CN113337095B - Self-polymerization microporous polymer fluorinated membrane and preparation method and application thereof - Google Patents
Self-polymerization microporous polymer fluorinated membrane and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a self-polymerization microporous polymer fluorinated membrane and a preparation method and application thereof, belonging to the field of polymer modification. The self-polymerization microporous polymer fluorinated membrane provided by the invention is obtained by directly carrying out hydrogen element substitution reaction on the surface of the self-polymerization microporous polymer membrane by using fluorine elements in fluorine-nitrogen mixed gas. The self-polymerization microporous polymer membrane provided by the invention forms a uniform polymer fluorinated layer on the surface of the polymer by using fluorine gas to sweep, and the size of the pore channel of the self-polymerization microporous polymer membrane is accurately regulated and controlled by using the substitution of fluorine element on hydrogen element on the polymer, so that the helium permeability and the helium/methane and helium/nitrogen selectivity of the self-polymerization microporous polymer are obviously improved, and the obtained self-polymerization microporous polymer fluorinated membrane has ideal helium/methane selectivity which can exceed 3000.
Description
Technical Field
The invention belongs to the field of polymer modification, and particularly relates to a self-polymerization microporous polymer fluorinated membrane, and a preparation method and application thereof.
Technical Field
Helium, also known as "gold gas," is a non-renewable resource that has very low melting point (-272 ℃), density (0.1786g/L), viscosity, and chemical stability, which are essential strategic resources for the military industry and high-tech industries. The method is widely applied to the fields of nuclear magnetism, medical CT, space launching, missile industry, high-precision welding, nuclear industry and the like. Most of helium used in China is imported from America, Kataler, Australia and the like, the external dependency degree reaches more than 90%, and the helium becomes a bottleneck problem in China. The major source of helium in the world is associated gas extracted from natural gas. The annual natural gas production in China breaks through 1500 billions of cubic meters per year, the average helium content is about 0.2 percent, the theoretical content of helium is about 5 ten thousand tons, and the theoretical content is more than 10 times of the current requirement (about 4000 tons) of China. The most main reason for the large gaps of helium in China is that the extraction technology of helium in low-abundance helium-containing natural gas in China is immature. Therefore, the development of an advanced helium enrichment technology for accurately separating helium in natural gas in China reduces the extraction cost of helium, and has very important significance for national defense and military industry, high and new technology industries and the like in China.
Currently, the most major challenge in natural gas stripping helium is how to obtain more than 99.99% helium from low-abundance helium (-0.2%) helium and further improve recovery. The traditional cryogenic rectification method and the pressure swing adsorption method consume huge energy and have extremely high cost if helium is extracted efficiently under the condition of extremely low helium concentration. The membrane separation method utilizes the difference of the transmission speed of helium and methane in the membrane to selectively sieve the helium and the methane. Enrichment of helium at low concentrations has a very significant advantage. However, in terms of the present, the most major challenge of the membrane separation method for preparing helium is that the permeability of an absolute part of polymer membrane material to helium is low, and meanwhile, the selectivity of helium/methane is difficult to reach the separation requirement (helium/methane selectivity > 1000). Therefore, if the above problems can be effectively solved, it would be of great significance to solve the problems encountered in the stripping of helium from natural gas.
Disclosure of Invention
The invention provides a self-polymerization microporous polymer fluorinated membrane and a preparation method and application thereof, the method utilizes the substitution of fluorine element on hydrogen element on a polymer to accurately regulate and control the size of a polymer pore passage, and can obviously improve the helium permeability and the helium/methane and helium/nitrogen selectivity of the self-polymerization microporous polymer, so that the obtained self-polymerization microporous polymer fluorinated membrane has ideal helium/methane selectivity.
In order to solve the technical problems, the invention provides a self-polymerization microporous polymer fluorinated membrane which is obtained by directly carrying out hydrogen element substitution reaction on the surface of the self-polymerization microporous polymer membrane by using fluorine elements in a fluorine-nitrogen mixed gas.
According to the scheme, the fluorine atoms can effectively regulate and control the pore structure of the microporous polymer, so that the membrane material is directly fluorinated in situ, methane molecules are difficult to permeate the polymer membrane material, and He can easily permeate the polymer membrane material, so that the application prospect of the self-polymerization microporous polymer fluorinated membrane in the field of gas separation, particularly helium separation and hydrogen separation in the field of natural gas helium stripping can be effectively improved.
Preferably, the substitution ratio of hydrogen element is 0.01 to 100%.
Preferably, the surface of the self-polymerization microporous polymer membrane is fluorinated for 10s to 20h by using a fluorine-nitrogen mixed gas under the conditions of the fluorination temperature of-80 to 100 ℃ and the pressure of the fluorination gas under the negative pressure of 0.1 to 500kPa, wherein the fluorine gas proportion in the fluorine-nitrogen mixed gas is 0.01 to 100 percent. It is understood that the fluorination temperature may be-70 deg.C, -60 deg.C, -50 deg.C, -40 deg.C, -30 deg.C, -20 deg.C, -10 deg.C, 0 deg.C, 10 deg.C, 20 deg.C, 30 deg.C, 40 deg.C, 50 deg.C, 60 deg.C, 70 deg.C, 80 deg.C, 90 deg.C or any value within the above range depending on the actual reaction conditions; the pressure condition may be a negative pressure of 1kPa, 2kPa, 3kPa, 5kPa, 10kPa, 20kPa, 30kPa, 40kPa, 50kPa, 60kPa, 70kPa, 80kPa, 90kPa, 100kPa, 150kPa, 200kPa, 250kPa, 300kPa, 350kPa, 400kPa, 450kPa, or any value within the above range; the fluorination time can also be 30s, 1min, 10min, 20min, 30min, 40min, 50min, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h or any point value in the range; the fluorine gas may be added in a proportion of 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or any value within the above range.
Preferably, the self-polymerized microporous polymer has the following general formula (I):
specifically, any one of the following:
in the above polymers a to k, R1Any one selected from hydrogen, halogen and methyl; r2Any one selected from hydrogen, methyl, ethyl and trifluoromethyl; r3Any one selected from hydrogen, halogen, methyl, ethyl, propyl, isopropyl, butyl, aromatic group and trifluoromethyl; r4Selected from any one of hydrogen, halogen, methyl, ethyl, propyl, isopropyl, butyl, aromatic group and trifluoromethyl.
It will be appreciated that the fluorination process using the self-polymerized microporous polymer of formula (I) above is as follows:
preferably, the self-polymerized microporous polymer is a self-polymerized microporous polyimide and has the following general formula (II):
in the above formula, a is selected from any one of the following:
in the above polymers l to v, R is selected from H, a halogen selected from any one of fluorine, chlorine, bromine and iodine, and has CxH2x+1Or CxH2x-1Alkyl of formula (la) wherein x is 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12), aryl CnH2n-6Wherein n is any one of 6, 7, 8, 9 or 10;
in the above formula, B is selected from any one of the following:
in the above-mentioned polymer w-h', R1Any one selected from hydrogen, methyl and hydroxyl; r2Any one selected from hydrogen, halogen, methyl, ethyl, propyl and butyl; r is3Any one selected from hydrogen, halogen, methyl, ethyl, propyl, butyl, phenyl, substituted phenyl and naphthyl; r4Selected from isopropyl, 6 fluoroisopropyl, sulfone group and carbonyl group.
It will be appreciated that the fluorination process using the self-microporous polyimide of formula (II) above is as follows:
preferably, the self-polymerized microporous polymer membrane is selected from any one of a homogeneous membrane prepared by a solvent evaporation method, a heterogeneous flat membrane prepared by a non-solvent phase inversion method, and a hollow fiber gas separation membrane prepared by a hollow spinning technique, and has a membrane structure as shown in fig. 1.
The invention also provides a preparation method of the self-polymerization microporous polymer fluorinated membrane according to any one of the technical schemes, which comprises the step of fluorinating the surface of the self-polymerization microporous polymer membrane for 10s-20h by using mixed fluorine and nitrogen gas under the conditions of fluorination temperature of-80-100 ℃ and fluorination gas pressure of 0.1kPa-500kPa, wherein the fluorine gas proportion in the mixed fluorine and nitrogen gas is 0.01-100%.
The invention also provides application of the self-polymerization microporous polymer fluorinated membrane in extracting helium from natural gas according to the technical scheme.
Preferably, the helium/nitrogen selectivity of the obtained self-polymerization microporous polymer fluorinated membrane is between 4 and 1000, and the helium/methane selectivity is between 3 and 5000.
The invention also provides a fluorination system for implementing the fluorination modification method according to any one of the technical schemes, as shown in figure 2, and the fluorination system comprises the following steps: the device comprises a fluorine-nitrogen mixed gas source channel, a nitrogen gas source channel, a gas flow control unit, a fluorination reaction kettle and a tail gas absorption unit.
The fluorine-nitrogen mixed gas is introduced into the fluorine-nitrogen mixed gas source channel, wherein the proportion of the mixed gas can be 0.01-100%, nitrogen is introduced into the nitrogen gas source channel and is mainly used for diluting the fluorine gas content in a reaction system, and the flow of the two gas sources is controlled by a mass flow meter MFC. And (3) putting a film to be fluorinated into a fluorination reaction kettle, controlling the temperature outside the reaction kettle by adopting constant-temperature water bath, and monitoring the pressure of mixed gas inside the reaction kettle by using a pressure gauge. And the fluorinated tail gas enters a tail gas absorption unit through the control of a valve so as to control the pressure in the fluorination reaction kettle.
The invention has the following beneficial effects:
the invention provides a self-polymerization microporous polymer fluorinated membrane and a preparation method thereof, wherein a uniform polymer fluorinated layer is formed on the surface of a polymer by sweeping fluorine gas, and hydrogen on the polymer is replaced by helium by fluorine
And methane
The size of the pore channel is accurately regulated and controlled, and the helium permeability and the helium/methane and helium/nitrogen selectivity of the self-polymerization microporous polymer are obviously improved, so that the obtained self-polymerization microporous polymer fluorinated membrane has ideal helium/methane selectivity which can exceed 3000 (example 1).
Drawings
FIG. 1 is a schematic diagram of a membrane structure that can be fluorinated in situ using the present invention;
FIG. 2 is a schematic diagram of a fluorination apparatus utilizing the present invention;
FIG. 3: the fluorinated PIM-1 and the reported separation capacities of helium/methane, helium/nitrogen, hydrogen/methane and helium/carbon dioxide of the polymer are shown, wherein a is a separation performance graph of helium/methane before fluorination and after fluorination, b is a separation performance graph of hydrogen/methane before fluorination and after fluorination, c is a separation performance graph of helium/nitrogen before fluorination and after fluorination, and d is a separation performance graph X of helium/carbon dioxide before fluorination and after fluorination.
Detailed Description
Example 1: preparation method of fluorinated PIM-1 membrane material (corresponding to polymer a, R1 is hydrogen)
Preparing a casting solution: weighing 0.2g of PIM-1 powder, dissolving the powder in 20mL of chloroform, stirring for 10h, filtering insoluble impurities by using a PVDF (polyvinylidene fluoride) filter membrane of 0.45 mu m, and preparing a PIM-1 homogeneous membrane with the thickness of about 45 mu m by adopting a solvent volatilization mode;
preparation of the fluorination at the beginning: putting the PIM-1 film which is dried in vacuum and has the diameter of 15mm into a fluorination reaction chamber, and exhausting air in the fluorination reaction chamber through nitrogen;
fluorination of PIM-1 films: and (3) introducing a fluorine-nitrogen mixed gas (fluorine gas volume is 5%) into the fluorination reaction chamber according to the proportion to ensure that the mixed gas pressure in the fluorination reaction chamber reaches 3bar, and fluorinating the PIM-1 at the room temperature of 20 ℃ for 1-30 min.
Post-treatment of fluorinated tail gas: discharging the high-pressure mixed gas in the reaction chamber through a tail gas treatment unit, absorbing the discharged unreacted fluorine gas by using alkali liquor, continuously introducing nitrogen into the fluorination reaction chamber to ensure that the fluorine gas is completely discharged, and opening the fluorination reaction chamber to obtain the fluorinated PIM-1.
Table 1: helium, methane permeability and He/CH of PIM-1 after fluorination4Ideal selectivity of
aData were derived from the literature sciences 2013,339, 303;
bdata are derived from the documents adv.mater.2014,26,3688;
cdata are from literature polymer2016,101,225;
ddata are from nat. mater.2017,16,932;
edata are derived from the documents j.membr.sci.2014,457, 95;
fdata are derived from the literature energyenviron.sci.2019,12,2733;
gdata are from document j.mater.chem.a2018,6,5661;
hdata are from Macromolecules2018,51,2489;
idata are derived from the documents j.membr.sci.2011,383, 70;
jdata are from document j.mater.chem.a2018,6,652;
kdata are from the literature Macromolecules2015,49,280;
lthe data are from the literature Ind.&Eng.Chem.1965,57,49；
mData are derived from the documents j.polym.sci.polym.phys.1999,37,1235;
ndata are from Polymer1991,32,840;
odata are derived from the documents j.polym.sci.pol.phys.1987,25,1999;
ptransmittance: unit Barrer, 1Barrer ═ 10-10cm3cmcm-2s-1cmHg-1；
qThe result of ideal selectivity is equal to the ratio of the two transmittances.
Fig. 3 shows the separation capacities of helium/methane (a), helium/nitrogen (c), hydrogen/methane (b), helium/carbon dioxide (d) of the above fluorinated PIM-1 and the reported polymers, wherein the impurities not only include methane but also may include carbon dioxide and nitrogen during the helium concentration process, and it can be seen from the selectivity of the above fluorinated polymer for ultra-high helium/methane, helium/nitrogen and helium/carbon dioxide that the above impurities have a smaller effect on the helium concentration with the film material.
In addition, with respect to current helium separation, polymer membrane materials can be divided into three categories, the first category being traditional polymers represented by polypyrrolone (PPY), which generally have very low helium permeability (below 100 Barrer); the second type is self-polymerization microporous polymer membrane material, the helium permeability of the material of the type is generally above 500Barrer, but the helium/methane selectivity is generally below 20, and the enrichment of helium in low-concentration helium-containing natural gas cannot be met; the third class is perfluorinated polymers, which exhibit high helium permeability and helium/methane selectivity, but which still present problems in mass production.
However, unlike the above-mentioned existing membrane material, the fluorinated PIM-1(FPIM-1) provided in this embodiment has the following advantages:
1: the helium permeability of FPIM-1 relative to PIM-1 reduces the helium permeability, but the selectivity of the helium/methane, helium/nitrogen and other gas pairs is far greater than that of the traditional polymer and some novel perfluorinated polymers;
2: the conditions of the direct fluorination self-polymerization microporous polymer and the self-polymerization microporous polyimide are mild and controllable;
3: the direct fluorination of the self-polymerization microporous polymer can obviously improve the helium/methane separation performance of the polymer membrane.
Example 2: fluorinated PIM-1 prepared in example 1 improves separation performance of helium/methane mixture
FPIM-1 is put into a fluorination reaction device, a helium/methane (0.6/99.4) mixed gas is used for simulating a natural gas containing real helium, and the separation capability of the mixed gas is tested by a method of changing the upstream pressure. The helium content of the gas mixture can be tested. The results are shown in Table 2:
table 2: separation Performance of helium/nitrogen mixture of FPIM-1
aHelium permeability, unit Barrer, 1Barrer ═ 10-10cm3cmcm-2s-1cmHg-1。bHelium/methane selectivity, the result of which is the ratio of the helium/methane peak areas obtained in the gas chromatograph multiplied by its correction factor.
Table 2 above shows that fluorinated PIM-1 membranes still show very good selectivity with a helium/methane mixture. Under actual conditions of natural gas stripping with helium, the operating pressure is generally high, and we find that the external pressure is 20 atmospheres in time, and the content of helium is close to the content of the helium in a real state. The helium/methane selectivity of the fluorinated PIM-1 can still reach over 869, and the helium content permeating through the membrane is still over 85 percent, so that a very good helium enrichment effect is achieved. And shows its highly efficient ability to extract helium resources from low concentration helium-containing natural gas.
Example 3: preparation of fluorinated membrane of self-polymerized microporous polyimide PIM-PI-1 (corresponding to polyimide synthesized by U + W polymer, wherein R is hydrogen and R1 site methyl) and helium separation performance thereof
Preparing a casting solution: weighing 0.2g of PIM-PI-1 powder, dissolving the powder in 20mL of chloroform, stirring for 12 hours, filtering insoluble impurities by using a 0.45 mu m PVDF filter membrane, and preparing a PIM-PI-1 homogeneous membrane by adopting a solvent volatilization mode;
preparation of the fluorination at the beginning: the same as example 1;
fluorination of PIM-PI-1 films: introducing a fluorine-nitrogen mixed gas (10% of the volume of fluorine gas) into the fluorination reaction chamber according to the proportion, allowing the fluorine-nitrogen to flow in the reaction chamber for 60s, and fluorinating the PIM-PI-1 for 1min under the atmospheric pressure of 1 atmosphere;
post-treatment of fluorinated tail gas: and (3) discharging tail gas in the reaction chamber through a treatment device, continuously introducing nitrogen into the fluorination reaction chamber after the fluorination reaction is finished, ensuring that fluorine gas is thoroughly removed, and opening the fluorination reaction chamber to obtain the fluorinated PIM-PI-1.
TABLE 3 He methane Permeability and Ideal gas Selectivity of fluorinated PIM-PI-1
aHelium permeability, unit Barrer, 1Barrer is 10-10cm3cmcm-2s-1cmHg-1。bHelium/methane selectivity is the ratio of the permeability of pure gas.
As can be seen from Table 3, the helium permeability of the fluorinated self-polymerized microporous polyimide (PIM-PI-1) reaches 590Barrer, and the helium/methane selectivity reaches 634. Is a very potential helium separation material. The performance of the polymer membrane material exceeds that of most of the reported polymer membrane materials (Table 1).
Example 4: preparation of fluorinated membrane of PIM-Trip-PI (polyimide synthesized by corresponding polymer I + D, wherein R1, R2 and R3 are all hydrogen) and helium separation performance thereof
Preparing a casting solution: weighing 0.2g of PIM-Trip-PI powder, dissolving the powder in 20mL of chloroform, stirring for 8h, filtering insoluble impurities by using a PVDF (polyvinylidene fluoride) filter membrane of 0.45 mu m, and preparing a PIM-Trip-PI homogeneous membrane by adopting a solvent volatilization mode;
preparation of the fluorination at the beginning: the same as example 1;
fluorination of PIM-Trip-PI films: introducing mixed fluorine-nitrogen gas (fluorine gas volume is 5%) into the fluorination reaction chamber according to the proportion, allowing the fluorine-nitrogen gas to flow in the reaction chamber for 180s, and fluorinating the PIM-Trip-PI for 1min under 1 atmosphere;
post-treatment of fluorinated tail gas: and (3) discharging tail gas in the reaction chamber through a treatment device, continuously introducing nitrogen into the fluorination reaction chamber after the fluorination reaction is finished, ensuring that fluorine gas is thoroughly removed, and opening the fluorination reaction chamber to obtain the fluorinated PIM-Trip-PI.
TABLE 4 He, CH of fluorinated PIM-Trip-PI4Permeability and desired gas selectivity
aHelium permeability, unit Barrer, 1Barrer ═ 10-10cm3cmcm-2s-1cmHg-1。bHelium/methane selectivity is the ratio of the permeability of pure gas.
It can be seen that the helium permeability of the fluorinated self-polymerized microporous polyimide (FPIM-Trip-PI-1) reaches 179Barrer, and the helium/methane selectivity reaches 597. Compared with FPIM-1 and FPIM-PI-1, the transmission rate is obviously reduced, but the material is still a helium separation material with very high potential. The performance of the polymer membrane material exceeds that of most of the reported polymer membrane materials (Table 1).
Claims (3)
1. A self-polymerizing microporous polymer fluorinated membrane, wherein the self-polymerizing microporous polymer is selected from any one of the following:
in the above polymers a to k, R1Any one selected from hydrogen, halogen and methyl; r2Any one selected from hydrogen, methyl, ethyl and trifluoromethyl; r3Any one selected from hydrogen, halogen, methyl, ethyl, propyl, isopropyl, butyl, aromatic group and trifluoromethyl; r4Any one selected from hydrogen, halogen, methyl, ethyl, propyl, isopropyl, butyl, aromatic group and trifluoromethyl; or
The self-polymerization microporous polymer is self-polymerization microporous polyimide and has the following general formula (II):
in the above formula, a is selected from any one of the following:
in the polymer l to v, R is selected from H, a halogen selected from any one of fluorine, chlorine, bromine and iodine, and has CxH2x+1Alkyl of the formula (II) in whichx is 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, or CxH2x-1Alkenyl or cycloalkyl of formula (la) wherein x is 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, or aryl CnH2n-6Wherein n = any one of 6, 7, 8, 9, or 10;
in the above formula, B is selected from any one of the following:
in the above-mentioned polymer w-h', R1Any one selected from hydrogen, methyl and hydroxyl; r2Any one selected from hydrogen, halogen, methyl, ethyl, propyl and butyl; r3Any one selected from hydrogen, halogen, methyl, ethyl, propyl, butyl, phenyl, substituted phenyl and naphthyl; r4Any one selected from isopropyl, 6-fluoroisopropyl, sulfone group and carbonyl group;
the self-polymerization microporous polymer fluorinated membrane is prepared by adopting the following method:
the self-polymerization microporous polymer membrane is obtained by directly carrying out hydrogen element substitution reaction on the surface of the self-polymerization microporous polymer membrane by using fluorine elements in a fluorine-nitrogen mixed gas, wherein the substitution proportion of the hydrogen elements is 0.01-100%;
specifically, fluorinating the surface of the self-polymerization microporous polymer membrane for 10s-20h by using a fluorine-nitrogen mixed gas under the conditions of fluorination temperature of-80-100 ℃ and fluorination gas pressure of 0.1-500 kPa, wherein the fluorine gas proportion in the fluorine-nitrogen mixed gas is 0.01-90%.
2. The self-polymerization microporous polymer fluorinated membrane according to claim 1, wherein the self-polymerization microporous polymer membrane is selected from any one of a homogeneous membrane prepared by a solvent evaporation method, a heterogeneous flat membrane prepared by a non-solvent phase inversion method, and a hollow fiber gas separation membrane prepared by a hollow spinning technique.
3. Use of the self-polymerizing microporous polymeric fluorinated membrane of claim 1 or 2 in stripping helium from natural gas.
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| CN106633033A (en) * | 2016-11-30 | 2017-05-10 | 大连理工大学 | Intrinsic microporous copolymer containing phthalazinone biphenyl structure and preparation method thereof |
| CN106861446A (en) * | 2015-12-12 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of microporous polymer membranes, its preparation method and application |
| CN108854604A (en) * | 2017-05-08 | 2018-11-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | A kind of polymeric membrane for separation, preparation method and application |
| CN110869107A (en) * | 2017-07-07 | 2020-03-06 | 沙特阿拉伯石油公司 | Multilayer aramid thin film composite membrane for separating gas mixtures |
| CN112646170A (en) * | 2020-12-21 | 2021-04-13 | 山东大学 | Chiral self-possessed microporous polymer and preparation method and application thereof |
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2021
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106861446A (en) * | 2015-12-12 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of microporous polymer membranes, its preparation method and application |
| CN106633033A (en) * | 2016-11-30 | 2017-05-10 | 大连理工大学 | Intrinsic microporous copolymer containing phthalazinone biphenyl structure and preparation method thereof |
| CN108854604A (en) * | 2017-05-08 | 2018-11-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | A kind of polymeric membrane for separation, preparation method and application |
| CN110869107A (en) * | 2017-07-07 | 2020-03-06 | 沙特阿拉伯石油公司 | Multilayer aramid thin film composite membrane for separating gas mixtures |
| CN112646170A (en) * | 2020-12-21 | 2021-04-13 | 山东大学 | Chiral self-possessed microporous polymer and preparation method and application thereof |
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