CN116173749A - Preparation method of high-performance porous coordination polymer membrane - Google Patents

Preparation method of high-performance porous coordination polymer membrane Download PDF

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CN116173749A
CN116173749A CN202211612028.1A CN202211612028A CN116173749A CN 116173749 A CN116173749 A CN 116173749A CN 202211612028 A CN202211612028 A CN 202211612028A CN 116173749 A CN116173749 A CN 116173749A
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membrane
porous coordination
mpsf
polydimethylsiloxane
coordination polymer
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乔志华
李都都
仲崇立
孙玉绣
郭翔宇
贾雪梦
奥德
李宁
马超
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Tianjin Polytechnic University
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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
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • 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
    • 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
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
    • 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
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • 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
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

Abstract

The invention discloses a preparation method of a high-performance porous coordination polymer membrane, which comprises the following preparation processes: firstly, synthesizing a series of halogen-induced porous coordination polymers, uniformly mixing the porous coordination polymers with polymer PEI to be used as a membrane building liquid, and coating the membrane building liquid on a polysulfone support layer modified by polydimethylsiloxane and polyvinyl alcohol to prepare the mixed matrix membrane. Next, metal-induced ordered microporous polymers were synthesized and coated on polydimethylsiloxane and polyvinyl alcohol modified polysulfone support layers to prepare MMP/mPSf membranes. The beneficial effects of the invention are as follows: the novel H-PCP and MMPs polymer material with the polarization rate screening characteristic is prepared, has lower energy consumption, and realizes the preferential permeation of low-concentration hydrocarbon with high polarization rate and has ultrathin, large-area and defect-free porous membrane with excellent gas separation performance.

Description

Preparation method of high-performance porous coordination polymer membrane
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to a preparation method of a high-performance porous coordination polymer membrane.
Background
As an emerging high-efficiency separation technology, the membrane separation technology has the advantages of high efficiency, energy conservation, environmental friendliness, small occupied area and the like. Mixed matrix membranes (M i xed Matr i x Membrane, MMMs) have been developed rapidly in applications such as gas mixture and liquid separation, combining the advantages of easy polymer processing, simple preparation and good separation properties of the filler. However, because the filler with good compatibility with the polymer has limited types and the pore structure advantage of the filler is difficult to fully utilize, the gas permeation selectivity of the mixed matrix membrane is difficult to be greatly improved, the separation system is single, and the large-scale preparation and application of the membrane are limited.
Novel porous polymers are a material of interest due to their designable backbone and pore structure. However, most porous materials follow molecular sieving mechanisms, separation systems are limited and defects are difficult to eliminate due to difficulties. There is no report of preferential permeation of alkane hydrocarbon gases in refinery gases and the fabrication of utility membranes with ultra-thin selective layers (thickness <200 nm) and large surface areas (> 50cm 2) remains a challenge, and therefore, there is a need to continue to develop porous materials for light hydrocarbon separations and to prepare mixed matrix membranes and membranes with ultra-thin large areas.
In summary, in order to realize preferential permeation of low-concentration hydrocarbon gas in refinery gas and preparation of ultra-thin large-area membrane, the invention aims to adopt asymmetric isophthalic dicarboxylic acid with halogen substituent groups at different positions to coordinate with metal and adopt a polymer-oriented chemical synthesis (PDCS) strategy to synthesize a novel H-PCPs material with polarization rate-dependent adsorption characteristics and a novel porous material-metal induced ordered microporous polymer (MMPs), and then the novel H-PCPs material and the novel porous material are used as filler layers to be dispersed in a polymer matrix completely to prepare a mixed matrix membrane and an ultra-thin, large-area and defect-free porous membrane with excellent gas separation performance. The process has low energy consumption, simple operation and wide application prospect.
Disclosure of Invention
The invention aims to overcome the defects that the prior membranes are H2 preferential permeable membranes and are difficult to eliminate to manufacture practical membranes with ultrathin selective layers (thickness <200 nm) and large surface areas (> 50cm <2 >), and the energy consumption is high, a series of halogen-induced porous coordination polymers and metal-induced ordered microporous polymers are synthesized for the first time, and are fully and uniformly dispersed in a polymer matrix as a filler layer, and the diffusion selectivity of the mixed matrix membrane is greatly inhibited due to the asymmetric structure and the existence of halogen. Consistent with the polarizability-dependent adsorption of H-PCPs, the mixed matrix membrane exhibits polarizability sieving separation performance, resulting in preferential permeation of highly polar gases. The metal-induced ordered microporous polymer is used as a filler to prepare an ultrathin, large-area and defect-free porous membrane. The method has low energy consumption, good gas separation performance and wide application prospect in the technical field of membrane separation.
The technical scheme of the invention is as follows: a method for preparing a high-performance porous coordination polymer film, which is characterized by comprising the following steps:
(1) By Zr 4+ And halogen substituted functional group X-isophthalic acid, synthesizing a series of halogen induced porous coordination polymers, namely H-PCPs;
(2) Selecting different linear polymers rich in amine, small organic joints and metal ions as reactants to synthesize a series of ordered metal-induced microporous polymers, namely MMPs;
(3) Sequentially coating a polydimethylsiloxane solution and a polyvinyl alcohol solution on the surface of the polysulfone ultrafiltration membrane to obtain an interface layer with high flux and hydrophilicity;
(4) Uniformly mixing the linear polymer rich in amine in the step (2) and the H-PCPS of the porous coordination polymer in the step (1) according to a certain proportion, then coating the mixture on the surface of the modified polysulfone ultrafiltration membrane, and obtaining the H-PCP/PE I/mPsf mixed matrix membrane through an interfacial self-assembly process.
(5) MMPs and aqueous solution are uniformly mixed according to a certain proportion, then the mixture is coated on the surface of a modified polysulfone ultrafiltration membrane, and an MMP/mPsf membrane is prepared by inducing ordered microporous polymers through metals.
Further, in the step (1), the halogen substituted functional group X-isophthalic acid is selected from 4-position or 5-position halogen substituted functional group X-isophthalic acid, X is C l or Br, the synthesis method adopts a solvothermal method, the reaction temperature of the solvothermal method is 150 ℃, the reaction time is 12 hours, the reaction is carried out in a polytetrafluoroethylene reaction kettle, the synthesized product is sequentially washed for 3 times by DMF, deionized water and methanol, and finally the target product is obtained by vacuum drying overnight at 100 ℃.
Further, in step (1), a series of halogen-induced porous coordination polymers are synthesized by solvothermal method, and the polydimethylsiloxane coating and the polyvinyl alcohol solution coating are carried out at room temperature.
Further, in the step (2), the linear polymer rich in amine is polyvinyl amine, namely PVAm, or commercial polyethylene imine PE I, and the molecular weight of the commercial polyethylene imine is 10kDa and 20kDa, so that two polymers of polyvinyl amine with different molecular weights, namely 10kDa to 15kDa and 25 kDa to 30kDa, are respectively synthesized. The small organic linker adopts acetyl chloride fenac and 4-chloroisophthalic acid two halogenated carboxylic acid linker. Metal ion selective Cu 2+ (CH3COO - ) 2 Or Zn 2+ (NO3 - ) 2 26H 2 O is used as divalent metal ion to produce copper-MMPs or zinc-MMPs respectively.
Further, in step (2), the rotational mean square diameter of the amine-rich linear polymer is measured by gel permeation chromatography in combination with a low angle laser scattering detector to adjust the crystal size of MMPs.
Further, in the step (2), metal ions are dissolved in water, then small organic joints are added, an acetone solution is poured into the solution to be stirred uniformly, and an aqueous solution of the polymer rich in amine is added into the solution to be stirred uniformly.
Further, in the step (3), the concentration of the polydimethylsiloxane was 0.4wt%, and the polydimethylsiloxane was coated on the surface of the polysulfone ultrafiltration membrane with a doctor blade, and then dried in a constant temperature and humidity oven at 30℃and 40% RH for at least 1 hour. The polydimethylsiloxane solution coated on the surface of the polysulfone ultrafiltration membrane can not only prevent the permeation of pores, but also improve the uniformity of the surface of the support membrane, and the solvent for dissolving the polydimethylsiloxane is n-heptane, so that the solvent is relatively easy to volatilize, and is dried in a constant temperature and humidity box at 30 ℃ and 40%RH for at least 1h.
Further, in the step (3), the polydimethylsiloxane solution is specifically: 0.2g of polydimethylsiloxane, 0.4g of tetraethoxysilane and 0.4g of dibutyltin dilaurate were mixed with 99g of n-heptane to obtain a 0.2wt% polydimethylsiloxane solution, which was uniformly coated on the surface of the polysulfone membrane by a coater with an accuracy of.+ -. 5. Mu.m, a predetermined wet coating thickness of 50. Mu.m, and then dried in a climatic chamber at 30℃and 40% RH for at least 24 hours.
In the step (3), the polysulfone ultrafiltration membrane, namely the PSf membrane, is a commercial ultrafiltration membrane, and the average pore diameter is 20-50nm.
Further, in the step (3), the polydimethylsiloxane solution is specifically: 0.2g of polydimethylsiloxane, 0.4g of tetraethoxysilane and 0.4g of dibutyltin dilaurate were mixed with 99g of n-heptane to obtain a 0.2wt% polydimethylsiloxane solution, which was uniformly coated on the surface of the polysulfone membrane by a coater with an accuracy of.+ -. 5. Mu.m, a predetermined wet coating thickness of 50. Mu.m, and then dried in a climatic chamber at 30℃and 40% RH for at least 24 hours.
Further, in the step (3), the concentration of the polyvinyl alcohol solution is 0.1%, 0.1wt% of the polyvinyl alcohol solution is coated on the polydimethylsiloxane modified polysulfone substrate, the thickness of the preset wet coating is 50 μm, the precision is + -5 μm, and the film is dried in a climatic chamber at 30 ℃ and 40% RH to obtain the mPSf film with a hydrophilic surface.
Further, in the step (4), the polyvinyl alcohol has a linear structure and a molecular weight of 70000, and a certain ratio of H-PCP/PE I ethanol/H 2 O (1:1Vol) solution is uniformly coated on the surface of the mPsf film, and the mixture is dried in a constant temperature and humidity box with the temperature of 30 ℃ and the relative humidity of 40% to prepare the H-PCP/PE I/mPsf mixed matrix film; when the filler content is 37.5wt%, the prepared porous coordination polymer membrane, namely the H-PCP/PE I/mPsf mixed matrix membrane material has optimal performance.
Further, in step (5), the MMP/mPsf film was prepared by uniformly coating 0.25wt% of MMP dispersion on the mPsf substrate with a coating thickness of 50 μm and a coating precision of.+ -. 5. Mu.m, and then drying in a climatic chamber at 30℃and 40% RH. MMP concentration of 0.25wt% can be uniformly coated and has an area of greater than 100cm 2 The MMP/mPsf film surface and cross-section are uniformly distributed.
Further, the prepared porous coordination polymer membrane H-PCP/PE I/mPsf mixed matrix membrane is used for gas separation, in particular for hydrocarbon (C1-C4) compound alkane gas with high polarizability and low polarizability H 2 Separation between.
Further, the prepared large-area ultrathin defect-free MMP/mPsf film (below 50 nm) and greater than 100cm 2 For gas separation, in particular CO 2 /N 2 Separation between.
The invention has the advantages that: the invention adopts metal ions and halogen to replace functional groups of X-isophthalic acid to successfully synthesize a series of halogen-induced porous coordination polymers (H-PCPs) for the first time and adopts a polymer-oriented chemical synthesis (PDCS) strategy to prepare a novel porous material, namely metal-induced ordered microporous polymers (MMPs), so as to prepare a non-defective mixed matrix membrane and an ultrathin, large-area and non-defective porous membrane with excellent gas separation performance. By utilizing the asymmetric structure and the existence of halogen, the diffusion selectivity of the mixed matrix membrane is greatly inhibited, so that the preferential permeation of high-polarity gas is realized.
Drawings
FIG. 1 is a porous coordination polymer membrane synthesized from halogen substituents at different positions in example 1;
a is an SEM image of N-PCP, b is an SEM image of 4-C l-PCP, and c is an SEM image of 5-C l-PCP.
FIG. 2 is a porous coordination polymer film synthesized from halogen substituents at different positions in example 1;
FIG. 2 is an SEM image of 4-Br-PCP on the top, and FIG. 2 is an SEM image of 5-Br-PCP on the bottom.
FIG. 3 is a topographical view of the crystalline particles of MMPs of example 2, specifically SEM images of MMP-1 and MMP-2.
FIG. 4 is a topographical view of the crystalline particles of MMPs of example 2, specifically SEM images of MMP-3 and MMP-4 d.
FIG. 5 is an infrared spectrum of a PE I/mPsf film, N-PCP and H-PCPs/PE I/mPsf mixed matrix film in example 3.
FIG. 6 is a graph showing the morphology characterization of the PE I/mPsf film, N-PCP, and H-PCPs/PE I/mPsf mixed matrix film in example 3, A1-F1 are low resolution SEM surface images, A2-F2 are high resolution SEM surface images, A3-F3 are SEM cross-sectional images, and A4-F4 are AFM images of the PCPs/PE I/mPsf film.
Figure 7 is a graph of an MMP/mPSf mixed matrix membrane in example 4,
a is a surface SEM image of MMP-1/mPsf film,
b is a cross-sectional SEM image of MMP-1/mPsf film,
c is a surface SEM image of MMP-3/mPsf film,
d is a cross-sectional SEM image of MMP-3/mPsf membrane.
FIG. 8 shows the pure gas (C1-C4) flux and gas/H2 ideal selectivity for the H-PCPs/PE I/mPsf mixed matrix membranes of example 3.
FIG. 9 is a graph of mixed gas CO2/N2 separation performance of MMP/mPsf mixed matrix membranes in example 4, with the upper graph showing CO2 separation performance of MMP-1/mPsf membranes and the lower graph showing CO2 separation performance of MMP-3/mPsf membranes.
Detailed Description
The technical solution of the present invention is further described below by means of several specific examples.
Example 1:
a method for preparing a high-performance porous coordination polymer film, which is characterized by comprising the following steps:
(1) With 1.166g (5.0 mmol) ZrC l 4 And 1.00g (5.0 mmol) of 4-chloroisophthalic acid, were successfully synthesized to form a chlorine-induced porous coordination polymer (4-C l-PCP).
(2) The chlorine-induced porous coordination polymer (5-C l-PCP) was successfully synthesized using 1.166g (5.0 mmo l) ZrC l 4 and 1.00g (5.0 mmo l) 5-chloroisophthalic acid.
(3) A bromine-induced porous coordination polymer (4-Br-PCP) was successfully synthesized using 1.166g (5.0 mmol) of ZrC l 4 and 1.23g (5.0 mmol) of 4-bromoisophthalic acid.
(4) A bromine-induced porous coordination polymer (5-Br-PCP) was successfully synthesized using 1.166g (5.0 mmol) of ZrC l 4 and 1.23g (5.0 mmol) of 5-bromoisophthalic acid.
(5) With 1.166g (5.0 mmol) ZrC l 4 And 0.83g (5.0 mmol) of isophthalic acid, to successfully synthesize a halogen-free porous coordination polymer (N-PCP).
Example 2:
a method for preparing a high-performance porous coordination polymer film, which is characterized by comprising the following steps:
(1) Cu < 2+ > (CH 3 COO-) 2 (0.9 g) was dissolved in 10m l deionized water and 3.6g of acetylclofenac was dissolved in 300m l acetone. The two solutions were mixed together while stirring for 5 minutes. Then, 0.21g PVAm (Mw 10-15 kDa) was dissolved in 50m l deionized water, and an aqueous PVAm solution was added to the above mixture, followed by stirring for 5 mIn. The reaction was then allowed to stir at 30 ℃ for 10 hours. Finally, the dispersion was washed 3 times with H2O, dimethylformamide (DMF) and methanol and dried at 80℃to give pale green MMP-1 crystals.
(2) Cu < 2+ > (CH 3 COO-) 2 (0.9 g) was dissolved in 10m l deionized water and 3.6g of acetylclofenac was dissolved in 300m l acetone. The two solutions were mixed together while stirring for 5 minutes. Then, 0.21g PVAm (Mw 25-30 kDa) was dissolved in 50m l deionized water, and an aqueous PVAm solution was added to the above mixture, followed by stirring for 5 mIn. The reaction was then allowed to stir at 30 ℃ for 10 hours. Finally, the dispersion was washed 3 times with H2O, dimethylformamide (DMF) and methanol and dried at 80℃to give pale green MMP-2 crystals.
(3) Cu < 2+ > (CH 3 COO-) 2 (4.8 g) was dissolved in 200m l deionized water, and 3.25g of 4-chloroisophthalic acid was dissolved in 375m l acetone. The two solutions were mixed together while stirring for 5 minutes. Then, 0.7g PE I (Mw 10 kDa) was dissolved in 50m l deionized water, and an aqueous PE I solution was added to the mixture, followed by stirring for 5 mIn. The reaction was stirred at 30℃for 6 hours. Finally, the dispersion was washed 3 times with H2O, dimethylformamide (DMF) and methanol and dried at 80℃to give pale green MMP-3 crystals.
(4) Cu < 2+ > (CH 3 COO-) 2 (4.8 g) was dissolved in 200m l deionized water, and 3.25g of 4-chloroisophthalic acid was dissolved in 375m l acetone. The two solutions were mixed together while stirring for 5 minutes. Then, 0.7g PE I (Mw 20 kDa) was dissolved in 50m l deionized water, and an aqueous PE I solution was added to the mixture, followed by stirring for 5 mIn. The reaction was stirred at 30℃for 6 hours. Finally, the dispersion was washed 3 times with H2O, dimethylformamide (DMF) and methanol and dried at 80℃to give pale green MMP-4 crystals.
Example 3:
a method for preparing a high-performance porous coordination polymer film, which is characterized by comprising the following steps:
(1) Coating 0.4wt% of Polydimethylsiloxane (PDMS) and 0.025wt% of polyvinyl alcohol (PVA) on the surface of polysulfone (PSf) with an average pore diameter of 20-50nm to prepare a hydrophilic modified polysulfone (mPsf) membrane surface;
(2) Uniformly mixing hydrophilic polymer polyethylenimine with porous coordination polymer, and coating on the surface of the mPsf film to obtain the H-PCP/PE I/mPsf mixed matrix film.
(3) A solution of 37.5wt% H-PCP/PE I in ethanol/H2O (1:1 vo l) was applied to the mPsf surface using a 100 μm doctor blade and dried in a constant temperature and humidity oven at 30℃with a relative humidity of 40% to prepare a H-PCP/PE I/mPsf mixed matrix film.
Example 4:
a method for preparing a high-performance porous coordination polymer film, which is characterized by comprising the following steps:
(1) 0.25wt% MMP-1 dispersion was coated on an mPsf substrate by an applicator to a wet coating thickness of 50 μm with a precision of + -5 μm, and then dried in a climatic chamber at 30℃and 40% relative humidity for 24h to give an MMP-1/mPsf mixed matrix film.
(2) 0.25wt% MMP-3 dispersion was coated on an mPsf substrate by an applicator to a wet coating thickness of 50 μm with a precision of + -5 μm and then dried in a climatic chamber at 30℃and 40% relative humidity for 24h to give an MMP-3/mPsf mixed matrix film.
The above detailed description is only for the detailed explanation of the technical scheme of the present invention, the present invention is not limited to the above embodiments, and it should be understood that those skilled in the art should not limit the present invention to the above embodiments, but should not limit the scope of the present invention.

Claims (10)

1. A method for preparing a high-performance porous coordination polymer film, which is characterized by comprising the following steps:
(1) By Zr 4+ And halogen substituted functional group X-isophthalic acid, synthesizing a series of halogen induced porous coordination polymers, namely H-PCPs;
(2) Selecting different linear polymers rich in amine, small organic joints and metal ions as reactants to synthesize a series of ordered metal-induced microporous polymers, namely MMPs;
(3) Sequentially coating a polydimethylsiloxane solution and a polyvinyl alcohol solution on the surface of the polysulfone ultrafiltration membrane to obtain an interface layer with high flux and hydrophilicity;
(4) Uniformly mixing the linear polymer rich in amine in the step (2) and the H-PCPS of the porous coordination polymer in the step (1) according to a certain proportion, then coating the mixture on the surface of a modified polysulfone ultrafiltration membrane, and obtaining the H-PCP/PE I/mPsf mixed matrix membrane through an interfacial self-assembly process;
(5) MMPs and aqueous solution are uniformly mixed according to a certain proportion, then the mixture is coated on the surface of a modified polysulfone ultrafiltration membrane, and an MMP/mPsf membrane is prepared by inducing ordered microporous polymers through metals.
2. The method for preparing a high-performance porous coordination polymer film according to claim 1, wherein:
further, in the step (1), the halogen substituted functional group X-isophthalic acid is selected from 4-position or 5-position halogen substituted functional group X-isophthalic acid, X is Cl or Br, the synthesis method adopts a solvothermal method, the reaction temperature of the solvothermal method is 150 ℃, the reaction time is 12 hours, the reactions are all carried out in a polytetrafluoroethylene reaction kettle, the synthesized product is sequentially washed for 3 times by DMF, deionized water and methanol, and finally the target product is obtained by vacuum drying overnight at 100 ℃; a series of halogen-induced porous coordination polymers were synthesized solvothermal, and both polydimethylsiloxane coating and polyvinyl alcohol solution coating were performed at room temperature.
3. The method for preparing a high-performance porous coordination polymer film according to claim 1, wherein:
in the step (2), the linear polymer rich in amine is polyvinyl amine, namely PVAm, or commercial polyethylene imine PE I, and the molecular weight of the commercial polyethylene imine is 10KDa and 20KDa, and two polymers of polyvinyl amine with different molecular weights, namely 10KDa to 15KDa and 25 KDa to 30KDa, are respectively synthesized;
the small organic joint adopts acetyl chloride fenac and 4-chloroisophthalic acid two halogenated carboxylic acid joints;
metal ion selective Cu 2+ (CH3COO - ) 2 Or Zn 2+ (NO3 - ) 2 ·6H 2 O is used as divalent metal ion to produce copper-MMPs or zinc-MMPs respectively.
4. The method for preparing a porous coordination polymer membrane according to claim 1, wherein the porous coordination polymer membrane is sieved according to a polarization ratio, wherein:
in step (2), measuring the rotational mean square diameter of the amine-enriched linear polymer by gel permeation chromatography in combination with a low angle laser scattering detector to adjust the crystal size of MMP;
in the step (2), metal ions are dissolved in water, then small organic joints are added, an acetone solution is poured into the solution to be stirred uniformly, and an aqueous solution of the polymer rich in amine is added into the solution to be stirred uniformly.
5. The method for preparing a high-performance porous coordination polymer film according to claim 1, wherein:
in the step (3), the concentration of the polydimethylsiloxane is 0.4 weight percent, and the polydimethylsiloxane is coated on the surface of the polysulfone ultrafiltration membrane by a scraper and then dried in a constant temperature and humidity box with 40 percent RH at 30 ℃ for at least 1 hour;
in the step (3), the polydimethylsiloxane solution is specifically: 0.2g of polydimethylsiloxane, 0.4g of tetraethoxysilane and 0.4g of dibutyltin dilaurate were mixed with 99g of n-heptane to obtain a 0.2wt% polydimethylsiloxane solution, which was uniformly coated on the surface of the polysulfone membrane by a coater with an accuracy of.+ -. 5. Mu.m, a predetermined wet coating thickness of 50. Mu.m, and then dried in a climatic chamber at 30℃and 40% RH for at least 24 hours.
6. The method for preparing a high-performance porous coordination polymer film according to claim 1, wherein:
in the step (3), the polydimethylsiloxane solution is specifically: mixing 0.2g of polydimethylsiloxane, 0.4g of tetraethoxysilane and 0.4g of dibutyltin dilaurate with 99g of n-heptane to obtain a 0.2wt% polydimethylsiloxane solution, uniformly coating the 0.2wt% polydimethylsiloxane solution on the surface of the polysulfone membrane by a coater with an accuracy of + -5 μm, a preset wet coating thickness of 50 μm, and then drying in a climatic chamber at 30 ℃ and 40% rh for at least 24 hours;
in the step (3), the concentration of the polyvinyl alcohol solution is 0.1%, 0.1wt% of the polyvinyl alcohol solution is coated on a polydimethylsiloxane modified polysulfone substrate, the thickness of a preset wet coating is 50 mu m, the precision is +/-5 mu m, and the film is dried in a climatic chamber at 30 ℃ and 40% RH to obtain the mPsf film with a hydrophilic surface.
7. The method for preparing a high-performance porous coordination polymer film according to claim 1, wherein:
in the step (4), the polyvinyl alcohol has a linear structure and a molecular weight of 70000, and a certain proportion of H-PCP/PEI ethanol/H 2 Uniformly coating the O solution on the surface of the mPsf film, and drying in a constant temperature and humidity box with the relative humidity of 40% at the temperature of 30 ℃ to prepare the H-PCP/PEI/mPsf mixed matrix film; when the filler content is 37.5wt%, the prepared porous coordination polymer membrane, namely the H-PCP/PEI/mPsf mixed matrix membrane material has optimal performance.
8. The method for preparing a high-performance porous coordination polymer film according to claim 1, wherein:
in the step (5), uniformly coating 0.25wt% of MMP dispersion on an mPsf substrate, wherein the thickness of the coating is 50 mu m, the precision of the coating is +/-5 mu m, and then drying in a climatic chamber at 30 ℃ and 40% RH to prepare the MMP/mPsf film;
MMP at a concentration of 0.25wt% was uniformly coated and an area greater than 100cm 2 The MMP/mPsf film surface and cross-section are uniformly distributed.
9. The method for preparing a high-performance porous coordination polymer film according to claim 1, wherein:
the prepared porous coordination polymer membrane H-PCP/PEI/mPsf mixed matrix membrane is used for gas separation, in particular for Gao Jihua-rate hydrocarbon alkane gas and low-polarization rate H 2 Separation between.
10. The method for preparing a high-performance porous coordination polymer film according to claim 1, wherein:
the prepared large-area ultrathin defect-free MMP/mPsf film and the size of the MMP/mPsf film is more than 100cm 2 For gas separation, in particular CO 2 /N 2 Separation between.
CN202211612028.1A 2022-12-03 2022-12-03 Preparation method of high-performance porous coordination polymer membrane Pending CN116173749A (en)

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Publication number Priority date Publication date Assignee Title
CN101816924A (en) * 2010-04-13 2010-09-01 东南大学 Metal organic framework material used for absorbing and separating CO2 and preparation method thereof
CN111744375A (en) * 2020-07-21 2020-10-09 天津工业大学 Mixed matrix membrane with high-selectivity gas channel and preparation method thereof
CN113893707A (en) * 2021-09-25 2022-01-07 天津工业大学 C1-C4Mixed matrix membrane with preferential permeation of hydrocarbon, preparation method and application thereof

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CN101816924A (en) * 2010-04-13 2010-09-01 东南大学 Metal organic framework material used for absorbing and separating CO2 and preparation method thereof
CN111744375A (en) * 2020-07-21 2020-10-09 天津工业大学 Mixed matrix membrane with high-selectivity gas channel and preparation method thereof
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