chemical formula 2-1: [Chemical Formula 2-1] (In Chemical Formula 2-1, R 5 is hydrogen or a C1-C10 alkyl group, X is O or NH, L1 is a direct bond or a C1-C10 alkylene group, and R 6 is a substituent containing nitrogen that has formed an ionic cross-link).

5. In claim 3, the ionic crosslinking is the R 4 Ionic cross-linking between nitrogen contained in and a halogen compound or the above R 4 A polymer for forming a separation membrane, comprising an ionic cross-linking between nitrogen contained therein and a sulfonate-based compound.

6. The polymer for forming a separation membrane according to claim 5, wherein the halogen compound comprises F, Cl, Br, or I.

7. The polymer for forming a separation membrane according to claim 5, wherein the sulfonate-based compound comprises a substituted or unsubstituted aryl sulfonate, a substituted or unsubstituted alkyl sulfonate, or a cyclic sulfonate.

8. The polymer for forming a separation membrane according to Claim 1, wherein the second repeating unit is represented by any one of the following chemical formulas 2-1-1 to 2-1-3: [Chemical Formula 2-1-1] [Chemical Formula 2-1-2] [Chemical Formula 2-1-3] (of chemical formulas 2-1-1 to 2-1-3, R 7 to R 12 is each independently hydrogen or a C1-C10 alkyl group, X is O or NH, Y is C or N, and L 11 and L 12 is each independently a directly bonded or C1-C10 alkylene group, L2 to L4 are each independently O, a substituted or unsubstituted alkylene group, a substituted or unsubstituted ether group, a substituted or unsubstituted alkenylene group, a substituted or unsubstituted cycloalkylene group, or a substituted or unsubstituted arylene group, n1 to n3 are each independently integers from 1 to 10, M is a halogen group or a sulfonate group, and ring A is a heterocyclic ring or a hydrocarbon ring).

9. A polymer for forming a separation membrane according to claim 8, wherein L2 to L4 are each independently O, a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C2-C80 ether group, a substituted or unsubstituted C2-C20 alkenylene group, a substituted or unsubstituted C3-C20 cycloalkylene group or a substituted or unsubstituted C6-C20 arylene group.

10. The polymer for forming a separation membrane according to claim 8, wherein ring A is represented by any one of the following chemical formulas: (In the chemical formula, R 13 is hydrogen or a C1-C10 alkyl group, and *- indicates the bonding part of the above chemical formula 2-1-2).

11. A polymer for forming a separation membrane according to claim 1, wherein the content of the first repeating unit is 60% to 95% by weight of the total weight of the first repeating unit and the second repeating unit.

12. A polymer for forming a separation membrane according to claim 1, wherein the content of the second repeating unit is 5% to 40% by weight of the total weight of the first repeating unit and the second repeating unit.

13. Support layer; and A separator including a selective layer, The above-mentioned selection layer comprises a polymer for forming a separation membrane according to claim 1, a separation membrane.

14. The separation membrane of claim 13, wherein the permeability of carbon dioxide gas (CO2) is 550 GPU or higher.

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