WO2021071034A1 - Copolymère réticulé, son procédé de préparation et membrane de séparation de gaz comprenant ledit copolymère réticulé - Google Patents

Copolymère réticulé, son procédé de préparation et membrane de séparation de gaz comprenant ledit copolymère réticulé Download PDF

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WO2021071034A1
WO2021071034A1 PCT/KR2020/003015 KR2020003015W WO2021071034A1 WO 2021071034 A1 WO2021071034 A1 WO 2021071034A1 KR 2020003015 W KR2020003015 W KR 2020003015W WO 2021071034 A1 WO2021071034 A1 WO 2021071034A1
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formula
crosslinked copolymer
norbornene
macromonomer
carbon dioxide
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Korean (ko)
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김태현
호세인이크발
김동영
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인천대학교 산학협력단
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/40—Imides, e.g. cyclic imides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide

Definitions

  • the present invention relates to a crosslinked copolymer, a method for preparing the same, and a gas separation membrane comprising the crosslinked copolymer.
  • the gas separation performance of the polymer membrane is evaluated by two variables: permeability and selectivity.
  • permeability and selectivity it is required to develop a polymer membrane with a balance of high permeability and selectivity, but trade-offs due to contradictory characteristics occur, and high permeability and selectivity exceeding the limit of the trade-off relationship known as'Robeson upper bound'. It is very difficult to prepare a polymer membrane equipped with.
  • the non-equilibrium free volume of the glassy polymer membrane decreases with the passage of time, resulting in a long-term stability problem of separation performance called an aging effect.
  • the CO 2 permeability is significantly reduced due to competitive adsorption of hydrocarbons (eg CH 4 , C 2 H 6, etc.) present in the gas mixture.
  • hydrocarbons eg CH 4 , C 2 H 6, etc.
  • Joel Vargas' group used a rigid crosslinking agent, 4,4′-(hexafluoroisopropylidene)bis( p -phenyleneoxy).
  • a soluble polymer film was prepared by crosslinking T.
  • the membrane thus prepared showed anti-plastic behavior of up to 14 atm for CO 2.
  • this membrane showed limitations in terms of permeability (10 ⁇ 12 Barrer) and selectivity ( ⁇ 23).
  • Tao Hong et al. conducted a study to include PDMS in norbornene-based crosslinked membranes to overcome low permeability. Since the PDMS polymer is known to have excellent CO 2 permeability of about 3800 Barrer, the degree of crosslinking was controlled.
  • the synthesized crosslinked membrane showed excellent CO 2 permeability of up to 6734 Barrer , but the CO 2 /N 2 selectivity (about 14) did not exceed the Robeson upper limit due to the low selectivity of PDMS (CO 2 /N 2 ⁇ 9.5). Further, in a subsequent study, Tao Hong's group modified the nitrile group of the comonomer with amidoxime having excellent solubility selectivity , and then increased the CO 2 /N 2 selectivity to 19 by controlling the pro-CO 2 property. However, studies on thermomechanical characteristics and aging and plasticizing performance have not been conducted.
  • a problem to be solved by the present invention is to provide a crosslinked copolymer having excellent carbon dioxide permeability and selectivity while preventing aging and preventing plasticization, a method for preparing the same, and a gas separation membrane comprising the crosslinked copolymer.
  • One aspect of the present invention relates to a crosslinked copolymer represented by the following formula (1).
  • X is a compound represented by Formula 2 below,
  • Y is a compound represented by the following formula (3),
  • M1 in Formula 2 is an integer of 0 to 50
  • l1 and n1 are each independently an integer of 0 to 20.
  • R 1 to R 6 are the same as or different from each other, and hydrogen or C 1 -C 3 alkyl
  • p1 is an integer from 1 to 35
  • q1 and r1 are each independently an integer of 1 to 10.
  • Another aspect of the present invention relates to a gas separation membrane comprising the crosslinked copolymer.
  • Another aspect of the present invention is (A) preparing a first macromonomer by reacting a first norbornene-based monomer and a first crosslinking agent; (B) preparing a second macromonomer by reacting a second norbornene-based monomer and a second crosslinking agent; And (C) preparing a crosslinked copolymer by mixing the first macromonomer and the second macromonomer; wherein the first crosslinking agent is a compound represented by the following formula (4), and the second crosslinking agent is represented by the following formula: It relates to a method for producing a crosslinked copolymer, which is a compound represented by 5.
  • M2 in Formula 4 is an integer of 0 to 50
  • l2 and n2 are each independently an integer of 0 to 20.
  • R 1 ′ to R 6 ′ are the same as or different from each other, and are hydrogen or C 1 -C 3 alkyl
  • p2 is an integer from 1 to 35
  • q2 and r2 are each independently an integer of 1 to 10.
  • Another aspect of the present invention relates to a method of manufacturing a gas separation membrane including the method of manufacturing the crosslinked copolymer.
  • the crosslinked copolymer according to the present invention and the gas separation membrane comprising the same show high carbon dioxide permeability and selectivity, including both a carbon dioxide soluble functional group and a carbon dioxide permeable functional group unit, and excellent anti-aging performance, plasticization prevention behavior through a stable chemical crosslinking structure, and It has thermal properties.
  • FIG. 1 is a schematic diagram showing a method of preparing a crosslinked copolymer by ring opening metathesis polymerization (ROMP) according to an embodiment of the present invention.
  • 3 is a 1 H-NMR spectrum of a macromonomer prepared according to an embodiment of the present invention.
  • Figure 4 is a norbornene dianhydride (norbornene dianhydride), polyethylene glycol / polypropylene glycol (PEG / PPG), a first macromonomer (DNB-PEG / PPG) used to prepare a crosslinked copolymer according to an embodiment of the present invention. ), a second macromonomer (DNB-PDMS), and a graph showing the ATR-IR analysis results of polydimethylsiloxane (PDMS).
  • PDMS polydimethylsiloxane
  • FIG. 5 is a graph showing the results of ATR-IR analysis of a crosslinked copolymer according to an embodiment of the present invention.
  • FIG. 6 is a graph showing UTM mechanical properties measurement results of a separator manufactured according to an embodiment of the present invention.
  • FIG. 7A is a graph showing the TGA analysis result of a separator according to an embodiment of the present invention
  • FIG. 7B is a first differential curve of the graph of FIG. 3A
  • FIG. 7C is a monomer of the separator according to an embodiment of the present invention.
  • FIG. 8A is a graph showing a DSC analysis result of a gas separation membrane according to an embodiment of the present invention
  • FIG. 8B is an enlarged view of FIG. 8A.
  • FIG. 9 is a graph showing a WAXRD analysis result of a gas separation membrane according to an embodiment of the present invention.
  • FIG. 10 is an image showing SEM and EDS analysis results of a gas separation membrane according to an embodiment of the present invention.
  • FIG. 11 is an image showing an AFM analysis result of a gas separation membrane according to an embodiment of the present invention.
  • FIG. 12 is a graph showing a result of measuring a single gas permeability and selectivity of a gas separation membrane according to an embodiment of the present invention.
  • FIG. 13 is a graph showing a result of measuring a change in diffusivity and solubility according to the PDMS content of a gas separation membrane according to an embodiment of the present invention.
  • FIG. 15A is a graph showing carbon dioxide permeability according to an increase in pressure of a separation membrane according to an embodiment of the present invention
  • FIG. 15B is a graph showing carbon dioxide selectivity.
  • 16 is a graph showing a result of measuring carbon dioxide and nitrogen permeability of a separation membrane according to an embodiment of the present invention for 230 days.
  • One aspect of the present invention provides a crosslinked copolymer represented by the following formula (1).
  • X is a compound represented by Formula 2 below,
  • Y is a compound represented by the following formula (3),
  • M1 in Formula 2 is an integer of 0 to 50
  • l1 and n1 are each independently an integer from 0 to 20,
  • R 1 to R 6 are the same as or different from each other, and hydrogen or C 1 -C 3 alkyl
  • P1 is an integer of 1 to 35
  • the q1 and r1 are each independently an integer of 1 to 10.
  • the form of the copolymer is expressed as described above for convenience, but is not particularly limited, and is a random copolymer, an alternate copolymer, a block copolymer, a graft copolymer, and Various forms, such as a star block copolymer, are possible, and preferably a random copolymer.
  • the crosslinked copolymer of the present invention includes a crosslinking agent having carbon dioxide solubility in polynorbornene and a crosslinking agent having carbon dioxide permeability, respectively, and significantly improved low permeability and carbon dioxide selectivity, which is a problem due to small free volume.
  • Polyethylene oxide or polyethylene glycol has the highest carbon dioxide affinity among the substances reported to date.
  • PEG membrane has limited application for gas separation because the material transport properties of the membrane are reduced due to its structured structure and crystallinity.
  • a copolymer (Formula 2) containing polyethylene glycol (PEG) and polypropylene glycol (PPG) is used as a carbon dioxide soluble crosslinking agent, while taking the effect of high carbon dioxide affinity expressed by polyethylene glycol.
  • the addition of glycol suppressed the dense packing (crystallization) of PEG.
  • the compound represented by Formula 3 was introduced as a crosslinking agent.
  • the compound represented by Chemical Formula 3 not only secured a free volume for gas permeation, but also exhibited anti-aging and plasticizing effects, thereby securing long-term stability of the gas separation membrane into which the crosslinked copolymer was introduced.
  • X and Y are preferably included in a molar ratio of 6:1 to 12:1.
  • Y is included in excess of the above range, the mechanical properties of the crosslinked copolymer may be reduced and cannot be used.
  • the effect of improving the gas permeability of the crosslinked copolymer is insufficient and undesirable.
  • the molecular weight of the compound represented by Formula 2 is 900 to 2900 g/mol, preferably 1400 to 2500 g/mol, and the molecular weight of the compound represented by Formula 3 is 1500 to 3500 g/mol, Preferably it may be 2000 to 3000 g/mol.
  • Selected in the above molecular weight range is that it is possible to form a desired crosslinking network by adjusting the chain lengths of different crosslinking agents to be similar to each other, and to prevent formation of crystals of polyethylene glycol and to form an appropriate free volume for gas permeation. desirable.
  • m1 is an integer of 10 to 39
  • l1 and n1 may be independently an integer of 0 to 15.
  • Inclusion in the above range is preferable in that it is possible to maintain excellent carbon dioxide permeability and selectivity while preventing the formation of crystals of ethylene glycol. If it is out of the above range, carbon dioxide permeability may be rapidly decreased or carbon dioxide solubility may be decreased due to packing of ethylene glycol.
  • the crosslinked copolymer may have a lower carbon dioxide permeability measured under 25 atm pressure compared to the carbon dioxide permeability measured under 10 atm pressure.
  • a gas permeability increases under high pressure conditions, but a plasticization phenomenon in which the selectivity rapidly decreases is likely to occur.
  • the separation membrane containing the crosslinked copolymer of the present invention prevents plasticization of increasing the selectivity, although the dioxide permeability decreases at a slow rate as the pressure increases under high pressure conditions of 10 atm or more. It can be confirmed that it is effective.
  • Another aspect of the present invention provides a gas separation membrane comprising the crosslinked copolymer.
  • the gas separation membrane is preferably used for carbon dioxide separation.
  • the gas separation membrane may have a carbon dioxide permeability of 380 barrels or more and a carbon dioxide/nitrogen selectivity of 50 or more measured under conditions of 1 bar and 30°C.
  • the carbon dioxide permeability is an index indicating the permeation rate of carbon dioxide through the gas separation membrane, and the unit may be expressed by Equation 1 below.
  • cm represents the thickness of the separator
  • cm 2 represents the area of the separator
  • s represents the time (seconds)
  • cm.Hg represents the upper pressure.
  • Another aspect of the present invention is (A) preparing a first macromonomer by reacting a first norbornene-based monomer and a first crosslinking agent; (B) preparing a second macromonomer by reacting a second norbornene-based monomer and a second crosslinking agent; And (C) preparing a crosslinked copolymer by mixing the first macromonomer and the second macromonomer; wherein the first crosslinking agent is a compound represented by the following formula (4), and the second crosslinking agent is represented by the following formula: It provides a method for producing a crosslinked copolymer, which is a compound represented by 5.
  • M2 in Formula 4 is an integer of 0 to 50
  • l2 and n2 are each independently an integer from 0 to 20,
  • R 1 ′ to R 6 ′ are the same as or different from each other, and are hydrogen or C 1 -C 3 alkyl
  • p2 is an integer from 1 to 35
  • q2 and r2 are each independently an integer of 1 to 10.
  • the first norbornene-based monomer and the second norbornene-based monomer are norbornene dicarboxylic anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride (exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride), methyl-5-norbornene-2,3-dicarboxylic anhydride (Methyl-5-norbornene-2,3-dicarboxylic anhydride), 3-methyl-4-cyclohexene-1,2-dicarboxylic Anhydride, 2-bromo-5-norbornene-2 ,3-dicarboxylic anhydride (2-bromo-5-norbornene-2,3-dicarboxylic anhydride) and bicyclo[2,2,2]oct-5-ene-2,3-dicarboxylic anhydride Ride (Bicyclo[2.2.2]oct-5-ene-2,3-dica
  • the first norbornene-based monomer and the second norbornene-based monomer may be the same as or different from each other, and preferably may be the same.
  • the first crosslinking agent and the first norbornene-based monomer in step (A) may be reacted in a molar ratio of 1:1 to 1:5, preferably 1:2 to 1:4,
  • the second crosslinking agent and the second norbornene-based monomer in step (B) may be reacted in a molar ratio of 1:1 to 1:5, preferably 1:2 to 1:4. It is preferable that the first and second crosslinking agents and the first and second norbornene-based monomers react at a molar ratio of 1:2 to 1:4 in that a crosslinked structure having anti-aging and plasticization properties can be formed.
  • the first macromonomer and the second macromonomer may be mixed in a ratio of 6:1 to 12:1.
  • the second macromonomer is included in excess of the above range, the mechanical properties of the crosslinked copolymer to be prepared cannot be reduced and cannot be used. If it is included below the above range, the effect of improving the gas permeability of the crosslinked copolymer is insufficient. It is not desirable.
  • the molecular weight of the compound represented by Formula 4 is 900 to 2900 g/mol, preferably 1400 to 2500 g/mol, and the molecular weight of the compound represented by Formula 5 is 1500 to 3500 g/mol , Preferably 2000 to 3000 g/mol.
  • Selected in the above molecular weight range is that it is possible to form a desired crosslinking network by adjusting the chain lengths of different crosslinking agents to be similar to each other, and to prevent formation of crystals of polyethylene glycol and to form an appropriate free volume for gas permeation. desirable.
  • m2 is an integer of 10 to 39
  • l2 and n2 may be independently an integer of 0 to 15.
  • What is included in the above range is preferable in that it can maintain excellent carbon dioxide permeability and selectivity while preventing the formation of crystals of ethylene glycol in the crosslinked copolymer to be prepared. If it is out of the above range, carbon dioxide permeability may be rapidly decreased or carbon dioxide solubility may be decreased due to packing of ethylene glycol generated in the crosslinked copolymer to be produced.
  • the reaction of step (C) may be performed under a second generation Grubb's catalyst.
  • a norbornene-based copolymer is prepared by ring-opening metathesis polymerization (ROMP) performed under a second generation Grub catalyst.
  • Another aspect of the present invention provides a method of manufacturing a gas separation membrane including the method of manufacturing the crosslinked copolymer.
  • dicarboxylic anhydride 1.728 g, 5.26 mmol, 1 eq
  • PEG/PPG polyethylene glycol/polypropylene glycol
  • 10 g, 10.52 mmol, 2 eq was added to the flask, and the reaction was heated for 10 hours. Then, the reaction was cooled to room temperature again and concentrated on a rotary evaporator.
  • the second macromonomer (DNB-PDMS) was synthesized in the same manner as in Preparation Example 1 except for using 3.0 g (1.2 mmol) of polydimethylsiloxane (PDMS) and 0.4 g (2.43 mmol) of NBDA and washing with ether.
  • FIG. 2 is a 1 H-NMR spectrum of the reactants used in Preparation Examples 1 and 2.
  • Figure 2a is NBDA
  • Figure 2b is PEG / PPG
  • Figure 2c is a 1 H-NMR spectrum of PDMS.
  • 3 is a 1 H-NMR spectrum of the first and second macromonomers.
  • 3A is a 1 H-NMR spectrum of the first macromonomer
  • FIG. 3B is a 1 H-NMR spectrum of the second macromonomer.
  • FIG. 1 is a schematic diagram showing a method of preparing a crosslinked copolymer by ring opening metathesis polymerization (ROMP) according to an embodiment of the present invention.
  • HPLC grade DCM was placed in a Schlenk flux tube. Pure N 2 gas was purged into the solvent for 1 hour. Then, the freeze-thaw method was applied to the solvent four times to remove the dissolved gas. Thereafter, 600 mg of the first macromonomer (DNB-PEG/PPG) was mixed with 0.064 mg of the second macromonomer (DNB-PDMS) to maintain the molar ratio of the first macromonomer and the second macromonomer at 12:1. Thus, a separator was prepared.
  • the polymerization was stopped by adding ethyl vinyl ether to DCM and dried for 3 hours.
  • the membrane obtained by evaporation of the solvent was washed several times with DCM, and then finally dried in an oven at 40° C. for 48 hours.
  • a separator was manufactured in the same manner as in Example 1, except that the molar ratio of the first macromonomer and the second macromonomer was adjusted to 10:1.
  • a separator was manufactured in the same manner as in Example 1, except that the molar ratio of the first macromonomer and the second macromonomer was adjusted to 8:1.
  • a separator was manufactured in the same manner as in Example 1, except that the molar ratio of the first macromonomer and the second macromonomer was adjusted to 6:1.
  • a separator was manufactured in the same manner as in Example 1, except that only the first macromonomer was used without using the second macromonomer.
  • FIG. 4 shows norbornene dianhydride, polyethylene glycol/polypropylene glycol (PEG/PPG), a first macromonomer (DNB-PEG/PPG), and a second macromonomer (DNB) used to prepare a crosslinked copolymer.
  • -PDMS polyethylene glycol/polypropylene glycol
  • PDMS polydimethylsiloxane
  • FIG. 5 is a graph showing the ATR-IR analysis results of the crosslinked copolymers prepared according to Examples 1 to 4 and Comparative Example 1 and the second macromonomer (DNB-PDMS).
  • 5A is a graph showing the results of the ATR-IR analysis
  • FIG. 5B is an enlarged graph of the results of FIG. 5A.
  • the maximum tensile stress was 10-11 MPa
  • the elongation breaks were 7.7-13.6%
  • the Young's modulus was 380-550 MPa.
  • the tensile stress was the best compared to the previously reported rubber polymer, and the mechanical properties were excellent because a rigid norbornene structure was formed due to effective crosslinking between the chains of the polymer and the flexible crosslinking agent.
  • Example 2 Conversely, as the PDMS content increases, the initial elongation properties of the membrane increase to a certain limit (Example 2) and then decrease after that (Example 3). In the case of Example 4, the mechanical flexibility was completely lost, and when the content of PDMS was further increased, the self-reliance ability rapidly decreased. This is because the mechanical properties of PDMS with a small molecular weight are poor.
  • TGA Thermogravimetric analysis
  • FIG. 7A is a graph showing the TGA analysis result of a separator according to an embodiment of the present invention
  • FIG. 7B is a first differential curve of the graph of FIG. 7A
  • FIG. 7C is a monomer of the separator according to an embodiment of the present invention.
  • the first weight loss of 100° C. or less was caused by evaporation of water in the separator.
  • the maximum weight loss occurred at 358 ⁇ 363 °C. This means that the crosslinking agent has excellent thermal stability of the membrane, especially in the case of a crosslinked separator in which the crosslinking agent is decomposed in a low temperature region.
  • the weight reduction due to thermal decomposition was not a single step, but two steps, which can be confirmed in the first derivative curve of Fig. 7b.
  • the total weight reduction was found by the differential curve of FIG. 7B, and showed a tendency to coincide with the composition of the macromonomer.
  • FIG. 8A is a graph showing a DSC analysis result of a gas separation membrane according to an embodiment of the present invention
  • FIG. 8B is an enlarged view of FIG. 8A.
  • Tg (-53 °C to -62.5 °C) and Tm (23.3 °C to 11.6 °C) decreased as the PDMS content in the copolymer increased.
  • Both Examples 1 to 4 and Comparative Example 1 were in a rubber state at 30°C, and Tg was distributed in the range of -53°C to -62.5°C.
  • WAXRD Wide-angle X-ray crystallographical diffraction
  • the methyl group present in the PPG block of the first macromonomer prevented crystallization of the PEG block and effectively improved gas diffusion.
  • the second macromonomer increases the flexibility of the copolymer chain, thereby increasing the free volume of the copolymer matrix, and consequently effectively improving the gas permeability.
  • SEM Scanning Electron Microscopy
  • EDS Energy Dispersive spectroscopy
  • FIGS. 10A to 10D are Comparative Example 1
  • FIGS. 10E to 10H are Example 1
  • FIGS. 10I to 10L are Example 2
  • FIGS. 10M to 10P are Example 3
  • FIGS. 10Q to 10U are Example 4
  • 10a e, i, m and q are SEM analysis images, respectively
  • Figs. 10b, f, j, n, and r are EDS analysis images, respectively
  • Fig. 10c, g, k, o and t are respectively carbon Element maps
  • Figs. 10d, h, l, p, and u are silicon element maps, respectively.
  • Example 1 65.99 26.95 7.06 0.262 0.107 0.408
  • Example 2 65.50 26.05 8.45 0.324 0.129 0.398
  • Example 3 65.29 25.84 8.87 0.343 0.136 0.396
  • Example 4 65.11 25.62 9.27 0.362 0.142 0.393
  • the polymer without PDMS showed a continuous phase morphology, and phase separation could not be confirmed. Specific bright areas or non-uniform areas appeared due to the hydrophobic chain skeleton.
  • the EDS analysis image of FIG. 10B shows that the atoms of the film are uniformly distributed throughout the film.
  • FIGS. 10E to 10U as the second macromonomer (DNB-PDMS) was applied, a shape having a clearly phase-separated network structure (a bright sphere shape) was confirmed.
  • the hydrophobic PDMS part was almost separated in a sphere shape and showed a honeycomb-shaped network structure. As the PDMS content increased, the number and density of separated spheres increased, and the network structure also changed.
  • FIG. 11A is an AFM analysis image of Comparative Example 1
  • FIG. 11B is Example 1
  • FIG. 11C is Example 2
  • FIG. 11D is Example 3 and FIG. 11E.
  • a dark region corresponds to a hydrophilic composition (PEG/PPG), and a bright region corresponds to a hydrophobicity (hydrocarbon chain and PDMS composition). As shown in FIG. 11, as the PDMS composition increases, the hydrophobic region gradually increases.
  • Example 1 301.23 5.09 16.85 59.2 17.52
  • Example 1 399.01 6.93 22.50 57.6 17.43
  • Example 2 437.02 7.78 25.16 56.2 17.37
  • Example 3 476.01 8.65 28.04 55.0 17.00
  • Example 4 561.33 11.29 38.56 49.7 14.56
  • 1 Barrer 10 -10 [cm 3 (STP).cm]/(cm 2 .s.cm.Hg).
  • the gas permeability was very high, about 301 Barrer, which was about 18 times the previously reported value for pure PNB membranes (10-17 Barrer).
  • Such a large increase in permeability is due to an increase in free volume due to the prevention of dense packing of norbornene moieties due to the PEG/PPG group having very high pro-carbon dioxide and the crosslinking network.
  • polyethylene oxide or polyethylene glycol is a material having the highest carbon dioxide affinity among the materials reported so far.
  • PEG membrane has limited application for gas separation because the material transport properties of the membrane are reduced due to its structured structure and crystallinity.
  • the present inventors used a block copolymer (PEG-b-PPG) containing PEG and PPG as a crosslinking agent.
  • PEG-b-PPG block copolymer
  • the methyl group of PPG acts as a spacer, interfering with hydrogen bonding with ether oxygen, and interfering with the orderly packing of PEG.
  • crystallinity is minimized to form a distinct morphology
  • the bulky PPG moiety present in the copolymer provides high permeability
  • the ethylene oxide moiety can provide very high CO 2 /N 2 selectivity.
  • FIG. 13A is an increase in the diffusion rate according to the content of PDMS in the copolymer
  • FIG. 13B is an increase in diffusion rate
  • FIG. 13C is a solubility coefficient
  • FIG. 13D is an increase in solubility.
  • the gas permeability linearly increased as the PDMS content increased for all gases. This is because gas diffusion is promoted due to an increase in the diffusion rate due to an increase in the free volume and chain flowability as the PDMS content increases.
  • Example 4 xR-6:1 containing 14 mol% of DNB-PDMS
  • the diffusion rate for all gases was almost as compared to Comparative Example 1 (xR-1:0) not containing PDMS. It increased three times.
  • the separation membrane according to the above example is suitable for carbon dioxide separation based on high CO 2 permeability (300 to 561 Barrer) and excellent CO 2 /N 2 selectivity (50 to 59).
  • FIG. 15A is a graph showing carbon dioxide permeability according to an increase in pressure of a separation membrane according to an embodiment of the present invention
  • FIG. 15B is a graph showing carbon dioxide selectivity.
  • the carbon dioxide permeability to the separation membranes of Example 1 (xR-12:1) and Example 2 (xR-10:1) increased to an initial 10 atm, and then to a range of 25 atm. It was confirmed that it gradually decreased very finely. This tendency corresponds to the plasticization prevention performance, and the chemical crosslinking structure of the copolymer effectively inhibits the growth of the chain and thus prevents plasticization. That is, the rigid structure formed by crosslinking tightly entangles the polymer chain and prevents it from moving, thereby preventing the plasticizing effect.
  • Example 3 (xR-8: 1) having a high PDMS content showed similar plasticization prevention behavior as in Examples 1 and 2 up to 15 atm, but plasticization started under a high pressure of 20 atm and continued up to 25 atm. Showed a tendency to become.
  • Example 4 (xR-6:1) having a higher PDMS content showed a tendency of increasing carbon dioxide permeability as the pressure increased over the entire pressure range of 1 to 25 atm. This corresponds to the fact that the degree of crosslinking of the film is insufficient to prevent plasticization due to the increase in the flexible PDMS content.
  • the crosslinked copolymer according to the present invention and the gas separation membrane comprising the same showed high carbon dioxide permeability and selectivity, including both a carbon dioxide soluble functional group and a carbon dioxide permeable functional group unit, and excellent anti-aging performance and plasticization through a stable chemical crosslinking structure. It has anti-behavior and thermal properties.

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  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

La présente invention concerne un copolymère réticulé, un procédé pour préparer celui-ci, et une membrane de séparation de gaz comprenant le copolymère réticulé. La membrane de séparation de gaz comprend à la fois une unité de groupe fonctionnel soluble dans le dioxyde de carbone et une unité de groupe fonctionnel perméable au dioxyde de carbone, et présente ainsi une perméabilité et une sélectivité élevées par rapport au dioxyde de carbone, et par l'intermédiaire de structures chimiques réticulées stables, présente une performance de résistance au vieillissement, un comportement de prévention de plastification et des caractéristiques thermiques remarquables.
PCT/KR2020/003015 2019-10-10 2020-03-03 Copolymère réticulé, son procédé de préparation et membrane de séparation de gaz comprenant ledit copolymère réticulé WO2021071034A1 (fr)

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KR10-2019-0125290 2019-10-10
KR1020190125290A KR102159668B1 (ko) 2019-10-10 2019-10-10 가교 공중합체, 이의 제조방법 및 상기 가교 공중합체를 포함하는 기체 분리막

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KR102538338B1 (ko) * 2021-03-19 2023-05-31 인천대학교 산학협력단 기체 분리 성능이 우수한 가교 공중합체, 이를 포함하는 기체 분리막, 가교 공중합체의 제조방법 및 기체 분리막의 제조방법

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US20170043303A1 (en) * 2015-08-14 2017-02-16 Ut-Battelle, Llc Cross-linked polymeric membranes for carbon dioxide separation
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