KR20190070249A - Hybrid polymeric hollow fiber membrane, carbon molecular sieve hollow fiber membrane, and processes for fabricating the same - Google Patents

Abstract

The present invention relates to a polymer hollow fiber membrane, a carbon molecular sieve hollow fiber membrane, and a method for manufacturing the same. Specifically, the present invention provides a hybrid polymer hollow fiber membrane comprising a glassy polymer matrix containing fluorine and a ladder-type polysilsesquioxane, a carbon molecular sieve hollow fiber membrane having excellent separation performance manufactured by thermal decomposition (carbonization) of the hybrid polymer hollow fiber membrane, and a method for manufacturing the same. The hybrid polymer hollow fiber membrane and the carbon molecular sieve hollow fiber membrane according to the embodiment of the present invention have excellent gas separation performance and can have a large surface area per unit volume, and thus can be usefully used for separating gas with high energy efficiency and large capacity.

Description

HYBRID POLYMERIC HOLLOW FIBER MEMBRANE, CARBON MOLECULAR SIEVE HOLLOW FIBER MEMBRANE, AND PROCESSES FOR FABRICATING THE SAME BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hybrid polymer hollow fiber membrane,

The present invention relates to a polymer hollow fiber membrane, a carbon molecular sieve hollow fiber membrane, and a method for producing the hollow fiber membrane. Specifically, the present invention relates to a hybrid polymer hollow fiber membrane containing a fluorine-containing glassy polymer matrix and a ladder-type polysilsesquioxane, a hybrid carbon molecular sieve hollow fiber membrane produced by pyrolysis (i.e., carbonization) .

In the petrochemical industry, ethylene / ethane and propylene / propane are very important compounds, forming a very large market size around the world. The separation of olefins / paraffins has been carried out mainly by cryogenic distillation, which has a disadvantage of consuming a lot of energy. Therefore, attempts have been made to replace this with separator technology that exhibits high energy efficiency.

In addition, studies have been actively made to remove carbon dioxide (CO ₂ ) contained in natural gas to a certain level (for example, 2%) or less by using membrane technology. However, in the case of gas separation involving a condensable gas, conventional polymer separation membranes have a problem in that the selectivity of gas separation is significantly reduced by plasticization of the polymer chains under high pressure conditions.

As such, carbon molecular sieves (CMS) have been attracting attention as separators having excellent performance in separating gas molecules that are difficult to separate or expensive in the prior art.

When a carbon molecular sieve separator is produced by pyrolysis of a polymer membrane precursor, sp ² hybrid carbon plates formed at the time of pyrolysis form a structure that is deviated from each other (that is, a turbostratic structure). At this time, (7 ~ 20 Å) of high permeability and ultrafine pores (<7 Å) of high selectivity can be formed together, so that the carbon molecular sieve has better gas permeability and selectivity than the polymer membrane precursor .

In general, since the hollow fiber membrane can have a large surface area per unit volume as compared with the plate type membrane, a dry-jet / wet-quench process is used to separate a large amount of gas Attempts have been made to fabricate hollow fiber membranes (see Figure 1).

Specifically, when a bore fluid such as a dope solution and an aqueous solution of N-methyl-2-pyrrolidone (NMP) is injected (that is, radiated) through a spinneret, A dense membrane is formed on the outer wall of the hollow fiber by the evaporation of the volatile solvent. Subsequently, when the hollow fiber membrane is submerged in water, the phase transition occurs due to the exchange of water and solvent to form a porous support layer (see FIG. 2). The conditions of the polymer hollow fiber membrane manufacturing process include polymer solution temperature, polymer solution injection speed, take-up drum rotation speed, air exposure height, and water temperature.

Thereafter, the carbon molecular sieve hollow fiber membrane is prepared by pyrolyzing (i.e., carbonizing) the polymer hollow fiber precursor obtained in the dry-jet / wet-quench process in a pyrolysis apparatus (see FIG. 3) . For example, an inert gas such as argon is continuously injected into a quartz tube containing a polymer hollow fiber membrane and heated to a pyrolytic temperature. Since glassy polymers generally have a higher thermal decomposition temperature than the glass transition temperature, polymer chains are loosened at a higher temperature than the glass transition temperature during the pyrolysis process of the hollow fiber membrane, thereby damaging the pores of the support layer and forming a thick resistive layer do. Due to the formation of such a thick resistive layer, conventional carbon molecular sieve hollow fibers have difficulty in realizing excellent permeability inherent to carbon molecular sieve materials (see J. Membr. Sci., 2011, 380, 138-147).

In order to solve this problem, the surface of the hollow fiber membrane was treated with vinyltrimethoxysilane ("V-treatment") before hydrolysis-condensation reaction of the polymer hollow fiber membrane To form a crosslinked silica layer. The rigid siloxane structure thus formed was able to inhibit the internal structure collapse of the carbon molecular sieve hollow fiber membrane (Carbon, 2014, 76, 417-434, U.S. Patent Application Publication No. 2013-0152793). However, the V-treatment method requires a number of additional steps, and there is still a disadvantage in that resistance is generated upon gas permeation due to an unnecessary crosslinked silica layer formed on the surface, thereby reducing the gas permeation efficiency.

On the other hand, in order to solve the internal structure collapse of the carbon molecular sieve hollow fiber membrane, a multilayer carbon containing nanoparticles such as silica (SiO ₂ ) and polyhedral oligomeric silsesquioxane (POSS) A molecular sieve hollow fiber membrane has recently been proposed (see U.S. Patent Application Publication No. 2017-0274327). The high thermal stability silica, POSS, supported the pores of the hollow fiber membranes and prevented the collapse of the pores in the pyrolysis process and prevented the deterioration of the permeability. However, the solution based on such particulate matter has a limitation in efficiently maintaining the pores of the hollow fiber membrane support due to the coagulation phenomenon occurring as the concentration of the particles increases.

In addition, the carbon molecular sieve separator has a problem that the gas permeability is drastically reduced over time due to the physical aging phenomenon. Since the carbon molecular sieve structure formed immediately after pyrolysis (i.e., carbonization) of the polymer hollow fiber membrane is in a thermodynamically unstable state, the carbon plate packing increases to reach equilibrium state, and the pore volume decreases accordingly. Particularly, the carbon molecular sieve hollow fiber membrane based on a glassy polymer hollow fiber membrane precursor having a large free volume can remarkably decrease the permeability (see Carbon, 2014, 80, 155-166).

U.S. Patent Application Publication No. 2013-0152793 U.S. Patent Application Publication No. 2017-0274327

 J. Membr. Sci., 2011, 380, 138-147  Carbon, 2014, 76, 417-434  Carbon, 2014, 80, 155-166

An object of the present invention is to provide a polymer hollow fiber membrane having excellent gas permeability and selectivity.

Another object of the present invention is to provide a method for producing the above polymer hollow fiber membrane.

Another object of the present invention is to provide a carbon molecular sieve hollow fiber membrane which is produced by pyrolyzing (i.e., carbonizing) the above polymer hollow fiber membrane and has excellent gas permeability and selectivity.

It is another object of the present invention to provide a method for producing the above carbon molecular sieve hollow fiber membrane.

According to one embodiment of the present invention for achieving the above object, there is provided a hybrid polymer hollow fiber membrane comprising a fluorine-containing glassy polymer matrix and a ladder-type polysilsesquioxane.

According to another embodiment of the present invention, there is provided a method for preparing a fluorine-containing polymer, comprising the steps of: (1) dissolving fluorine-containing glassy polymer matrix and ladder-type polysilsesquioxane in an organic solvent to obtain a polymer solution; (2) spinning a polymer solution and a bore fluid through a spinneret to form a polymer hollow fiber membrane; (3) cooling the polymer hollow fiber membrane with a cooling medium; And (4) winding the polymer hollow fiber membrane. The present invention also provides a method for producing a hybrid polymer hollow fiber membrane.

According to another embodiment of the present invention, there is provided a hybrid carbon molecular sieve including a carbide of a hybrid polymer hollow fiber membrane containing a fluorine-containing glassy polymer matrix and a ladder-type polysilsesquioxane A hollow fiber membrane is provided.

According to another embodiment of the present invention, there is provided a method for producing a fluorine-containing polymer, comprising the steps of: (1) dissolving fluorine-containing glassy polymer matrix and ladder-type polysilsesquioxane in an organic solvent to obtain a polymer solution; (2) spinning a polymer solution and a bore fluid through a spinneret to form a polymer hollow fiber membrane; (3) cooling the polymer hollow fiber membrane with a cooling medium; (4) winding the polymer hollow fiber membrane; And (5) pyrolyzing the polymer hollow fiber membrane. The present invention also provides a method for producing a hybrid carbon molecular sieve hollow fiber membrane.

The hybrid polymer hollow fiber membrane of the present invention comprising a fluorine-containing glassy polymer matrix and ladder-type polysilsesquioxane exhibits a cow and an aging effect of polysilsesquioxane having a rigid double siloxane structure in the form of a ladder .

In addition, the carbon molecular sieve hollow fiber membrane produced therefrom increases the glass transition temperature of the glassy polymer due to the polysilsesquioxane having a rigid double siloxane structure in the form of a ladder, thereby minimizing the collapse of the porous support during pyrolysis . Through this, it is possible to realize excellent separation performance (for example, gas permeability and selectivity) inherent to carbon molecular sieve, particularly high permeability. Polysilsesquioxane is well mixed with glassy polymer because it contains an organic functional group. Like the hybrid polymer hollow fiber membrane, a rigid double siloxane structure can effectively delay the aging phenomenon of the carbon molecular sieve separator. In addition, there is an advantage that no additional resistance layer is formed on the outer wall of the polymer hollow fiber membrane.

The hybrid polymer hollow fiber membrane and the carbon molecular sieve hollow fiber membrane of the present invention are simple to manufacture.

1 is a schematic diagram of a dry-jet / wet-process process for producing a polymer hollow fiber membrane.
2 is a schematic view of a general polymer hollow fiber membrane.
3 is a schematic view of an apparatus for pyrolyzing a polymer hollow fiber membrane.
4 is a ternary diagram for the preparation of a hybrid precursor hollow fiber membrane comprising 6FDA-DAM: DABA (3: 2) and LPPyr 64, in one embodiment of the present invention.
FIG. 5 is a graph showing the results obtained by scanning the polymer hollow fiber membranes (a to c) containing 6FDA-DAM: DABA (3: 2) and LPPyr64 and the carbon molecular sieve hollow fibers (d to f) It is an electron microscope (SEM) photograph.
FIG. 6 is a graph showing the results of measurement of a carbon molecular sieve hollow fiber membrane obtained from a polymer hollow fiber membrane containing 6FDA-DAM: DABA (3: 2) and LPPyr 64 and a carbon molecular sieve hollow body coated with poly (dimethylsiloxane) This is a graph evaluating the gas separation performance of the desert.

Hereinafter, the present invention will be described in more detail.

hybrid  Polymer hollow fiber membrane

The hybrid polymer hollow fiber membrane according to an embodiment of the present invention includes a glassy polymer matrix containing fluorine and a ladder-structured polysilsesquioxane (LPSQ).

The hybrid polymer hollow fiber membrane may be prepared from a hybrid composition comprising a fluorine-containing glassy polymer matrix and ladder-type polysilsesquioxane (LPSQ).

Specifically, the fluorine-containing vitreous polymer as one component of the hybrid polymer hollow fiber membrane may be a fluorine-containing polyimide.

In one embodiment, the polyimide containing fluorine in the molecule can be obtained by a condensation reaction of an aromatic carboxylic dianhydride and an aromatic diamine by a known method.

As a preferred embodiment, the polyimide containing fluorine in the molecule may be a fluorine-containing polyimide obtained by condensation reaction of an aromatic carboxylic acid dianhydride and an aromatic diamine.

The aromatic carboxylic acid dianhydride that can be used in the synthesis of the fluorine-containing polyimide of the present invention includes pyromellitic dianhydride, 4,4'-diphthalic anhydride, 4 4,4'- (hexafluoroisopropylidene) diphthalic anhydride (6FDA), 4'-carbonyldiphthalic anhydride, 4,4'- (hexafluoroisopropylidene) diphthalic anhydride, 4,4'-oxydiphthalic anhydride, 4,4'-sulfonyldiphthalic anhydride, and 4,4 '- (4,4'-oxydiphthalic anhydride) (4,4 '- (4,4'-isopropylidene-diphenoxy) diphthalic anhydride). However, the aromatic carboxylic acid dianhydride capable of producing the fluorine-containing polyimide is not limited thereto.

Preferably, the aromatic carboxylic acid dianhydride which can be used for synthesizing the fluorine-containing polyimide may be 4,4 '- (hexafluoroisopropylidene) diphthalic acid dianhydride (6FDA) having the structure represented by the following formula have.

[Chemical Formula 1]

The aromatic diamine that can be used in the synthesis of the fluorine-containing polyimide of the present invention is 2,4,6-trimethyl-1,3-diaminobenzene (DAM), 3, (DABA), 1,4-phenylenediamine (p-PDA), 1,3-phenylenediamine, m -PDA), 2,3,5,6-tetramethyl-1,4-phenylenediamine (Durene), 2,4,5,6- Tetrafluoro-1,3-phenylenediamine, 2,3,5,6-tetrafluoro-1,4-phenylenediamine (2, , 3,5,6-tetrafluoro-1,4-phenylenediamine, and 3,5-diaminobenzoic acid. However, the aromatic diamine capable of producing the fluorine-containing polyimide is not limited thereto.

Preferably, the aromatic diamine that can be used for the synthesis of the fluorine-containing polyimide is 2,4,6-trimethyl-1,3-diaminobenzene (DAM) having the structure represented by the following formula (2) Diamine benzoic acid (DABA) having a structure represented by the following formula (2), 1,4-phenylenediamine (p-PDA) having a structure represented by the formula 2 (c) Tetramethyl-p-phenylenediamine (Durene) having a structure represented by the following formula (2), and a mixture thereof: 1,3-phenylenediamine (m-PDA) Can be selected.

(2)

In one preferred embodiment, the polyimide containing fluorine in the molecule may be a 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride-based polyimide having a repeating unit represented by the following formula (3).

(3)

Wherein R is a C _1-20 aliphatic alkyl containing or not containing fluorine; Alicyclic alkyl including monocyclic ring, dicyclic ring, heterocyclic ring or multicyclic; Or an aromatic ring.

Specifically, the 6FDA-based polyimide is poly (2,4,6-trimethyl-1,3-pentylene-4,4 '- (hexafluoropropylidene) diphenylimide) (hexafluoroisopropylidene) diphthalimide (6FDA-DAM)), poly (1,3-phenylene-4,4'-hexafluoropropylidene) diphthalimide (6FDA-mPDA), poly (3,5-benzoic acid-4,4'- (hexafluoropropylidene) diphthalimide), poly (3,3-phenylene-4,4'- hexafluoroisopropylidene diphthalimide (poly (3,5-benzoic acid-4,4 '- (hexafluoroisopropylidene) diphthalimide (6FDA-DABA)), poly (diethyltoluene- poly (2,4,6-trimethyl-1,3-phenylene- (4,4 '- (hexafluoropropylidene) Dioctyl-1,3,6-trimethyl-1,3-phenylene-4,4'-biphenylimide) (poly (2,4,6- 4,4 '- (hexafluoroisopropylidene) diphthalimide-co-2,4,6-trimethyl-1,3-phenylene- bipthalimide (6FDA: BPDA-DAM (1: 1)), poly (1,5-naphthalene-4,4'- (hexafluoropropylidene) dipyrimid- 4,4'- (hexafluoropropylidene) diphthalimide) (poly (1,5-naphthalene-4,4 '- (hexafluoroisopropylidene) diphthalimide-co- (hexafluoroisopropylidene) diphthalimide (6FDA-1,5-ND: ODA (1: 1)), poly (diethyltoluene-4,4'- (hexafluoropropylidene) dipyrimid- , 6-trimethyl-1,3-pentylene-4,4 '- (hexafluoropropylidene) diphthalimide) (poly (diethyltoluene-4,4'- (hexafluoroisopropylidene) diphthalimide- 6-trimethyl-1,3-phenylene-4,4 '- (hexafluoroisopropylidene) dipthalimide (6FDA-DETDA: DABA Poly (1,3-phenylene-4,4 '- ((4-fluorophenyl) propylidene) diphthalimide-co-3,5-benzoic acid-4,4'- (hexafluoropropylidene) diphthalimide) hexafluoroisopropylidene) diphthalimide-co-3,5-benzoic acid-4,4 '- (hexafluoroisopropylidene) diphthalimide)) ( 6FDA-mPDA: DAM (3: 2)), poly (2,4,6-trimethyl-1,4-pentylene-4,4'- (hexafluoropropylidene) dipyrimid- Synthesis of poly (2,4,6-trimethyl-1,3-phenylene-4,4 '- (hexafluoroisopropylidene) diphthalimide-co- (6FDA-DAM: DABA (3: 2)) and poly (1,3-phenylene-4,4'- (hexafluorosopropylidene) diphthalimide) (1,3-phenylene-4,4 '- (hexafluoroisopropylidene) diphthalimide (diphenylphosphine) diphthalimide) (6FDA-mPDA: DABA (3: 2)), but the present invention is not limited thereto. Here, the ratio in parentheses represents the molar ratio of each polymer component.

In one preferred embodiment, the 6FDA-based polyimide may be 6FDA-DAM: DABA (3: 2) represented by the following formula 3a.

[Chemical Formula 3]

In the above formula (3a), n is an integer selected from 10 ² to 10 ⁴ .

The ladder-type polysilsesquioxane, which is another component of the hybrid polymer hollow fiber membrane according to the embodiment of the present invention, may have a structure represented by the following Chemical Formula 4.

[Chemical Formula 4]

Wherein R ₁ , R ₂ and R ₃ are each independently selected from the group consisting of aromatic phenyl, heteroaromatic phenyl, aliphatic alkyl, cyclic aliphatic alkyl, vinyl, aryl, methacrylate, acrylate, And n, m and l are integers selected from 0 to 100, respectively.

The molar ratio of R ₁ to R ₃ (that is, n: l) is 0.1: 99.9 to 99.9: 0.1, and m may be 0, as a copolymer proportion of the organic functional group of the ladder type polysilsesquioxane. Also, the molar ratio of R ₂ to R ₃ (i.e., m: l) is 0.1: 99.9 to 99.9: 0.1, and n may be 0.

Specifically, the R ₁ : R ₃ on the molar basis is 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, 50:50 to 70:30, 55:45 to 65: 35, and more specifically, the molar basis R ₁ : R ₃ may be about 6: 4. Where m can be zero. The molar ratio of R _{2 to} R ₃ is in the range of 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, 50:50 to 70:30, 55:45 to 65:35 Range, and more specifically the molar basis of R ₂ : R ₃ may be about 6: 4. Where n can be zero.

The molar ratio of R ₁ : R ₂ : R ₃ (ie, n: m: l) may preferably be about 3: 3: 4, 3: 4: 3, or 4: 3: But is not limited to a ratio.

The number average molecular weight of polysilsesquioxane may be from 10 ² to 10 ⁸ g / mol, more specifically from 10 ³ to 10 ⁷ g / mol or from 10 ⁴ to 10 ⁶ g / mol.

For example, the ladder-type polysilsesquioxane may be a ladder-type poly (phenyl-co-methacryloxypropyl) silsesquioxane, a ladder-type poly (phenyl- (Phenyl-co-glycidoxypropyl) silsesquioxane, ladder-like poly (phenyl-co-pyridylethyl) silsesquioxane (ladder-structured poly co-pyridylethyl silsesquioxane, ladder-like poly (cyclohexyl-co-pyridylethyl) silsesquioxane, ladder-type poly (cyclohexyl- (Cyclohexyl-co-phenyl-co-pyridylethyl) silsesquioxane) and mixtures thereof. However, the ladder-type polysilsesquioxane is not limited thereto.

Preferably, the ladder-type polysilsesquioxane is a ladder-type poly (phenyl-co-methacryloxypropyl) silsesquioxane (LPMA64) having a molar ratio of R ₁ and R ₃ of 6: 4 4), ladder-type poly (phenyl-co-glycidoxypropyl) silsesquioxane (LPG64, see the following formula 4b) having a molar ratio of R ₁ and R ₃ of the formula (4) of R ₁ and R ₃ is 6: the ladder-type poly having a molar ratio of 4 (phenyl-co-pyridyl ethyl) silsesquioxane (LPPyr64; see formula 4c below), the R ₂ and R ₃ of the formula 46 (LCPyr 64; see Formula 4d below) and R ₁ , R _2, and R ₃ in Formula 4 have a molar ratio of 3: 3: 4 At least one selected from the group consisting of ladder-type poly (cyclohexyl-co-phenyl-co-pyridylethyl) silsesquioxane (LCPPyr334; Can.

[Chemical Formula 4a]

(4b)

[Chemical Formula 4c]

[Chemical formula 4d]

[Chemical Formula 4e]

The ladder-type polysilsesquioxane can be obtained by a hydrolysis-condensation reaction of a silane monomer by a known method. Specifically, the ladder-type polysilsesquioxane can be obtained by hydrolysis-condensation reaction of at least one member selected from the group consisting of (a) aliphatic monomers, (b) aromatic monomers and (c) .

Specifically, when the silane monomer is (propyl) trimethoxysilane, (3-bromopropyl) trimethoxysilane, (acetoxy) methyltrimethoxysilane ( (acetoxy) methyltrimethoxysilane, (cyclohexyl) trimethoxysilane, (phenyl) trimethoxysilane, ((chloromethyl) phenylethyl) trimethoxysilane (( chloromethyl) phenylethyl trimethoxysilane, 2- (2-pyridylethyl) trimethoxysilane, (3-glycidoxypropyl) trimethoxysilane ), (Methacryloxypropyl) trimethoxysilane, and (butenyltrimethoxysilane). The term &quot; (meth) acryloxypropyl &quot; However, the silane monomers capable of producing the ladder-type polysilsesquioxane are not limited thereto.

Preferably, the aliphatic silane monomers that can be used for the synthesis of the ladder-type polysilsesquioxane are (propyl) trimethoxysilane, (3-bromopropyl) trimethoxysilane, (Phenyl) trimethoxysilane represented by the following formula 5 (b), (((meth) acryloxypropyltrimethoxysilane, (2-pyridylethyl) trimethoxysilane, and the cross-linkable silane monomer may include at least one of (3) -Glycidoxypropyl) trimethoxysilane, (methacryloxypropyl) trimethoxysilane, and (butenyl) trimethoxysilane.

[Chemical Formula 5]

The hybrid polymer hollow fiber membrane according to the embodiment of the present invention may be produced by mixing the fluorine-containing glassy polymer and the ladder-type polysilsesquioxane in a weight ratio of 0.1: 99.9 to 99.9: 0.1, specifically 20: 80 to 90: , More specifically in a weight ratio of 70:30 to 95: 5. According to the mixing ratio of the fluorine-containing glassy polymer and the ladder-type polysilsesquioxane in the hybrid polymer hollow fiber membrane according to the embodiment of the present invention, the gas separation performance of the hybrid polymer hollow fiber membrane and the carbon molecular sieve hollow fiber membrane produced therefrom is controlled .

In general, the polymer separator does not have micropores in the selected layer, but a vacancy, that is, a free volume, is formed between the chains by the thermal fluctuation of the polymer chains, and the gas permeates through the free volume. Conventional polymer membranes, however, exhibit aging at which the permeability decreases over time and plasticization at which the selectivity to high-pressure condensable gas decreases.

On the other hand, in the case of the hybrid polymer hollow fiber membrane according to the embodiment of the present invention, the siloxane structure of the rigid double strand of the ladder-type polysilsesquioxane material added to the fluorine-containing polyimide matrix having a large free volume, (Ie, antiaging effect), and also plasticization (antiplasticization effect).

Meanwhile, the polymer hollow fiber membrane according to the embodiment of the present invention may have an outer diameter of 200 to 400 탆 and an inner diameter of 100 to 200 탆. Preferably, the outer diameter of the polymer hollow fiber membrane is 250 to 350 占 퐉 and the inner diameter is 120 to 180 占 퐉.

Preferably, the hybrid polymer hollow fiber membrane according to the embodiment of the present invention can be used as a precursor of the carbon molecular sieve hollow fiber membrane.

hybrid  Manufacturing method of polymer hollow fiber membrane

According to another embodiment of the present invention, there is provided a method of preparing a hybrid polymer hollow fiber membrane, comprising: (1) dissolving a fluorine-containing glassy polymer matrix and ladder-type polysilsesquioxane in an organic solvent to obtain a polymer solution; (2) spinning a polymer solution and a bore fluid through a spinneret to form a polymer hollow fiber membrane; (3) cooling the polymer hollow fiber membrane with a cooling medium; And (4) winding the polymer hollow fiber membrane.

Referring to FIG. 1, a process for producing a hybrid polymer hollow fiber membrane according to an embodiment of the present invention will be described.

First, in step (1), a fluorine-containing glassy polymer matrix and ladder-type polysilsesquioxane are dissolved in an organic solvent to obtain a polymer solution.

Details of the fluorine-containing glassy polymer matrix and the ladder-type polysilsesquioxane are as described above in connection with the hybrid polymer hollow fiber membrane.

The organic solvent is not particularly limited as long as it can dissolve the fluorine-containing glassy polymer matrix and the ladder-type polysilsesquioxane and can be removed thereafter. Preferably, the organic solvent is selected from the group consisting of N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), tetrahydrofuran (THF) chloride (MC), dimethyl sulfoxide (DMSO), and mixtures thereof.

The weight ratio of the fluorine-containing glassy polymer matrix dissolved in the organic solvent to the ladder-type polysilsesquioxane is 0.1: 99.9 to 99.9: 0.1, specifically 20:80 to 90:10, more specifically 70:30 to 95: . By controlling the weight ratio of the fluorine-containing glassy polymer matrix and the ladder-type polysilsesquioxane dissolved in the organic solvent, the gas separation performance of the hybrid polymer hollow fiber membrane and the carbon molecular sieve hollow fiber membrane produced therefrom can be controlled. For example, as the content of polysilsesquioxane increases, the permeability of carbon dioxide decreases while the selectivity of carbon dioxide / methane increases.

The ratio of the weight of the organic solvent to the total weight of the fluorine-containing glassy polymer matrix and the ladder-type polysilsesquioxane may be 0.1: 99.9 to 40: 60. Specifically, the solid content weight of the fluorine-containing glassy polymer matrix and the ladder-type polysilsesquioxane is 0.1% or more, 1% or more, , More than 5%, 10%, 15%, 20%, 25%, 30%, 35%, or 40% Less than 20%, less than 15%, less than 10%, less than 5%, less than 1%, or 0.1%. More specifically, the solids weight of the fluorine-containing glassy polymer matrix and the ladder-type polysilsesquioxane is 0.1 to 40%, preferably 1 to 40%, based on the total weight of the fluorine-containing glassy polymer matrix, ladder-type polysilsesquioxane, 30%, 5-20%, or 7-13%. If the total weight of the fluorine-containing glassy polymer matrix and the ladder-type polysilsesquioxane exceeds 40% of the total weight of the fluorine-containing glassy polymer matrix, ladder-type polysilsesquioxane and organic solvent, molding of the carbon molecular sieve hollow fiber membrane If it is less than 0.1%, the gas separation performance may be lowered.

Preferably, the polymer solution may comprise a non-solvent. At this time, the non-solvent may be selected from aliphatic alcohols such as methanol and ethanol, but is not limited thereto. The non-solvent plays a role in controlling the phase separation rate from the spinning tip to the solid phase through the air gap and the cooling medium. In order to perform this role, the non-solvent content in the polymer solution may generally be in the range of 10 to 20% by weight.

On the other hand, the polymer solution may contain at least one additive selected from the group consisting of lithium nitrate (LiNO ₃ ) and polyvinylpyrrolidone. Preferably, the polymer solution may contain lithium nitrate. Lithium nitrate is easily dissolved in water to help form a porous support, and it can also control the phase transfer rate of the polymer solution. The content of the additive in the polymer solution may be in the range of 0.1 to 10% by weight.

In step (2), the polymer solution is injected (radiated) together with the bore fluid through a spinneret to form a polymer hollow fiber membrane.

The bore fluid that is injected with the polymer solution may be a mixture of an organic solvent and a non-solvent. The organic solvent of the bore fluid may be at least one selected from the group consisting of N-methyl-2-pyrrolidone (NMP) and dimethylformamide (DMF), but is not limited thereto. The non-solvent water of the bore fluid may be used, but is not limited thereto. The weight ratio of the organic solvent to the non-solvent of the bore fluid may be in the range of 60:40 to 90:10, but is not particularly limited to this range.

The temperature of the polymer solution and the bore fluid, the temperature of the pump, and the temperature of the line during spinning are preferably maintained at 50 to 70 ° C, but the temperature is not particularly limited.

The flow rates of the polymer solution and the bore fluid are preferably maintained at 1.5 to 3.0 ml / min and 0.5 to 1.0 ml / min, respectively, but the flow rate is not particularly limited.

It is preferable to use a cylindrical tip having a diameter of 200 to 300 占 퐉 and an injection tip of a polymer solution having a diameter of 1,300 to 1,500 占 퐉, but the size is not particularly limited.

The volatilized solvent is evaporated while the radiated polymer yarn passes through the air gap, and a dense film is formed on the outer wall of the polymer hollow fiber. The height of the air gap may be, for example, 5 cm or more, 10 cm or more, or 20 cm or more, but is not particularly limited to this height. Generally, a dense film can be formed on the outer wall of the polymer hollow fiber due to the evaporation of the volatile solvent as the air gap is increased to a certain degree of air gap.

In step (3), the polymer hollow fiber membrane is cooled with a cooling medium.

At this time, deionized water is suitable as the cooling medium, but it is not particularly limited thereto. The temperature of the cooling medium is suitably from 25 to 50 DEG C, but is not particularly limited to this temperature.

During the passage of the polymer hollow fiber membrane through the cooling medium, the phase transition occurs by the exchange of the cooling medium such as water with the organic solvent, and a solid state hollow fiber membrane is obtained.

In step (4), the obtained solid polymer hollow fiber membrane is wound. For example, a solid polymer hollow fiber membrane can be wound on a take-up drum. The winding speed is preferably 10 to 20 m / min, but is not particularly limited to this speed.

The winding drum is partially immersed in a container containing deionized water at room temperature. Therefore, the polymer hollow fiber membrane can be immersed in deionized water for about 10 to 20 minutes while being wound around a winding drum.

Then, the polymer hollow fiber membrane may be cut to an appropriate length (for example, 20 to 50 cm) and immersed in separate deionized water for about 2 to 3 days to completely remove the solvent remaining in the polymer hollow fiber membrane. Thereafter, the polymer hollow fiber membrane in which the solvent was completely removed was subjected to a solvent exchange in a non-solvent manner such as methanol and hexane to remove remaining water and then exposed to air for one hour to remove hexane and then dried in an oven .

hybrid  Carbon molecular sieve hollow fiber membrane

The hybrid carbon molecular sieve hollow fiber membrane according to another embodiment of the present invention includes a glassy polymer matrix containing fluorine and a carbide of ladder type polysilsesquioxane.

Since the hybrid polymer hollow fiber membrane which is a precursor of the hybrid carbon molecular sieve hollow fiber membrane contains a fluorine-containing glassy polymer (specifically, fluorine-containing polyimide), when the polymer hollow fiber membrane is pyrolyzed ₃ ) or an etching gas such as hydrogen fluoride (HF).

On the other hand, the polysilsesquioxane can form a secondary bond containing a hydrogen bond with the fluorine-containing glassy polymer and can be homogeneously bonded or non-uniformly dispersed without hydrogen bonding. In the present specification, the term "secondary bond" Quot; means a bond between a molecule and a molecule. These secondary bonds include hydrogen bonds, van der Waals bonds, and are distinguished from primary bonds, which are bonds between elements, such as ionic bonds.

By using a hybrid polymer hollow fiber membrane in which a fluorine-containing polyimide matrix and ladder-type polysilsesquioxane are well mixed by secondary bonding such as hydrogen bonding as a precursor of a carbon molecular sieve hollow fiber membrane, the polymer hollow fiber membrane is thermally decomposed (That is, carbonization), the siloxane structure of the double-stranded double strand of the ladder-type polysilsesquioxane material delays the heat-induced relaxation of the polyimide polymer chain, and thus the pore structure of the porous support collapses And by keeping the thin selective layer accordingly, high transmittance of the carbon molecular sieve separating membrane can be realized.

The hybrid carbon molecular sieve hollow fiber membrane according to an embodiment of the present invention may include a selective layer having a thickness of 100 nm to 3 占 퐉. Specifically, the average thickness of the selective layer may be 200 nm to 2 占 퐉 or 300 nm to 2 占 퐉, and preferably 300 nm to 1 占 퐉.

The hybrid carbon molecular sieve hollow fiber membrane according to an embodiment of the present invention may include ultrafine pores having an average size of 1 Å or more and less than 7 Å. Specifically, the average size of the ultrafine pores may be between 4 Å and 7 Å. Alternatively, the carbon molecular sieve hollow fiber membranes may include micropores having an average size of less than 7 Å and micropores having an average size of 7 to 20 Å. In this case, the sizes of the ultrafine pores and micro pores can be measured by analyzing the carbon dioxide (CO ₂ ) adsorption results measured at a low temperature of the carbon molecular sieve hollow fiber membrane by the density functional theory.

Specifically, in the carbon molecular sieve hollow fiber membrane, the ultrafine pores and the micro pores may be contained in a volume or an area ratio of 0.1: 99.9 to 10.0: 90.0. The carbon molecular sieve hollow fiber membrane according to the embodiment of the present invention includes micropores having molecular sieve function in addition to micropores having high permeability of gas and has a double structure of micropores and ultrafine pores, Can be effectively separated.

The carbon molecular sieve hollow fiber membranes according to embodiments of the present invention can effectively separate gases having molecular size differences of, for example, from 0.1 A to 5 A. Specifically, the molecular size difference of the detachable gases is greater than 0.1 A, greater than 0.15 A, greater than 0.2 A, greater than 0.3 A, greater than 0.4 A, greater than 0.5 A, greater than 1 A, greater than 2 A, greater than 3 A, greater than 4 A Less than or equal to 5 Å and less than or equal to 4 Å, less than or equal to 3 Å, less than or equal to 2 Å, less than or equal to 1.5 Å, less than or equal to 1 Å, less than or equal to 0.8 Å, less than or equal to 0.6 Å, less than or equal to 0.5 Å, Less than or equal to 0.2 angstroms, and less than or equal to 0.1 angstroms.

The carbon molecular sieve hollow fiber membrane according to the embodiment of the present invention may have an outer diameter of 100 to 300 탆 and an inner diameter of 75 to 150 탆. Preferably, the carbon molecular sieve hollow fiber membrane has an outer diameter of 150 to 250 占 퐉 and an inner diameter of 80 to 130 占 퐉.

Preferably, the hybrid carbon molecular sieve hollow fiber membrane according to the embodiment of the present invention may be coated with poly (dimethylsiloxane) (PDMS). Hybrid carbon molecular sieve hollow fiber membranes coated with poly (dimethyl siloxane) can alleviate physical aging phenomena.

The carbon molecular sieve hollow fiber membranes according to one embodiment of the present invention may include gases selected from the group consisting of oxygen / nitrogen, carbon dioxide / carbon tetrachloride, carbon dioxide / nitrogen, nitrogen / carbon tetrachloride, propylene / propane, ethylene / They can be separated from each other. Preferably, the carbon molecular sieve hollow fiber membrane can be effectively used to separate propylene / propane from each other.

hybrid  Manufacturing method of carbon molecular sieve hollow fiber membrane

According to another embodiment of the present invention, there is provided a method for producing a hybrid carbon molecular sieve hollow fiber membrane, comprising the steps of: (1) dissolving fluorine-containing glassy polymer matrix and ladder-type polysilsesquioxane in an organic solvent to obtain a polymer solution; (2) spinning a polymer solution and a bore fluid through a spinneret to form a polymer hollow fiber membrane; (3) cooling the polymer hollow fiber membrane with a cooling medium; (4) winding the polymer hollow fiber membrane; And (5) pyrolyzing the polymer hollow fiber membrane.

The above steps (1) to (4) are substantially the same as the steps (1) to (4) described in the production method of the hybrid polymer hollow fiber membrane.

In step (5), the dried polymer hollow fiber membrane is pyrolyzed (i.e., carbonized).

The pyrolysis (i.e., carbonization) process of the polymer hollow fiber membrane will be described with reference to FIG. The dried polymer hollow fiber membrane is placed on a quartz plate in a quartz tube of a pyrolysis apparatus. Subsequently, an inert gas such as argon is continuously injected to raise the temperature to a temperature at which pyrolysis is possible. Preferably, from pyrolysis at room temperature to 250 ° C at 10 ° C / min, from 250 ° C to T _soaking (ie, final carbonization temperature) to 15 ° C at 3.85 ° C / min, T _soaking - from 15 ° C to T _soaking at 0.25 ° C / min And maintaining the temperature at the final carbonization temperature (T _soaking ) for 2 hours is not particularly limited to this pyrolysis condition. The final thermal decomposition temperature of the hybrid polymer hollow fiber membrane of the present invention is preferably 500 to 800 ° C. It is preferable to keep it at the final pyrolysis temperature for 1 to 2 hours.

In order to alleviate the physical aging phenomenon of the hybrid carbon molecular sieve hollow fiber membrane thus obtained, the method for producing the hybrid carbon molecular sieve hollow fiber membrane according to the embodiment of the present invention comprises coating the hybrid carbon molecular sieve with poly (dimethylsiloxane) (PDMS) The method comprising the steps of:

Specifically, heptane was added to a mixture of a poly (dimethylsiloxane) resin and a crosslinking agent (compound name) in a weight ratio of 9: 1 to prepare a coating precursor solution of 90 to 99 wt%, followed by stirring for 12 hours, Cross-linking. Dip the carbon molecular sieve hollow fiber membrane into this solution and take out after 5-10 minutes. Then, it is dried at room temperature for 30 to 60 minutes and then dried at 100 ° C under vacuum for 12 to 24 hours.

Example

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

Manufacturing example  1: Preparation of carbon molecular sieve hollow fiber membrane

20 g of 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 4.06 g of 2,4,6-trimethyl-1,3- A mixture of 2,4,6-trimethyl-1,3-diaminobenzene (DAM) / 3,5-diaminobenzoic acid (DABA) (molar ratio 3: 2) N-methyl-2-pyrrolidone (NMP) was added to prepare a 20 wt% monomer solution. The mixture was stirred at about 5 ° C for 24 hours to obtain a high molecular weight polyamic acid solution. 4.3 g of? -Picoline and 43.2 g of acetic anhydride were added to the polyamic acid solution and imidized by stirring at room temperature for 24 hours. The precipitated polyimide (6FDA-DAM: DABA (3: 2)) was washed with methanol and dried at 180 캜 under vacuum for 24 hours to give 24.1 g of 6FDA-DAM: DABA (3: 2).

A 100 mL round bottom flask was charged with 0.04 g of potassium carbonate, 4.8 g of deionized water and 8 g of tetrahydrofuran (THF) to give a clear solution. To this, 9.52 g of phenyltrimethoxysilane and 7.27 g of 2- (2-pyridylethyl) trimethoxysilane were added dropwise under nitrogen. The reaction mixture was vigorously stirred for 5 days. After the volatiles were evaporated, the white dendritic portion was dissolved in 100 mL of dichloromethane and extracted several times with water. The organic material was collected, dried over anhydrous magnesium sulfate, filtered, and dichloromethane was evaporated to obtain 12.1 g of a white powder, LPPyr 64 (yield: 88%).

The above obtained 6FDA-DAM: DABA (3: 2) (Formula 3a) and LPPyr64 (Formula 4c) were mixed at a weight ratio of 80:20. This polymer mixture was dissolved in an organic solvent in which N-methyl-2-pyrrolidone (NMP) and lithium nitrate (LiNO ₃ ) were mixed. To this was added tetrahydrofuran (THF) and ethanol. Separately, a mixture of N-methyl-2-pyrrolidone (NMP) and water was prepared as a bore fluid. The content of each component constituting the polymer solution is as shown in Table 1 below. The composition of the bore fluid is shown in Table 2 below.

Polymer solution composition Weight portion 6FDA-DAM: DABA (3: 2) 23.0 LPPyr64 5.75 NMP 40.25 THF 10.0 ethanol 16.0 LiNO ₃ 5.0 Sum 100.0

Bohr fluid composition Weight portion NMP 80 water 20 Sum 100.0

In the ternary diagram of FIG. 4, the empty square (1) represents the phase boundary of the polymer mixture containing 6FDA-DAM: DABA (3: 2) and LPPyr 64 at a ratio of 80:20 , The hollow triangle (2) represents the upper boundary of 6FDA-DAM: DABA (3: 2), and the red square represents the polymer composition for disposal of Preparation Example 1. From this figure, it can be seen that the two substances are homogeneously mixed well due to the hydrogen bonding between the carboxyl group in 6FDA-DAM: DABA (3: 2) and the pyridyl group of LPPyr64.

The polymer solution and the non-solvent were spin-cast using the dry-jet / wet-process of FIG. 1 to prepare a hybrid polymer hollow fiber membrane. The spinning conditions are shown in Table 3 below. The outer diameter and inner diameter of the obtained polymer hollow fiber membrane were 320 탆 and 170 탆, respectively.

Polymer solution flow rate (ml / min) 1.5 Bore fluid flow rate (ml / min) 0.5 Air gap (cm) 15 Pump temperature (℃) 70 Line temperature (캜) 70 Spray temperature (℃) 70 Cooling medium temperature (캜) 50 Winding speed (m / min) 20

The polymer hollow fiber membrane was removed from the winding drum, cut to a length of about 30 cm, and soaked in deionized water for 3 days. At this time, deionized water was changed every day. The polymer hollow fiber membrane was then washed three times for 30 minutes with methanol and three times with hexane. Next, the polymer hollow fiber membrane was dried in air at room temperature for one hour and then dried at 75 DEG C under vacuum for 12 hours.

The dried polymer hollow fiber membrane was placed on a quartz plate (United Silica Products, USA) in a quartz tube (MTI, USA) and both ends of the quartz tube were sealed with a metal flange having a silicone o-ring. The pyrolysis unit was a 3-zone pyrolysis furnace (Thermcraft, USA) to accurately and uniformly control the temperature inside the tube. Argon was continuously injected into the quartz tube at a rate of 400 cm &lt; ³ &gt; / min, and the temperature was raised to a temperature at which pyrolysis was possible. At this time, the temperature and the heating rate are as shown in Table 4 below. The outer diameter and the inner diameter of the obtained carbon molecular sieve hollow fiber membrane were 220 탆 and 115 탆, respectively.

Initial temperature (℃) Final temperature (캜) Heating rate (° C / min) 50 250 13.3 250 650 3.85 660 660 0.25 675 675 Maintain for 2 hours

Manufacturing example  2: Preparation of plate-like carbon molecular sieve separator

5 g of a polymer prepared by mixing 6FDA-DAM: DABA (3: 2) and LPPyr64 in a weight ratio of 80:20 as used in Production Example 1 was completely dissolved in 95 g of tetrahydrofuran (THF). Subsequently, a film was prepared by a melt casting technique on a Teflon plate with a Teflon casting ring. In order to allow the solvent to evaporate slowly, the melt casting was carried out in a glove bag saturated with THF. After 12 hours, it was dried under vacuum at 12O &lt; 0 &gt; C for 12 hours to remove residual solvent of the vitrified film. The dried film was cut into a circular shape with a sharp die cutter hammered down to reduce cutting stress. The thickness of the produced film was uniformly 80 ± 10 μm. The obtained film was washed, dried and pyrolyzed in the same manner as in Production Example 1 to obtain a plate-like carbon molecular sieve separator.

Manufacturing example  3: PDMS  Preparation of coated carbon molecular sieve hollow fiber membranes

The carbon molecular sieve hollow fiber membrane obtained in Production Example 1 was coated with poly (dimethylsiloxane) (PDMS). Heptane was added to a mixture of a poly (dimethylsiloxane) resin (Sylgard 184A, Dow Corning) and a crosslinking agent (Sylgard 184B, Dow Corning) in a weight ratio of 9: 1 to prepare a coating solution of 99 wt% For a period of time. The carbon molecular sieve hollow fiber membrane is immersed in this solution, and taken out after 10 minutes. Then, it is dried at room temperature for 30 minutes and dried at 100 캜 under vacuum for 12 hours.

Experimental Example  1: Pore structure of polymer hollow fiber membrane and carbon molecular sieve hollow fiber membrane

5 is a photograph of a cross-section of a hybrid polymer hollow fiber membrane according to an embodiment of the present invention obtained in Production Example 1 and a carbon molecular sieve hollow fiber membrane obtained by the observation with a scanning electron microscope (SEM).

Both the polymer hollow fiber membrane and the carbon molecular sieve hollow fiber membrane were found to have a well-developed pore structure (Fig. 5 (a) and (d)). The inner diameter and outer diameter of the carbon molecular sieve hollow fiber membranes were reduced by 23% and 31%, respectively, compared with the inner diameter and outer diameter of the polymer hollow fiber membrane, the precursor thereof. In addition, it was confirmed that the carbon molecular sieve hollow fiber membrane had a selective layer of about 2.7 탆 thick (Fig. 5 (f)).

Thus, when the fluorine-containing glassy polymer is thermally decomposed, the polysilsesquioxane having a rigid double siloxane structure in the form of a ladder can retard the conversion of the chain of the fluorine-containing glassy polymer into the rubbery polymer, thereby maintaining the porous support form, It was confirmed that a carbon molecular sieve hollow fiber membrane having a high-density selective layer was produced.

Experimental Example  2: Gas permeability and selectivity of polymer hollow fiber membranes

Obtained in Production Example 1 using various single gases (for example, CO ₂ , O ₂ , N ₂ , CH ₄ , C ₃ H _{6, and} C ₃ H ₈ ) at 1 atm and 35 ° C. The gas separation performance of the hybrid polymer hollow fiber membrane according to the Example and the plate type polymer membrane according to Production Example 2 and the selectivities of O ₂ / N ₂ , CO ₂ / CH _4, and C ₃ H ₆ / C ₃ H ₈ were evaluated. The results are shown in Table 5. In Table 5, the single gas permeability of the polymer hollow fiber membranes is GPU unit, and the permeability of the flat polymer membranes is Barrer unit.

CO ₂ O ₂ N ₂ CH ₄ C ₃ H ₆ C ₃ H ₈ O ₂ / N ₂ CO ₂ / N ₂ CO ₂ / CH ₄ C ₃ H ₆ / C ₃ H ₈ Polymer hollow fiber membrane 148.04 36.68 5.64 4.43 3.26 0.25 6.5 26.3 33.4 13.0 Flat plate polymer membrane 97.32 - 3.11 2.13 2.13 0.18 - 23.4 30.1 11.8

Considering that the selectivity of the hybrid polymer hollow fiber membrane of Production Example 1 was similar to that of the plate polymer membrane of Production Example 2, it was found that a defect-free polymer hollow fiber membrane was produced.

Experimental Example  3: Polymer hollow fiber membrane My aging  Performance

On the other hand, under the same conditions as Experimental Example 2, the separation performance of the hybrid polymer hollow fiber membrane according to the embodiment of the present invention obtained in Production Example 1 was evaluated for 60 days, and the results are shown in Table 6.

CO ₂ Specularity (GPU) CO ₂ / CH ₄ selectivity Polymer hollow fiber membrane (0 day) 148.04 33.4 Polymer hollow fiber membrane (60 days) 135.81 34.1

In the case of the hybrid hollow fiber membrane according to the present invention, physical aging of the hollow fiber membrane was suppressed by the polysilsesquioxane having a rigid double siloxane structure in the form of a ladder, and it was confirmed that excellent carbon dioxide gas permeability was maintained even after 60 days of manufacture.

Experimental Example  4: Gas permeability and selectivity of polymer hollow fiber membrane and carbon molecular sieve hollow fiber membrane

Under the same conditions as Experimental Example 2, the carbon dioxide (CO ₂ ) permeability and CO ₂ / CH ₄ selectivity of the hybrid polymer hollow fiber membrane and the carbon molecular sieve hollow fiber membrane according to the embodiment of the present invention obtained in Production Example 1 were evaluated, The results are shown in Table 7.

CO ₂ Specularity (GPU) CO ₂ / CH ₄ selectivity Polymer hollow fiber membrane 148.04 33.4 Carbon molecular sieve hollow fiber membrane 956 50.2

The CO ₂ permeability and CO ₂ / CH ₄ selectivity of the carbon molecular sieve hollow fiber membranes increased by 546% and 50%, respectively, compared with the polymer hollow fiber membranes. This is understood to be due to the presence of a thin selective film formed on the surface of the carbon molecular sieve hollow fiber.

Experimental Example  5: Coating effect of carbon molecular sieve hollow fiber membrane

1 atmosphere, at 35 ℃ condition, Preparation Example 1 obtained uncoated carbon minutes from poly obtained in itself a hollow fiber membrane as in Preparation Example 3 (dimethyl siloxane) (PDMS) with carbon molecular CO ₂ dumping of its hollow fiber membranes coated with the help CO ₂ / CH ₄ selectivity was evaluated for 72 days, and the results are shown in FIG.

It was confirmed that the physical aging phenomenon over time was suppressed in the case of the hybrid carbon molecular sieve hollow fiber membrane coated with PDMS (see Fig. 6 (a)). Further, 50: 50 weight ratio of CO ₂ / CH ₄ The evaluation of the mixture of the hybrid carbon molecular sieve membrane using a mixture gas permeability, even though the CO ₂ partial pressure increases and the CO ₂ / CH ₄ selectivity does not decrease And thus it was confirmed that it had resistance to plasticization up to a partial pressure of CO ₂ of 13 atmospheres (see Fig. 6 (b)).

The hybrid polymer hollow fiber membrane and the carbon molecular sieve hollow fiber membrane according to the embodiment of the present invention are excellent in gas separation performance and selectivity and can have a large surface area per unit volume so that they are useful for separating gases with high energy efficiency and large capacity Can be used.

Claims (23)

A hybrid polymer hollow fiber membrane comprising a fluorine-containing glassy polymer matrix and ladder-type polysilsesquioxane. The hybrid polymer hollow fiber membrane according to claim 1, wherein the fluorine-containing vitreous polymer is a fluorine-containing polyimide obtained by condensation reaction of an aromatic carboxylic dianhydride and an aromatic diamine . The process according to claim 2, wherein the aromatic carboxylic acid dianhydride is 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride having a structure represented by the following formula (1). 6FDA). &Lt; / RTI &gt;
[Chemical Formula 1]

. 3. The process according to claim 2, wherein the aromatic diamine is 2,4,6-trimethyl-1,3-diaminobenzene having a structure represented by the following formula (2). DAM), 3,5-diaminobenzoic acid (DABA) having the structure represented by the formula 2 (b), 1,4-phenylenediamine (1 (3-phenylenediamine; m-PDA) having a structure represented by the formula (2) (d) , 3,5,6-tetramethyl-p-phenylenediamine (Durene), and mixtures thereof. The hybrid polymer hollow fiber membrane according to claim 1, :
(2)

. The polyimide according to claim 2, wherein the polyimide containing fluorine in the molecule is 2,6-bis (3,4-carboxyphenyl) hexafluoropropane dianhydride-based polyimide having a repeating unit represented by the following formula Hybrid polymer hollow fiber membrane characterized by:
(3)

Wherein R is a C _1-20 aliphatic alkyl containing or not containing fluorine; Alicyclic alkyl including monocyclic ring, dicyclic ring, heterocyclic ring or multicyclic; Or an aromatic ring. 6. The method of claim 5, wherein the 6FDA polyimide is selected from the group consisting of 6FDA-DAM, 6FDA-mPDA, 6FDA-DABA, 6FDA-DETDA, 6FDA: BPDA (1: 6FDA-DETDA: selected from the group consisting of DABA (3: 2), 6FDA-mPDA: DAM (3: 2), 6FDA-DAM: DABA Wherein the ratio in the parentheses is the molar ratio of each polymer component. [7] The hybrid polymer hollow fiber membrane according to claim 6, wherein the 6FDA-based polyimide is 6FDA-DAM: DABA (3: 2)
[Chemical Formula 3]

In the above formula (3a), n is an integer selected from 10 ² to 10 ⁴ . The hybrid polymer hollow fiber membrane according to claim 1, wherein the ladder-type polysilsesquioxane has a structure represented by the following Chemical Formula 4:
[Chemical Formula 4]

Wherein R ₁ , R ₂ and R ₃ are each independently selected from the group consisting of aromatic phenyl, heteroaromatic phenyl, aliphatic alkyl, cyclic aliphatic alkyl, vinyl, aryl, methacrylate, acrylate, And n, m and l are integers selected from 0 to 100, respectively. The method of claim 8, wherein the ladder-type polysilsesquioxane is selected from the group consisting of ladder-type poly (phenyl-co-methacryloxypropyl) silsesquioxane, ladder- Phenyl-co-glycidoxypropyl silsesquioxane, ladder-type poly (phenyl-co-pyridylethyl) silsesquioxane (ladder-structured poly phenyl-co-pyridylethyl) silsesquioxane, ladder-like poly (cyclohexyl-co-pyridylethyl) silsesquioxane, ladder-like poly (cyclohexyl- Phenyl-co-pyridylethyl) silsesquioxane), and mixtures thereof. The hybrid polymer hollow fiber membrane according to claim 1, wherein the polymeric hollow fiber membrane is selected from the group consisting of poly (phenyl-co-pyridylethyl) silsesquioxane and ladder-structured poly (cyclohexyl-co-phenyl-co-pyridylethyl) silsesquioxane. 10. The method according to claim 9, wherein the ladder-type polysilsesquioxane is ladder-like poly (phenyl-co-methacryloxypropyl) silsesquioxane (LPMA64) having a structure represented by the following Formula 4a, Ladder-type poly (phenyl-co-glycidoxypropyl) silsesquioxane (LPG64) having a structure represented by the following Chemical Formula 4c, ladder-type poly LPPyr64), ladder-type poly (cyclohexyl-co-pyridylethyl) silsesquioxane (LCPyr64) represented by the following Chemical Formula 4d and ladder-type poly (cyclohexyl-co- (LCPPyr 334). The hybrid polymer hollow fiber membrane according to claim 1,
[Chemical Formula 4a]

(4b)

[Chemical Formula 4c]

[Chemical formula 4d]

[Chemical Formula 4e]

. The hybrid polymer hollow fiber membrane according to claim 1, wherein the fluorine-containing vitreous polymer and the ladder-type polysilsesquioxane are contained in a weight ratio of 0.1: 99.9 to 99.9: 0.1. (1) a step of dissolving fluorine-containing glassy polymer matrix and ladder-type polysilsesquioxane in an organic solvent to obtain a polymer solution; (2) spinning a polymer solution and a bore fluid through a spinneret to form a polymer hollow fiber membrane; (3) cooling the polymer hollow fiber membrane with a cooling medium; And (4) winding the polymer hollow fiber membrane. 13. The method of claim 12, wherein the organic solvent of step (1) is selected from the group consisting of N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), tetrahydrofuran Wherein the polymer is selected from the group consisting of THF, methylene chloride (MC), dimethyl sulfoxide (DMSO), and mixtures thereof. 13. The method of claim 12, wherein the bore fluid of step (2) is a mixture of N-methyl-2-pyrrolidone (NMP) and water. 13. The method of claim 12, wherein the cooling medium in step (3) is deionized water. 11. A hybrid carbon molecular sieve hollow fiber membrane comprising a hybrid polymer hollow fiber membrane carbide according to any one of claims 1 to 11, comprising a fluorine-containing glassy polymer matrix and ladder-type polysilsesquioxane. 17. The hybrid carbon molecular sieve hollow fiber membrane according to claim 16, comprising a selective layer having an average thickness of 100 nm to 3 mu m. 17. The hybrid carbon molecular sieve hollow fiber membrane according to claim 16, comprising an ultramicropore having an average size of less than 1 Å and less than 7 Å, and a micropore having an average size of 7 to 20 Å. 19. The hybrid carbon molecular sieve hollow fiber membrane according to claim 18, wherein the ultrafine pores and the micropores are contained in a volume or area ratio of 0.1: 99.9 to 10.0: 90.0. 17. The hybrid carbon molecular sieve hollow fiber membrane according to claim 16, which is coated with poly (dimethylsiloxane) (PDMS). (1) a step of dissolving fluorine-containing glassy polymer matrix and ladder-type polysilsesquioxane in an organic solvent to obtain a polymer solution; (2) spinning a polymer solution and a bore fluid through a spinneret to form a polymer hollow fiber membrane; (3) cooling the polymer hollow fiber membrane with a cooling medium; (4) winding the polymer hollow fiber membrane; And (5) pyrolyzing the polymer hollow fiber membrane. The method for producing a hybrid carbon molecular sieve hollow fiber membrane according to claim 21, wherein the pyrolysis temperature in step (5) is 500 to 800 ° C. 22. The method of claim 21, further comprising coating the hybrid carbon molecular sieve with poly (dimethylsiloxane) (PDMS).

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