KR20170100857A - Method for preparation of hollow fiber membranes and hollow fiber membranes prepared thereby - Google Patents

Method for preparation of hollow fiber membranes and hollow fiber membranes prepared thereby Download PDF

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KR20170100857A
KR20170100857A KR1020160023250A KR20160023250A KR20170100857A KR 20170100857 A KR20170100857 A KR 20170100857A KR 1020160023250 A KR1020160023250 A KR 1020160023250A KR 20160023250 A KR20160023250 A KR 20160023250A KR 20170100857 A KR20170100857 A KR 20170100857A
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hollow fiber
fiber membrane
solution
solvent
gas separation
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남상용
박정호
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경상대학교산학협력단
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B01D69/087—Details relating to the spinning process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/02—Hollow fibre modules
    • B01D63/021—Manufacturing thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
    • B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B01D2325/022—Asymmetric membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/20—Specific permeability or cut-off range
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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    • Y02C20/20—Capture or disposal of greenhouse gases of methane

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Abstract

The present invention relates to a hollow fiber membrane for gas separation and a preparation method thereof. The hollow fiber membrane for gas separation in an asymmetric structure comprising polyimide-poly(ethylene glycol) copolymer is manufactured by using a phase-separation method so selectivity with respect to gas such as oxygen, nitrogen, carbon dioxide and methane, especially carbon dioxide can be improved.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hollow fiber membrane for gas separation and a hollow fiber membrane for gas separation,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a hollow fiber membrane for gas separation and a hollow fiber membrane for gas separation produced thereby. More particularly, the present invention relates to a method for manufacturing a hollow fiber membrane for separating gas including polyimide-polyethylene glycol copolymer The present invention relates to a technique for improving the selectivity to gases such as oxygen, nitrogen, carbon dioxide and methane, in particular, carbon dioxide by preparing an asymmetric structure gas separation hollow fiber membrane.

Due to climate change caused by global warming phenomenon, there is a sudden glacial loss of the world's largest ice cap, extreme weather such as extreme climate and heat, and international organizations such as WMO and UNEP cooperate and cope Is in the process of being. Global warming emits greenhouse gases such as methane, freon, and carbon dioxide. CO2 accounts for more than half of all greenhouse gases. Controlling large volumes of greenhouse gas emissions from each industry sector is a real challenge, so to mitigate this, it is necessary to isolate the air before it is released.

In general, cryogenic separation, adsorption, absorption, and membrane separation are mainly used for separating carbon dioxide. Here, the membrane separation method separates the gas according to the principle of separating the gas depending on the degree of dissolution of the gas into the inside of the membrane and the degree of diffusion in the membrane. Polymer materials such as polysulfone are most widely used for practical purposes, and porous separators having a dense selective separation layer on the membrane surface and a minimum permeation resistance on the bottom of the membrane It is reported that it is preferable to produce the asymmetric structure.

As a method for producing a polyimide-polyethylene glycol copolymer separation membrane for separating carbon dioxide as such a gas separation membrane, there has been disclosed a technique for preparing a separation membrane by pouring a polyimide-polyethylene glycol copolymer onto a Petri dish and drying the membrane. (Patent Document 1).

A technique has also been developed for preparing a hollow composite membrane for carbon dioxide / methane separation by using an organopolysiloxane copolymer in which repeating units grafted with polyethylene glycol or polyethylene / propylene glycol are grafted onto the surfaces of the glassy polymer and the hollow fiber membrane by spinning (Patent Document 2).

On the other hand, a phase transfer method has been used as a method for manufacturing an asymmetric gas separation membrane. However, studies have been continued to make the cross section of the asymmetric gas separation membrane more compact.

For example, an additive may be added to the separator by the phase transfer method. For example, a method of producing a polyetherimide gas separator using glycerol as an additive in the phase transfer method has been developed (Non-Patent Document 1).

Polyimide-polyethylene glycol copolymers are attracting attention as a material for gas separation membranes for separating carbon dioxide, but polyethylene glycol is contained in the polymer chain of the copolymer, and a gas separation membrane can not be produced by the phase transfer method.

Accordingly, the present inventors have found that when a phase transfer method is employed in the production of a polyimide-polyethylene glycol copolymer hollow fiber membrane for gas separation, the polyimide-polyethylene glycol copolymer hollow fiber membrane for gas separation having a densely formed asymmetric structure The present invention has been completed in view of the fact that the selectivity to carbon dioxide can be improved.

Korean Patent Publication No. 10-2015-0044713 Korean Patent Publication No. 10-2014-0014905

 Jung, Jae Jae et al .; Proceedings of the Membrane Society of Korea Conference, 1997; Oct. 01, 1997, pp.94-95

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide an asymmetric structure capable of improving selectivity for gases such as oxygen, nitrogen, carbon dioxide and methane, A hollow fiber membrane for gas separation and a method of manufacturing the same.

In order to accomplish the above object, the present invention provides a polyimide resin composition comprising (I) (i) a polyimide-polyethylene glycol copolymer; (ii) a solvent; (iii) co-solvent; And (iv) a normal phase;

(II) supplying a first coagulating liquid for forming a hollow fiber and the mixed solution to an inner spinning nozzle and an outer spinning nozzle of the double spinning nozzle, and simultaneously discharging the mixed solution from the double spinning nozzle to obtain a hollow fiber solution; And

(III) exposing the hollow fiber solution to air, and then dipping the hollow fiber membrane into a second coagulating solution for forming a hollow fiber membrane to form a hollow fiber membrane.

The method for producing a hollow fiber membrane for gas separation may further comprise the step of (IV) washing and drying the hollow fiber membrane to obtain a hollow fiber membrane.

The polyimide-polyethylene glycol copolymer (i) is characterized by being represented by the following formula (1)

≪ Formula 1 >

Figure pat00001

Wherein n is an integer of 100 to 3000 in terms of the number of repeating units according to the molecular weight of polyethylene glycol, x and y are x + y = 1, x is a real number of 0.75 to 0.98 and y is a real number of 0.02 to 0.25 .

(Ii) the solvent is at least one organic solvent selected from N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc) and dimethylformamide (DMF).

(Iii) the cosolvent is one or more volatile solvents selected from tetrahydrofuran (THF), ethyl acetate and acetone.

And (iii) the co-solvent has a boiling point of 50 to 80 ° C.

(Iv) The phase transition is characterized by being at least one lithium compound selected from lithium chloride (LiCl), lithium nitrate (LiNO 3 ) and lithium sulfate (LiSO 4 ).

15 to 40% by weight of the (i) polyimide-polyethylene glycol copolymer; (ii) 30 to 83 wt% solvent; (iii) 1 to 20% by weight of a co-solvent; And (iv) 1 to 10% by weight of a phase transition is now obtained.

And the temperature of the double spinning nozzle is 30 to 70 ° C.

The first coagulating liquid for forming a hollow fiber is heated to 30 to 50 캜 and supplied to the inner spinning nozzle.

And exposing the hollow fiber solution to air while the hollow fiber solution discharged from the double spinning nozzle is transferred to the coagulation bath supporting the second coagulating solution for forming a hollow fiber membrane.

The first coagulation solution for forming a hollow fiber is at least one selected from the group consisting of ultrapure water, a mixture of ultrapure water and organic solvent, and alcohol. The organic solvent is selected from the group consisting of N-methyl-2-pyrrolidone (NMP), dimethylacetamide ) And dimethylformamide (DMF).

The second coagulating liquid for forming the hollow fiber membrane is at least one selected from water and alcohol, and the alcohol is at least one selected from methanol, ethanol and isopropyl alcohol.

The present invention also provides a polyimide-polyethylene glycol copolymer hollow fiber membrane for gas separation having an asymmetric structure comprising a porous support layer for gas permeation and a selective layer for gas separation formed on the support layer, do.

According to the present invention, it is possible to produce a polyimide-polyethylene glycol copolymer hollow fiber membrane for gas separation having an asymmetric structure in which the surface of the membrane is densely formed by a phase transfer method.

In addition, the polyimide-polyethylene glycol copolymer hollow fiber membrane for gas separation can control the selectivity and permeability to gases such as oxygen, nitrogen, carbon dioxide and methane, in particular, carbon dioxide, Effect.

1 is a schematic view of a symmetrical structure (a) and an asymmetric structure (a), respectively, as longitudinal sections of a separation membrane.
FIG. 2 is a graph of thermogravimetric analysis (TGA) of the polyimide-polyethylene glycol copolymer synthesized in Synthesis Example 1. FIG.
3 is an SEM sectional view of the hollow fiber membrane for gas separation prepared in Example 1. Fig.
Fig. 4 is a schematic view of a gas permeation amount measuring instrument (a) and a foam flow meter (b).

Hereinafter, a method of manufacturing a hollow fiber membrane for gas separation according to the present invention will be described in detail with reference to the accompanying drawings.

1 is a schematic view of a symmetrical structure (a) and an asymmetric structure (a), respectively, as longitudinal sections of a separation membrane.

As shown in FIG. 1 (a), the symmetrical structure of the separation membrane means that the longitudinal section of the separation membrane has a uniform structure as a whole.

1 (b), the "asymmetric structure" of the hollow fiber membrane 10 for gas separation used in the present invention is a structure in which the longitudinal section of the separation membrane 10 is the supporting layer 11, the support layer 11, And a selective layer (12) formed on the substrate. The selective layer 12 is formed on the surface of the separation membrane 10 and has a dense structure composed of micropores capable of selectively separating gas particles. The support layer 11 includes relatively large pores, The transmittance can be improved.

(I) a polyimide-polyethylene glycol copolymer; (ii) a solvent; (iii) co-solvent; And (iv) a normal phase;

(II) supplying a first coagulating liquid for forming a hollow fiber and the mixed solution to an inner spinning nozzle and an outer spinning nozzle of the double spinning nozzle, and simultaneously discharging the mixed solution from the double spinning nozzle to obtain a hollow fiber solution; And

(III) exposing the hollow fiber solution to air, and then dipping the hollow fiber membrane into a second coagulation solution for forming a hollow fiber membrane to form a hollow fiber membrane.

The polyimide-polyethylene glycol copolymer (i) may be represented by the following general formula (1).

≪ Formula 1 >

Figure pat00002

Wherein n is an integer of 100 to 3000 in terms of the number of repeating units according to the molecular weight of polyethylene glycol, x and y are x + y = 1, x is a real number of 0.75 to 0.98 and y is a real number of 0.02 to 0.25 .

If x is less than 0.75, the y value becomes relatively large, so that the phase separation does not occur and the gas separation membrane can not be produced even though the phase transition is used. If it exceeds 0.98, the selectivity of the gas may be significantly lowered.

If y is less than 0.02, the selectivity of the gas may be significantly deteriorated. If y is more than 0.25, the phase transition may not occur and the gas separation membrane may not be produced.

The weight of the polyimide-polyethylene glycol copolymer (i) may be from 15 to 30% by weight based on the total weight of the mixed solution, and if it is less than 15% by weight, the content of the copolymer in the mixed solution is low, It may be difficult to serve as a gas separation membrane due to a large amount of defects on the surface of the hollow fiber membrane. If it exceeds 30% by weight, the mixed solution may not be formed into a single phase and may not be radiated in the step (II) have.

The solvent (ii) is not evaporated when the hollow fiber solution is exposed to air in the step (III), and when the hollow fiber solution is immersed in the second coagulation solution for forming a hollow fiber membrane, (Ii) the solvent in the solution is exchanged with the second coagulating solution so that the (ii) solvent is replaced with the second coagulating solution in the solution, and the second coagulating solution is easily removed to form a solid-phase hollow fiber membrane have. Particularly, in the hollow fiber solution, (ii) the portion where the solvent has escaped can form a large pore to form a supporting layer of the asymmetric structure of the hollow fiber membrane.

Therefore, it is preferable that the (ii) solvent exhibits high affinity to the second coagulating solution while dissolving the (i) polyimide-polyethylene glycol copolymer, and the second coagulating solution is, for example, , It is preferable that the (ii) solvent has a high affinity with water.

The solvent (ii) may be one or more organic solvents selected from N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc) and dimethylformamide (DMF) -Polyethylene glycol copolymer can be widely used as an organic solvent having high solubility.

The weight of the solvent (ii) may be 40 to 83% by weight based on the total weight of the mixed solution. If the amount of the solvent is less than 40% by weight, the copolymer can not be sufficiently dissolved, %, The viscosity of the mixed solution may be low and the hollow fiber membrane may not be produced.

In addition, (iii) the cosolvent may be one or more volatile solvents selected from tetrahydrofuran (THF), ethyl acetate and acetone.

Since the cosolvent (iii) is a volatile solvent, the hollow fiber solution may be rapidly evaporated from the surface of the hollow fiber when the hollow fiber solution is exposed to air in the step (III). At this time, when the asymmetric hollow fiber membrane including the support layer and the selective layer formed on the surface of the hollow fiber with a relatively high concentration of the copolymer is formed, the selective layer can be formed hard and densely.

The weight of the cosolvent (iii) may be from 1 to 20% by weight based on the total weight of the mixed solution. If it is less than 1% by weight, it may be difficult to form a selective layer having an asymmetric structure. Layer, the thickness of the selective layer becomes thick, so that surface defects of the hollow fiber membrane are not generated, but the gas permeability may be lowered.

Accordingly, the co-solvent of (iii) may have a boiling point of 50 to 80 ° C, and when the co-solvent has a boiling point of less than 50 ° C, evaporation is not sufficient when the hollow fiber is exposed to air in the step (III) The selective layer can not be formed. If the temperature is higher than 80 DEG C, the first coagulant is vaporized in the step (II), so that bubbles are generated and it is difficult to form a hollow fiber membrane.

The (iv) phase transition may be at least one lithium compound selected from lithium chloride (LiCl), lithium nitrate (LiNO 3 ) and lithium sulfate (LiSO 4 ).

In the step (iv), the copolymer in the mixed solution is allowed to undergo phase transition to the hollow fiber so that the hollow fiber can be formed when the hollow fiber solution is obtained by discharging the mixed solution after discharging the mixed solution in the step (II).

The weight of the (iv) phase transition may be 1 to 10% by weight based on the total weight of the mixed solution. When the amount of the phase transition is less than 1% by weight, the phase transition to the hollow fiber itself does not occur, %, It may be difficult to obtain a mixed solution of a single phase in the step (I), so that the step (II) may not be carried out.

In the step (II), the first coagulating liquid for forming a hollow fiber and the mixed solution are supplied to the inner spinning nozzle and the outer spinning nozzle of the double spinning nozzle, respectively, and then discharged and discharged to obtain a hollow fiber solution. The first coagulating liquid for forming a hollow fiber can be supplied to the inner spinning nozzle using a pump, and the mixed solution can be supplied to the outer spinning nozzle using a gear pump after deaeration, To obtain a hollow fiber solution.

The diameter of the cross section of the hollow fiber contained in the hollow fiber solution may be 300 to 400 탆.

At this time, the double spinning nozzle may be maintained at a temperature of 50 to 70 ° C to form a dense layer by rapidly volatilizing the solvent in the hollow fiber solution supplied to the double spinning nozzle.

The first coagulating liquid for forming a hollow fiber plays a role of becoming a hollow fiber after the phase of the mixed solution is transformed. The first coagulating liquid for forming the hollow fiber is a mixture of ultrapure water, a mixture of ultrapure water and an organic solvent, And the like.

The organic solvent may be one or more selected from N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc) and dimethylformamide (DMF), and the alcohol may be at least one selected from the group consisting of methanol, ethanol, isopropyl alcohol It may be at least one selected.

The first coagulating liquid for forming a hollow fiber may be heated to 30 to 50 캜 to be supplied to the inner spinning nozzle so that the inner air bubbles can be removed.

In the step (III), the hollow fiber solution may be exposed to air and then immersed in a second coagulant for forming a hollow fiber membrane to form a hollow fiber membrane.

At this time, the hollow fiber solution may be exposed to the air while the hollow fiber solution discharged from the double spinning nozzle is transferred to the coagulation bath in which the second coagulation solution for forming a hollow fiber membrane is carried.

The distance from the double spinning nozzle to the coagulation bath may be referred to as an air gap, and the air gap may be 10 to 30 cm.

While the hollow fiber solution discharged from the double spinning nozzle is being transported by the distance of the air gap and exposed to the air, the volatile copolymer (iii) evaporates to increase the concentration of the copolymer on the surface of the hollow fiber, And a selective layer formed on the support layer, the selective layer can be formed firmly and densely when the hollow fiber membrane is formed.

The hollow fiber solution transferred by the distance of the air gap is immersed in the second coagulating solution for forming a hollow fiber membrane, and the solvent (i) in the hollow fiber solution is discharged into the second coagulating solution for forming a hollow fiber membrane (I) a large pore is formed in the place where the solvent is exited to form a support layer having an asymmetric layer structure.

As a result, an asymmetric hollow fiber membrane including a selective layer formed when the hollow fiber solution is exposed to air and a support layer formed by immersing the hollow fiber solution in the second coagulation solution for forming a hollow fiber membrane can be obtained.

At this time, the second coagulating solution for forming the hollow fiber membrane plays a role of forming a hollow fiber membrane form, and the second coagulating solution for forming the hollow fiber membrane is at least one selected from water and alcohol, Methanol, ethanol, and isopropyl alcohol.

Thereafter, in the step (IV), the asymmetric hollow fiber membrane may be washed to remove the residual solvent and then wound. In addition, the asymmetric hollow fiber membrane may be subjected to hydrothermal treatment to remove remaining fine solvent, followed by drying.

As described above, (iv) a polyimide-polyethylene glycol copolymer for gas separation having an asymmetric structure comprising a porous support layer for gas permeation and a selective layer for gas separation formed on the support layer by a phase transfer method using phase transition A hollow fiber membrane can be produced.

Also, a polyimide-polyethylene glycol copolymer hollow fiber membrane for separating carbon dioxide having the asymmetric structure comprising a porous support layer for permeation of carbon dioxide and a selective layer for separating carbon dioxide formed on the support layer may be prepared.

By the phase transfer method as described above, a hollow fiber membrane for gas separation comprising a polyimide-polyethylene glycol copolymer represented by the following general formula (1) can be produced.

≪ Formula 1 >

Figure pat00003

N is an integer of 100 to 3000, x and y are x + y = 1, x is a real number of 0.75 to 0.98, and y is a real number of 0.02 to 0.25.

In Formula 1, n is the number of repeating units according to the molecular weight of polyethylene glycol, and x and y are mole fractions of duren and polyethylene glycol used in the preparation of the copolymer.

The polyimide-polyethylene glycol copolymer represented by Formula 1 is obtained by reacting a diamine containing a Durene group with 6FDA (2,2'-bis- (3,4-dicarboxyphenyl) hexafluoropropanediamine hydrate) (Polyethylene glycol (PEG)) into polyimide (PI).

In other words, the polyimide-polyethylene glycol copolymer represented by the above formula (1) may be a polycondensate prepared by condensation polymerization of the diamine containing the durene group, the polyethylene glycol and the 6FDA.

The diamine containing the durenne group may be represented by the following formula (2), the polyethylene glycol may be represented by the following formula (3), and the 6FDA may be represented by the following formula (4).

(2)

Figure pat00004

(3)

Figure pat00005

In the above formula, n is an integer of 100 to 3000.

≪ Formula 4 >

Figure pat00006

The weight average molecular weight of the polyimide-polyethylene glycol copolymer represented by Formula 1 may be 130,000 to 300,000 Mw.

The gas separation hollow fiber membrane may selectively separate gas from at least two mixed gases selected from oxygen, nitrogen, carbon dioxide, and methane, and in particular, may be advantageous for selectively separating the carbon dioxide from the gas mixture containing carbon dioxide .

Hereinafter, embodiments and comparative examples according to the present invention will be described in detail.

[Synthesis Example 1] Synthesis of polyimide-polyethylene glycol (PI-PEG-0.05) copolymer

24.58 g of 2,3,5,6-tetramethyl-1,4-phenylenediamine (Durene) of the above formula 2; 11.81 g of the poly (ethyleneglycol) bis (3-aminopropyl) terminated PEG (number average molecular weight = ~ 1500 g / mol) of the above formula 3 was dissolved in 1000 ml four- After adding 425.6 ml (20 wt%) of dimethylacetamide (DMAc) into the flask, the monomers were completely dissolved at room temperature with a mechanical stirrer while continuously flowing nitrogen. After cooling to 0 ° C, 70 g of 2,2'-bis- (3,4-dicarboxylphenyl) hexafluoropropanediamine hydrate and 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride of Formula 4 And then reacted at room temperature for 12 hours.

To the chemical imidization reaction, 63.78 g and 64.35 g of triethylamine (TEA) and acetic anhydride were respectively dropped at 50 ° C and reacted at 120 ° C for 3 hours.

The prepared viscous polymer solution was precipitated in methanol, washed several times, and dried in a vacuum oven at 60 ° C. for 48 hours to synthesize a PI-PEG copolymer (FIG. 2).

Synthesis Example 2 Synthesis of Polyimide-Polyethylene Glycol (PI-PEG-0.10) Copolymer

2,3,5,6-Tetramethyl-1,4-phenylenediamine (Durene) 23.29 of Formula 2 was obtained in the same manner as in Synthesis Example 1, g; 23.65 g of poly (ethyleneglycol) bis (3-aminopropyl) terminated PEG (number average molecular weight = 1500 g / mol) of the above formula (3), 23.65 g of dimethylacetamide ) Was synthesized by using 467.6 ml.

[ Synthetic example  3] polyimide- Polyethylene glycol ( PI - PEG -0.20) Copolymer Synthesis

(2,3,5,6-Tetramethyl-1,4-phenylenediamine, Durene) of Formula 2 was carried out in the same manner as in Synthesis Example 1, g; 47.27 g of poly (ethyleneglycol) bis (3-aminopropyl) terminated PEG (number average molecular weight = 1500 g / mol) represented by Formula 3, 47.27 g of dimethylacetamide (DMAc ) Were synthesized using 551.9 ml of distilled water.

[Synthesis Example 4] Synthesis of polyimide-polyethylene glycol (PI-PEG-0.03) copolymer

2,3,5,6-Tetramethyl-1,4-phenylenediamine (Durene) 25.10 (2) was prepared in the same manner as in Synthesis Example 1, g; 7.09 g of poly (ethyleneglycol) bis (3-aminopropyl) terminated PEG (number average molecular weight =? 1500 g / mol) of Formula 3, ).

[Synthesis Example 5] Synthesis of polyimide-polyethylene glycol (PI-PEG-0) copolymer

2,3,5,6-Tetramethyl-1,4-phenylenediamine (Durene) 25.88 of Formula 2 was performed in the same manner as in Synthesis Example 1 g; 0 g of poly (ethyleneglycol) bis (3-aminopropyl) terminated PEG (number average molecular weight = 1500 g / mol) represented by the above formula 3 and 50 g of dimethylacetamide (DMAc ) Was synthesized by using 385.3 ml.

[Synthesis Example 6] Synthesis of polyimide-polyethylene glycol (PI-PEG-4) copolymer

2,3,5,6-Tetramethyl-1,4-phenylenediamine (Durene) 25.10 (2) was prepared in the same manner as in Synthesis Example 1, g; 7.09 g of poly (ethyleneglycol) bis (3-aminopropyl) terminated PEG (number average molecular weight =? 1500 g / mol) of Formula 3, ).

Example 1

Synthesized in the above Synthesis Example 1 (i) PI-PEG copolymer of 20% by weight, (ii) dimethylacetamide (DMAc) 67 wt%, (iii) Tra tetrahydrofuran (THF) 10 wt% and (iv) LiNO 3 3 wt% of a mixed solution was obtained.

The mixed solution was placed in a tank in which a gear pump was connected for 24 hours to remove bubbles and then transferred to a double spinning nozzle maintained at 70 ° C. Then, distilled water heated to 40 ° C as a first coagulation liquid for forming a hollow fiber was supplied to the internal spinning nozzle of the double spinning nozzle at a uniform rate of 1.5 cc / min, and the mixed solution was supplied to an external spinning nozzle, A hollow fiber solution containing a hollow fiber formed by phase transfer from the double spinning nozzle was obtained.

After fixing the distance between the double spinning nozzle and the coagulation tank carrying the second coagulating solution for hollow fiber membrane formation, that is, the air gap at 30 cm, the hollow fiber solution discharged from the double spinning nozzle was pumped into the air Exposed and immersed in the second coagulating solution for forming a hollow fiber membrane to form a hollow fiber membrane, washed, and then wound.

The wound hollow fiber membrane was hydrothermally treated and then dried at room temperature for 24 hours to produce a hollow fiber membrane for gas separation (FIG. 3).

Example 2

(I) 20 wt% of the PI-PEG copolymer synthesized in Synthesis Example 1, (ii) 57 wt% of dimethylacetamide (DMAc), (iii) tetrahydrofuran (THF ), And (iv) 3 % by weight of LiNO 3 were mixed to prepare a hollow fiber membrane for gas separation.

Example 3

(Ii) 72% by weight of dimethylacetamide (DMAc), (iii) tetrahydrofuran (THF) in the same manner as in Example 1 except that 20% by weight of the PI- ), And (iv) 3 % by weight of LiNO 3 were mixed to prepare a hollow fiber membrane for gas separation.

Example 4

(Ii) 76% by weight of dimethylacetamide (DMAc), (iii) tetrahydrofuran (THF) in the same manner as in Example 1 except that 20% by weight of the PI- ), And (iv) 3 % by weight of LiNO 3 , to prepare a gas separation hollow fiber membrane.

Example 5

(I) 23 wt% of the PI-PEG copolymer synthesized in Synthesis Example 1, (ii) 64 wt% of dimethylacetamide (DMAc), (iii) tetrahydrofuran (THF ), And (iv) 3 % by weight of LiNO 3 were mixed to prepare a hollow fiber membrane for gas separation.

Example 6

(I) 25 wt% of the PI-PEG copolymer synthesized in Synthesis Example 1, (ii) 62 wt% of dimethylacetamide (DMAc), (iii) tetrahydrofuran (THF ), And (iv) 3 % by weight of LiNO 3 were mixed to prepare a hollow fiber membrane for gas separation.

Example 7

The hollow fiber membrane for gas separation was prepared in the same manner as in Example 4 except that the polymer synthesized in Synthesis Example 2 was used.

Example 8

The hollow fiber membrane for gas separation was prepared in the same manner as in Example 4 except that the polymer synthesized in Synthesis Example 3 was used.

Example 9

The hollow fiber membrane for gas separation was prepared in the same manner as in Example 4 except that the polymer synthesized in Synthesis Example 4 was used.

Comparative Example 1

(I) 40 wt% of the PI-PEG copolymer synthesized in Synthesis Example 1, (ii) 47 wt% of dimethylacetamide (DMAc), (iii) tetrahydrofuran (THF ) And (iv) 3 wt% of LiNO 3 .

Comparative Example 2

The same procedure as in Example 1 was carried out except that the temperature of the double spinning nozzle was kept at 25 캜.

Comparative Example 3

(I) 20 wt% of the PI-PEG copolymer synthesized in Synthesis Example 1, (ii) 55 wt% of dimethylacetamide (DMAc), (iii) tetrahydrofuran (THF ) And (iv) 15 wt% of LiNO 3 .

Comparative Example 4

(I) 20 wt% of the PI-PEG copolymer synthesized in Synthesis Example 1, (ii) 70 wt% of dimethylacetamide (DMAc), (iii) tetrahydrofuran (THF ) Was 10% by weight, and (iv) LiNO 3 was not used.

Comparative Example 5

The hollow fiber membrane for gas separation was prepared in the same manner as in Example 4 except that the PI-PEG copolymer synthesized in Synthesis Example 5 was used.

Comparative Example 6

The hollow fiber membrane for gas separation was prepared in the same manner as in Example 4 except that the PI-PEG copolymer synthesized in Synthesis Example 6 was used.

The following Table 1 shows the changes in the amounts of 2,3,5,6-tetramethyl-1,4-phenylenediamine of Formula 2 and poly (ethylene glycol) bis (3-aminopropyl) (1), wherein the poly (ethylene glycol) bis (3-aminopropyl) amine represented by the formula (1) is obtained by reacting 2,3,5,6-tetramethyl- ) In the formula (1).

(2) (3) PI-PEG copolymer (Formula 1) x y Synthesis Example 1 24.58 g 11.81 g 0.95 0.05 Synthesis Example 2 23.29 g 23.65 g 0.90 0.10 Synthesis Example 3 20.75 g 47.27 g 0.80 0.20 Synthesis Example 4 25.10 g 7.09 g 0.97 0.03 Synthesis Example 5 25.88 g 0 g 1.0 0 Synthesis Example 6 15.52 g 94.54 g 0.6 0.4

The gas permeability was measured by using nitrogen and carbon dioxide as a single gas for the gas separation hollow fiber membranes prepared in Examples and Comparative Examples in the compositions shown in Tables 2 and 3 below.

The gas permeability was measured by the following equation (1) using the flow rate measured using the gas permeability measuring instrument and the foam flow meter shown in FIG. 4, and the results are shown in Table 3. The gas permeability unit is G.P.U (Gas Permeation Unit, 10).

≪ Formula 1 >

Gas permeability = 1 x 10 6 x [measured flow rate / (unit time x membrane area x measured pressure)]

The CO 2 / N 2 selectivity is also calculated as the ratio of CO 2 gas permeability to N 2 gas permeability.

division Used polymer PI-PEG copolymer
(weight%) menstruum
(weight%) Quiet
(weight%) Now,
(weight%) Double spinning nozzle temperature (℃) Example 1 Synthesis Example 1 20 67 10 3 70 Example 2 Synthesis Example 1 20 57 20 3 70 Example 3 Synthesis Example 1 20 72 5 3 70 Example 4 Synthesis Example 1 20 76 One 3 70 Example 5 Synthesis Example 1 23 64 10 3 70 Example 6 Synthesis Example 1 25 62 10 3 70 Example 7 Synthesis Example 2 20 76 One 3 70 Example 8 Synthesis Example 3 20 76 One 3 70 Example 9 Synthesis Example 4 20 76 One 3 70 Comparative Example 1 Synthesis Example 1 40 47 10 3 70 Comparative Example 2 Synthesis Example 1 20 67 10 3 25 Comparative Example 3 Synthesis Example 1 20 55 10 15 70 Comparative Example 4 Synthesis Example 1 20 70 10 0 70 Comparative Example 5 Synthesis Example 5 20 76 One 3 70 Comparative Example 6 Synthesis Example 6 20 76 One 3 70

division N 2 transmittance CO 2 permeability CO 2 / N 2 selectivity Other Example 1 2.17 46.2 21.2 Example 2 0.844 25.32 30 Example 3 2.42 57.2 23.6 Example 4 12.7 280 22 Example 5 3.33 238 23 - Example 6 7.3 190 26 Example 7 5.17 150 29 Example 8 0.875 35 40 Example 9 70.31 1350 19.2 Comparative Example 1 - - - Polymer solution preparation not proceeding Comparative Example 2 40,000 38,000 0.95 Comparative Example 3 - - - Polymer solution preparation not proceeding Comparative Example 4 - - -  The hollow fiber membrane is not formed and is broken. Comparative Example 5 162.5 1820 11.2 - Comparative Example 6 - - - Polymer solution preparation not proceeding

As shown in Tables 2 and 3, when the amount of the PI-PEG copolymer is excessively large as in Comparative Example 1, the polymer solution can not be prepared.

Also, as in Comparative Example 2, the CO 2 / N 2 selectivity of the hollow fiber membrane was remarkably low when the temperature of the double spinning nozzle was low.

In Comparative Example 3, the polymer solution was not produced when the amount of the phase transition was excessively large. In Comparative Example 4, the hollow fiber membrane itself was not produced when the phase transition was not used.

Further, as shown in Examples 1 to 4, as the weight of the cosolvent is decreased, the N 2 permeability and the CO 2 permeability are increased. This is because the content of the cosolvent as a volatile solvent is small and the thickness of the selective layer is decreased Which is caused by a decrease in the resistance that the gas permeates. Particularly, in Example 2, the weight of the cosolvent was the highest, and the permeability was low, indicating that the amount of the cosolvent as a volatile solvent was much thicker than the selectivity.

Further, in Examples 4, 5 and 6, it can be seen that as the weight of the PI-PEG copolymer increases, the CO 2 / N 2 selectivity increases, but the N 2 permeability and CO 2 permeability decrease. This is due to the fact that as the weight of the PI-PEG copolymer increases, the selectivity layer is well formed, while the resistivity of the penetrating gas increases.

Examples 4, 7, and 8 are hollow fiber membranes for gas separation prepared using the PI-PEG copolymer prepared in Synthesis Examples 1, 2, and 3, respectively. Synthesis Examples 1, 2, and 3 are synthesis examples of PI-PEG copolymers having different contents of poly (ethylene glycol) bis (3-aminopropyl) of Formula 3 and Table 2, As the y-value increases in PI-PEG, the selectivity of CO 2 / N 2 increases.

Example 3 and Comparative Example 5 are hollow fiber membranes for gas separation prepared using the PI-PEG copolymer prepared in Synthesis Examples 1 and 5, respectively, and the PI-PEG copolymer prepared in Synthesis Example 5 As shown in Table 3, y = 0 in the formula (1), the gas separation membrane prepared using the PI-PEG copolymer prepared in the above Synthesis Example 5 had a high CO 2 permeability but a relatively high CO 2 / N 2 The selectivity was low.

In Comparative Example 6, when the PI-PEG copolymer (y = 0.4 in Formula (1)) of Synthesis Example 6 was used, the phase separation did not occur and the gas separation membrane could not be produced even though the phase transition was added.

From these experimental results, it can be seen that the selectivity and permeability of the gas can be controlled by controlling the x and y values, particularly the y value, in the PI-PEG copolymer represented by the general formula (1).

It will be apparent to those skilled in the art that the present invention is not limited to the embodiments described above and that various changes and modifications may be made without departing from the spirit and scope of the present invention as defined by the appended claims. As shown in FIG.

It will be understood by those skilled in the art that the present invention may be embodied in many other specific forms without departing from the spirit or scope of the invention as defined by the appended claims and their equivalents. .

10: hollow fiber membrane for gas separation
11: Support layer
12: selected layer

Claims (14)

(I) (i) a polyimide-polyethylene glycol copolymer; (ii) a solvent; (iii) co-solvent; And (iv) a normal phase;
(II) supplying a first coagulating liquid for forming a hollow fiber and the mixed solution to an inner spinning nozzle and an outer spinning nozzle of the double spinning nozzle, and simultaneously discharging the mixed solution from the double spinning nozzle to obtain a hollow fiber solution; And
(III) exposing the hollow fiber solution to air, and then dipping the hollow fiber membrane into a second coagulating solution for forming a hollow fiber membrane to form a hollow fiber membrane. The method of claim 1, further comprising, after the step (III), washing and drying the hollow fiber membrane (IV). The method for producing a hollow fiber membrane for gas separation according to claim 1, wherein the polyimide-polyethylene glycol copolymer (i) is represented by the following formula (1)
≪ Formula 1 >
Figure pat00007

Wherein x is an integer of 0.75 to 0.96, and y is a real number of 0.02 to 0.25. The method of claim 1, wherein the solvent (ii) is at least one organic solvent selected from N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc), and dimethylformamide Wherein the hollow fiber membrane is separated from the hollow fiber membrane. 2. The hollow fiber membrane for gas separation according to claim 1, wherein the cosolvent (iii) is at least one volatile solvent selected from tetrahydrofuran (THF), ethyl acetate and acetone. Way. The method according to claim 1, wherein the co-solvent (iii) has a boiling point of 50 to 80 ° C. The hollow fiber membrane for gas separation according to claim 1, wherein (iv) the phase transition is at least one lithium compound selected from lithium chloride (LiCl), lithium nitrate (LiNO 3 ) and lithium sulfate (LiSO 4 ) Way. The polyimide resin composition according to claim 1, which comprises (i) 15 to 30% by weight of a polyimide-polyethylene glycol copolymer; (ii) 40-83 wt% solvent; (iii) 1 to 20% by weight of a co-solvent; And (iv) 1 to 10% by weight of a phase transition is obtained. [Claim 7] The method for producing a hollow fiber membrane for gas separation according to claim 1, The method of claim 1, wherein the double spinning nozzle has a temperature of 50 to 70 ° C. The method of claim 1, wherein the first coagulating solution for forming hollow fibers is heated to 30 to 50 캜 and supplied to the inner spinning nozzle. 2. The method according to claim 1, wherein the hollow fiber solution is exposed to air while the hollow fiber solution discharged from the double spinning nozzle is transferred to the coagulation bath having the second coagulating solution- (Method for producing hollow fiber membrane). The method according to claim 1, wherein the first coagulation solution for forming hollow fibers is at least one selected from the group consisting of ultrapure water, a mixture of ultrapure water and organic solvent, and alcohol, and the organic solvent is selected from the group consisting of N-methyl-2-pyrrolidone (NMP) , Dimethylacetamide (DMAc), and dimethylformamide (DMF). ≪ RTI ID = 0.0 > 11. < / RTI > The hollow fiber membrane according to claim 1, wherein the second coagulating liquid for hollow fiber membrane formation is at least one selected from water and alcohol, and the alcohol is at least one selected from methanol, ethanol and isopropyl alcohol. Method of manufacturing desert. A polyimide-polyethylene glycol composition for gas separation, which is produced by the production method of any one of claims 1 to 13 and has an asymmetric structure comprising a porous support layer for gas permeation and a selective layer for gas separation formed on the support layer Copper hollow fiber membranes.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109433032A (en) * 2018-11-06 2019-03-08 黄山学院 A kind of preparation method of ZIF-8 film

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109433032A (en) * 2018-11-06 2019-03-08 黄山学院 A kind of preparation method of ZIF-8 film

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