CN111375390A - Ultramicropore ionic polymer material and preparation method and application thereof - Google Patents

Ultramicropore ionic polymer material and preparation method and application thereof Download PDF

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CN111375390A
CN111375390A CN202010235304.1A CN202010235304A CN111375390A CN 111375390 A CN111375390 A CN 111375390A CN 202010235304 A CN202010235304 A CN 202010235304A CN 111375390 A CN111375390 A CN 111375390A
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邢华斌
锁显
崔希利
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Zhejiang University ZJU
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Abstract

The invention discloses a hyperbranched ionic liquid-based ultramicropore ionic polymer material, a preparation method thereof and an alkyne/alkene separation application thereof. The ultramicropore ionic polymer material has the characteristics of high anion density and narrow pore size distribution, and the structural property of the ultramicropore ionic polymer material is regulated and controlled by changing a hyperbranched structure and the types of anions and cations. The acetylene and the propyne are separated in high selectivity by utilizing a strong hydrogen bond environment and size screening effect constructed by high anion density, so that the alkyne in the alkyne and alkene mixed gas is removed to a very low degree, and the alkene gas with extremely low alkyne content is obtained. The material prepared by the method has high stability, is simple to prepare, has strong controllability of material structural properties, good adsorption performance, easy desorption, environmental friendliness and good industrial application prospect.

Description

Ultramicropore ionic polymer material and preparation method and application thereof
Technical Field
The invention relates to the technical field of high molecular materials, in particular to an ultramicropore ionic polymer material and a preparation method and application thereof.
Background
The separation of alkynes/alkenes is an important separation process in the petrochemical industry. Ethylene is a basic raw material of three major synthetic materials, is called as the mother material of petrochemical industry, and has the global yield of more than 1.7 hundred million tons in 2016. In industry, the content of acetylene impurities inevitably generated in the production process of steam cracking and the like is about 0.1-1% (mole fraction), and the existence of trace acetylene can cause catalyst deactivation and even explosion in the polymerization process, so that acetylene is required to be removed to 0.05ppm as required by the production of downstream polyethylene. The industrial acetylene and ethylene separation method mainly comprises a selective catalytic hydrogenation method, a solvent absorption method, an adsorption method, a cryogenic separation method and the like. For example, the selective catalytic hydrogenation method (such as CN102898266A, CN108147938A) uses noble metal catalyst, the production cost is high, and the ethylene also undergoes hydrogenation reaction to reduce the yield; acetylene adsorbed on the surface of the catalyst is also easy to be subjected to hydrogenation polymerization, so that the activity of the catalyst is reduced.
The separation of propyne propylene is of great significance, the global production capacity of propylene in 2017 is over 1.2 million tons, the carbon-three fraction contains propylene and 1-7% of propyne, the content of propyne is required to be less than 5ppm for general polymerization-grade propylene, and the content of propyne is required to be even less than 1ppm for the newly developed propylene polymerization catalyst. The propyne is separated mainly by adopting catalytic hydrogenation and low-temperature rectification processes, and the defects of high energy consumption, low selectivity and the like exist.
Therefore, the method can realize the high-selectivity separation of alkyne and olefin by adopting a green low-energy-consumption adsorption separation mode, and has important industrial and scientific significance. In recent years, relevant research focuses on the separation of alkynes and alkenes by using Metal Organic Frameworks (MOFs) (Science 2016,353, 141-144; CN108671893A, CN108014751A, CN109153005A), but MOFs are generally difficult to ensure stability, structure and performance are not easy to maintain for a long time, metal ions are introduced, synthesis and purification costs are high, and the application of MOFs in industry is limited.
As a novel green solvent, the ionic liquid has the advantages of low vapor pressure, low toxicity, high thermal stability, easy regulation and control of structure and function and the like, and shows excellent performance in the aspect of alkyne and alkene separation at present. For example, the research results of Zhao et al (AIChEJ 61 (6); 2016-2027) show that the ionic liquid of quaternary phosphine cations and long-chain fatty acid radical anions has strong hydrogen bond recognition capability, and the selectivity can reach 2-5 times of that of the conventional solvent. However, the ionic liquid has low absorption capacity, and has the defects of high viscosity, slow mass transfer, difficult recovery and the like due to the essential characteristics of liquid molten salt at room temperature.
The porous ionic liquid polymer has the advantages of both the ionic liquid and the porous polymer, and the pore structure and the hydrogen bond alkalinity of the material are regulated and controlled according to the small difference between the size of alkyne olefin molecules and the hydrogen bond acidity, so that the defects of the ionic liquid are overcome. The ultramicropore ionic liquid polymer is designed and prepared, and a new path is expected to be opened up for the adsorption and separation of alkyne and olefin.
Disclosure of Invention
Aiming at the defects in the field, the invention provides a super-microporous ionic polymer material, which is a super-branched ionic liquid monomer-based super-microporous ionic material with high anion density and narrow pore size distribution and can be used for high-selectivity separation of acetylene/ethylene mixed gas and propyne/propylene mixed gas.
A kind of ultramicropore ionic polymer material is obtained by polymerization of hyperbranched ionic liquid; the hyperbranched ionic liquid consists of a hyperbranched benzene ring framework and a cation M+And the anion N-The structure of the three parts is shown in the following formulas (1) to (5):
Figure BDA0002430754520000021
wherein R is1～R8Each independently selected from one of H and alkyl;
the cation M+Is one of imidazole cation, quaternary ammonium cation and quaternary phosphine cation, and the structures are respectively shown in formulas (I) to (III) as follows:
Figure BDA0002430754520000022
wherein m is an integer of 0-3, R9Is a polymerizable group, R10～R12Are respectively and independently selected from one of H, alkyl and aromatic hydrocarbon group, and R10～R12At least one of the hyperbranched polymers is connected with the hyperbranched benzene ring skeleton through covalent bonds;
the anion N-Is halogen ion, thiocyanate ion (SCN)-) Dicyandiamide ion (N (CN)2 -) Tetrafluoroborate ion (BF)4 -) Hexafluorophosphate ion (PF)6 -) Hexafluorosilicate ion (SiF)6 2-) Bis (trifluoromethylsulfonyl) imide ion (Tf)2N-) Trifluoromethanesulfonate ion (CF)3SO3 -) Sulfate ion (SO)4 2-) Formate ion (COO)-) Acetate ion (CH)3COO-) Any one of them.
The ultramicropore ionic material can selectively adsorb alkyne and exclude olefin, thereby removing alkyne in mixed gas to a very low degree and obtaining olefin gas with very low alkyne content (less than 1 ppm). In addition, the method can also obtain alkyne with higher purity, and realize high-efficiency utilization of the alkyne.
The invention can realize the construction of ultramicropore structure and the regulation and control of the hydrogen bond recognition capability of anions by changing the hyperbranched degree, introducing different rigid frameworks and changing the species of anions and cations, realize the exclusion of olefin molecules by size screening and strengthen the molecule recognition capability, thereby further improving the adsorption selectivity and capacity. Compared with the reported porous polymer material, the ultramicropore ionic polymer shows higher alkyne adsorption separation selectivity and adsorption capacity. Meanwhile, the material shows excellent stability and recycling performance, and is expected to meet the requirement of industrial production.
Preferably, R9Is one of vinyl, styryl, acrylamide and acrylic groups, and the structures of the compounds are respectively shown in the following formulas (A) to (D):
Figure BDA0002430754520000031
wherein R is13And R14Each independently selected from H and alkyl.
The invention takes hyperbranched ionic liquid as a monomer, and can prepare the ultramicropore ionic polymer with high anion density and narrow pore size distribution by regulating and controlling a hyperbranched structure and anion and cation species.
The ultra-microporous ionic polymer material has narrow pore size distribution
Figure BDA0002430754520000032
Is mainly distributed in
Figure BDA0002430754520000033
Preferably, the cation M is+Is one of vinyl imidazole, benzyl imidazole, (methyl) acrylamide (alkyl imidazole), benzyl trialkyl ammonium, (methyl) acrylic acid (trialkyl ammonium) and benzyl trialkyl phosphine;
the anion N-Is any one of halogen ion, tetrafluoroborate ion, hexafluorosilicate ion, formate ion and acetate ion.
The halide ion is preferably Cl-、Br-。
With anion being Br-For example, the preferable structure of the hyperbranched ionic liquid is shown as the following formula (1-1), (2-1), (3-1) and (4-1):
Figure BDA0002430754520000041
the structure of the ultramicropore ionic polymer obtained by polymerization reaction of the hyperbranched ionic liquid with the structural formula shown as (2-1) is shown as figure 1, wherein,
Figure BDA0002430754520000042
is a hyper branched benzene ring framework,
Figure BDA0002430754520000043
is an imidazole cation, and the cationic group of the imidazole,
Figure BDA0002430754520000044
is an anion.
The invention also provides a preparation method of the ultramicropore ionic polymer material, which comprises the following steps:
(a) dissolving the hyperbranched ionic liquid in a mixed solution of a solvent A and water, carrying out polymerization reaction at 70-120 ℃, stirring for 12-48 hours, and filtering to obtain a solid precipitate product; the solvent A is one of N, N-dimethylformamide, methanol, ethanol, acetonitrile and acetone;
(b) and washing the obtained solid precipitate product with water and methanol in sequence to remove unreacted raw materials, and then carrying out vacuum drying at the temperature of 50-100 ℃ for 12-24 hours to obtain the ultramicropore ionic polymer material.
The preparation method of the ultramicropore ionic polymer material is simple, strong in controllability of structural properties, good in stability, excellent in adsorption performance, easy to desorb and regenerate, green and environment-friendly.
Preferably, in the mixed solution of the solvent A and water, the volume ratio of the solvent A to the water is 1-100: 2.
Preferably, the solvent A is a mixed solution of ethanol and water
In the preparation method of the invention, the polymerization reaction temperature is too low and too high, and the stirring reaction time is too short, so that the ultramicropore ionic polymer cannot be obtained. Preferably, the polymerization reaction temperature is 60-100 ℃, and the stirring time is 12-24 hours.
The invention also provides the application of the ultramicropore ionic polymer material in selective adsorption separation of alkyne/alkene, wherein the ultramicropore ionic polymer material is used as an adsorbent, and the adsorbent is contacted with mixed gas containing alkyne/alkene to realize selective separation of alkyne and alkene;
the mixed gas is mixed gas containing acetylene/ethylene or mixed gas containing propyne/propylene.
The contact mode of the adsorbent and the mixed gas can be any one of fixed bed adsorption, fluidized bed adsorption and moving bed adsorption.
Preferably, the temperature of the selective adsorption separation is-5 to 50 ℃, the total pressure of the mixed gas is 100 to 1000kPa, and the content of acetylene or propyne in the mixed gas is 50ppm to 70 vol%.
The ultramicropore ionic polymer material can selectively adsorb alkyne and exclude alkene. The adsorbent of the invention has weak physical acting force with alkyne, and desorption and regeneration are easy.
After selective adsorption and separation, the ultramicropore ionic polymer material adsorbed with alkyne is desorbed to obtain alkyne, and the regeneration of the ultramicropore ionic polymer material is realized.
The temperature of desorption is preferably 25-150 ℃. If the temperature is too high, the alkyne is easy to explode, and if the temperature is too low, the time required for desorption is relatively long.
The pressure of desorption can be 0-100 kPa.
The mixed gas may also contain impurities such as one or more of carbon dioxide, methane, nitrogen, ethane and propane.
After the mixed gas is selectively absorbed and separated, the content of acetylene or propyne is not more than 1 ppm.
Compared with the prior art, the invention has the main advantages that:
1) the invention takes hyperbranched ionic liquid as a monomer to carry out simple polymerization reaction to obtain the ultramicropore ionic polymer; the synthesis method is simple and easy to implement, mild in reaction condition, environment-friendly and easy for industrial implementation; the ultramicropore ionic polymer has the structural characteristics of high stability and shows excellent air and hydrothermal stability;
2) the ultramicropore ionic polymer can fully utilize a strong hydrogen bond environment constructed by high anion density, realize selective recognition of alkyne, realize high selective separation of alkyne/alkene mixed gas and high-capacity adsorption of alkyne, and regulate and control the properties of a material by changing a hyperbranched structure and anion and cation types of hyperbranched ionic liquid;
3) the ultra-microporous ionic polymer can fully utilize narrow-distribution ultra-microporous
Figure BDA0002430754520000051
The separation selectivity of alkyne/alkene is further improved through the size screening effect;
4) the desorption and regeneration are easy, and meanwhile, the material can be regenerated and reused, and the high-efficiency separation selectivity can be still maintained after regeneration.
Drawings
FIG. 1 is a schematic structural diagram of a supermicroporous ionic polymer obtained by polymerization of a hyperbranched ionic liquid with a structural formula shown as (2-1);
FIG. 2 is CO of P (Ph-3MVim-Br) prepared in example 22(195K) And N2(77K) Adsorption isotherm diagram of (a);
FIG. 3 is a graph showing the ultramicropore size distribution of P (Ph-3MVIm-Br) prepared in example 2;
FIG. 4 is a thermogravimetric plot of P (Ph-3MVim-Br) prepared in example 2;
FIG. 5 is an adsorption isotherm plot of P (Ph-3MVIm-Br) separated ethylene/acetylene prepared in example 2 at 298K and at 0-100 kPa;
FIG. 6 is a graph of the breakthrough of the P (Ph-3MVIm-Br) fixed bed prepared in example 2 with a mixed gas of ethylene content 99 vol% and acetylene content 1 vol%;
FIG. 7 is a graph showing the results of cycling the P (Ph-3MVIm-Br) breakthrough curves prepared in example 2, with a mixed gas having an ethylene content of 99 vol% and an acetylene content of 1 vol%;
FIG. 8 is a graph of the breakthrough of the fixed bed of P (Ph-3MVIm-Br) prepared in example 2 with a gas mixture of ethylene content 50 vol% and acetylene content 50 vol%;
FIG. 9 is an adsorption isotherm plot of propylene/propyne for P (Ph-3MVim-Br) separation prepared in example 2 at 298K and at a pressure of 0 to 100 kPa;
FIG. 10 is an adsorption isotherm plot of propylene/propyne for P (Ph-3MVim-Cl) separation prepared in example 3 at 298K and at a pressure of 0 to 100 kPa;
FIG. 11 is a graph showing the breakthrough of a fixed bed of P (Ph-3MVIm-Cl) prepared in example 3, with a mixed gas containing 99 vol% propylene and 1 vol% propyne.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
5g of 1,3, 5-tris (bromomethyl) benzene and 4.35g of vinylimidazole were weighed out, added to 250mL of acetonitrile, mixed and dissolved with stirring, and then heated to 50 ℃ for reaction for 36 hours. The obtained product is filtered and washed by acetonitrile, and then is dried for 24 hours in vacuum at 65 ℃ to obtain a white solid, namely hyperbranched ionic liquid Ph-3MVIm-Br (Ph is a benzene ring group, 3 represents hyperbranched number, MVIm represents 1-vinyl-3 methylimidazole cation, and Br is anion), the molecular structure of which is shown as formula (2-1), and the yield is about 80%.
Figure BDA0002430754520000071
Example 2
1.0g of hyperbranched ionic liquid Ph-3MVIm-Br obtained in example 1 and 0.03g of azobisisobutyronitrile were weighed and added to a mixed solution of 10mL of ethanol and 5mL of water, mixed and dissolved with stirring, and then heated to 70 ℃ for reaction for 12 hours. The resulting product P (Ph-3MVIm-Br) was filtered, washed with water and methanol, and then dried under vacuum at 65 ℃ for 24 hours to give a white solid powder with a yield of about 85%. As shown in FIGS. 2 and 3, the material is in CO2(195K) Under the condition of medium, the specific surface area of Langmuir is measured to be 244m2(g) total pore volume of 0.104cm3Per g, pore diameter of
Figure BDA0002430754520000072
Adsorbent P (Ph-3MVim-Br) in N2(77K) The specific surface area is only 10.0m under the condition of medium2(ii) in terms of/g. The results indicate that P (Ph-3MVIm-Br) is an ultra microporous material. As shown in FIG. 4, the thermogravimetric result shows that the material has excellent thermal stability and the thermal decomposition temperature is as high as 250 ℃.
The adsorption isotherms for acetylene and ethylene for the P (Ph-3MVIm-Br) material 298K are shown in FIG. 5.
P (Ph-3MVIm-Br) with the mass of 0.913g is activated at 100 ℃, then an adsorbent is filled into an adsorption column (the inner diameter is 4.6mm, the length is 150mm), mixed gas with the ethylene content of 99 vol% and the acetylene content of 1 vol% is introduced into the adsorption column at the room temperature of 25 ℃ at the rate of 0.70mL/min, the penetration curve is shown in FIG. 6, ethylene with the extremely low acetylene content (<0.05ppm) is obtained in the first 70min, and the adsorption is stopped. The adsorption column can be repeatedly used when the acetylene is desorbed by helium purging at 60 ℃. As shown in figure 7, the material still has stable adsorption performance after 8 adsorption-regeneration cycles.
At room temperature of 25 ℃, mixed gas with 50 vol% of ethylene content and 50 vol% of acetylene content is introduced into an adsorption column at the rate of 0.70mL/min, and the penetration curve is shown in figure 8, so that the material shows excellent dynamic separation performance.
The adsorption isotherms for propyne and propylene for the P (Ph-3MVIm-Br) material 298K are shown in FIG. 9. The material also shows excellent propyne propylene separation performance.
Example 3
5g of 1,3, 5-tris (chloromethyl) benzene and 6.95g of vinylimidazole were weighed out, added to 250mL of acetonitrile, mixed and dissolved with stirring, and then heated to 50 ℃ for reaction for 36 hours. The resulting product was filtered and washed with acetonitrile and then vacuum dried at 65 ℃ for 24 hours to give a white solid, hyperbranched ionic liquid Ph-3MVIm-Cl, with a yield of about 80%.
1.0g of hyperbranched ionic liquid Ph-3MVIm-Cl and 0.03g of azobisisobutyronitrile are weighed and added into a mixed solution of 10mL of N, N-dimethylformamide and 5mL of water, mixed and dissolved under stirring, and then heated to 80 ℃ for reaction for 12 hours. The resulting product P (Ph-3MVim-Cl) was filtered, washed with water and methanol, and then dried under vacuum at 65 ℃ for 24 hours to give a white solid powder with a yield of about 80%. CO at 195K2The result of the adsorption isotherm shows that the specific surface area of the material Langmuir is 184m2Per g, total pore volume of 0.081cm3Per g, pore diameter of
Figure BDA0002430754520000081
N at 77K2The adsorption result shows that the material ratio tableThe area is only 9.2m2(ii) in terms of/g. The results show that the material is an ultra-microporous material.
P (Ph-3MVIm-Cl) with the mass of 1.090g is activated at 70 ℃, an adsorbent is filled into an adsorption column (the inner diameter is 4.6mm, the length is 150mm), mixed gas with 99 vol% of propylene content and 1 vol% of propyne content is introduced into the adsorption column at 25 ℃ at 0.50mL/min, propylene with extremely low propyne content (<1ppm) is obtained in the first 120min, and the adsorption is stopped. Helium is used for purging and desorbing the propyne at the temperature of 60 ℃, and the adsorption column can be repeatedly used. The material still has stable adsorption performance after 5 times of adsorption-regeneration cycles.
The adsorption isotherms for the P (Ph-3MVIm-Cl) material 298K for propyne and propylene are shown in fig. 10.
A mixed gas of 99 vol% propylene content and 1 vol% propyne content was introduced into an adsorption column at room temperature of 25 ℃ at a rate of 0.50mL/min, and the permeation curve is shown in FIG. 11, whereby the material exhibited excellent dynamic separation performance.
Example 4
5.00g of Ph-6MVIm-Br (4.17mmol) and silver tetrafluoroborate (4.87g) were weighed out and dissolved in 40mL of water, and mixed in a 250mL flask, and a yellow-green floc was formed immediately, followed by stirring thoroughly for 24 hours in a dark environment. Filtering the precipitate, and performing rotary evaporation on the filtrate to sufficiently remove the solvent; the crude product was dissolved in acetonitrile and the filtrate was rotary evaporated thoroughly. The obtained solid is dried in vacuum for 24 hours at the temperature of 65 ℃, and the product Ph-6MVIm-BF4The yield is 83-93%.
Weighing 1.0g of hyperbranched ionic liquid Ph-6MVIm-BF4And 0.03g of azobisisobutyronitrile were added to a mixed solution of 10mL of acetonitrile and 1mL of water, mixed and dissolved with stirring, and then heated to 90 ℃ to react for 12 hours. The obtained product P (Ph-6 MVim-BF)4) Filtration, washing with water and methanol, followed by vacuum drying at 65 ℃ for 24 hours gave a white solid powder with a yield of about 90%. CO at 195K2The result of the adsorption isotherm shows that the specific surface area of the material Langmuir is 400m2Per g, total pore volume of 0.170cm3Per g, pore diameter of
Figure BDA0002430754520000091
N at 77K2AdsorptionThe result shows that the specific surface area of the material is only 11.1m2(ii) in terms of/g. The results show that the material is an ultra-microporous material.
Activating the ultramicropore material at 80 ℃, filling an adsorbent into an adsorption column (the inner diameter is 4.6mm, the length is 150mm), introducing mixed gas containing 99 vol% of ethylene and 1 vol% of acetylene into the adsorption column at 30 ℃ at 0.80mL/min, obtaining ethylene with extremely low acetylene content (<1ppm) in the first 70min, and stopping adsorption. The adsorption column can be repeatedly used when the acetylene is desorbed by helium purging at 50 ℃. The material still has stable adsorption performance after 5 times of adsorption-regeneration cycles.
Example 5
5g of 4, 4' -dichloromethylbiphenyl and 4.34g N, N-dimethylacrylamide were weighed out, added to 250mL of acetonitrile, mixed and dissolved with stirring, and then heated to 60 ℃ to react for 36 hours. The resulting product was filtered and washed with acetonitrile and then vacuum dried at 65 ℃ for 24 hours to give a white solid, i.e., a hyperbranched ionic liquid, with a yield of about 85%.
1.0g of the obtained hyperbranched ionic liquid and 0.05g of azobisisobutyronitrile were weighed and added to a mixed solution of 10mL of ethanol and 1mL of water, mixed and dissolved with stirring, and then heated to 80 ℃ for reaction for 24 hours. The resulting product was filtered, washed with water and methanol, and then dried under vacuum at 65 ℃ for 24 hours to give a pale yellow solid powder with a yield of about 90%. CO at 195K2The adsorption isotherm results showed that the specific surface area of Langmuir was 200m2(g) total pore volume of 0.120cm3Per g, pore diameter of
Figure BDA0002430754520000092
N at 77K2The adsorption result shows that the specific surface area of the material is only 10.4m2(ii) in terms of/g. The results show that the material is an ultra-microporous material.
Activating the ultramicropore material at 80 ℃, filling an adsorbent into an adsorption column (the inner diameter is 4.6mm, the length is 150mm), introducing mixed gas containing 99 vol% of propylene and 1 vol% of propyne into the adsorption column at 40 ℃ at 0.50mL/min, obtaining propylene with extremely low propyne content (<1ppm) in the first 80min, and stopping adsorption. Helium is used for purging and desorbing the propyne at 50 ℃, and the adsorption column can be repeatedly used. The material still has stable adsorption performance after 4 times of adsorption-regeneration cycles.
Example 6
5.00g of Ph-2MVIm-Br (11.06mmol) and an equimolar amount of ammonium hexafluorosilicate (4.87g) were weighed, respectively dissolved in 40mL of water, and mixed in a 250mL flask, followed by thorough stirring for 24 hours. Filtering the precipitate, and performing rotary evaporation on the filtrate to sufficiently remove the solvent; the crude product was dissolved in acetonitrile and the filtrate was rotary evaporated thoroughly. The obtained solid is dried in vacuum for 24 hours at the temperature of 65 ℃, and the product Ph-2MVIm-SiF6The yield was about 75%.
Weighing 1.0g of hyperbranched ionic liquid Ph-2MVIm-SiF6And 0.03g of azobisisobutyronitrile were added to a mixed solution of 10mL of ethanol and 2mL of water, mixed and dissolved with stirring, and then heated to 90 ℃ to react for 12 hours. The obtained product P (Ph-2 MVIm-SiF)6) Filtration, washing with water and methanol, followed by vacuum drying at 65 ℃ for 24 hours gave a white solid powder with a yield of about 90%. CO at 195K2The adsorption isotherm results showed that the Langmuir specific surface area was 40m2(g) total pore volume of 0.060cm3Per g, pore diameter of
Figure BDA0002430754520000101
N at 77K2The adsorption result shows that the specific surface area of the material is only 6.0m2(ii) in terms of/g. The results show that the material is an ultra-microporous material.
Activating the ultramicropore material at 70 ℃, filling an adsorbent into an adsorption column (the inner diameter is 4.6mm, the length is 150mm), introducing mixed gas containing 99 vol% of ethylene and 1 vol% of acetylene into the adsorption column at 20 ℃ at 0.40mL/min, obtaining ethylene with extremely low acetylene content (<1ppm) in the first 80min, and stopping adsorption. At 50 deg.C, helium gas is used to sweep acetylene, and the adsorption column can be reused. The material still has stable adsorption performance after 4 times of adsorption-regeneration cycles.
Example 7
5g of 1,2,4, 5-tetrabromomethylbenzene and 10.04g N-4-vinylphenyl-N, N-dimethylamine were weighed out, added to 400mL of acetonitrile, mixed and dissolved with stirring, and then heated to 55 ℃ to react for 48 hours. The resulting product was filtered and washed with acetonitrile and then vacuum dried at 65 ℃ for 24 hours to give a white solid, i.e., a hyperbranched ionic liquid, with a yield of about 85%.
1.0g of the obtained hyperbranched ionic liquid and 0.05g of azobisisobutyronitrile were weighed and added to a mixed solution of 10mL of acetone and 3mL of water, mixed and dissolved with stirring, and then heated to 80 ℃ for reaction for 24 hours. The resulting product was filtered, washed with water and methanol, and then dried under vacuum at 65 ℃ for 24 hours to give a pale red solid powder with a yield of about 82%. CO at 195K2The adsorption isotherm results showed that the specific surface area of Langmuir was 204m2Per g, total pore volume of 0.081cm3Per g, pore diameter of
Figure BDA0002430754520000111
Figure BDA0002430754520000112
N at 77K2The adsorption result shows that the specific surface area of the material is only 15.3m2(ii) in terms of/g. The results show that the material is an ultra-microporous material.
Activating the ultramicropore material at 80 ℃, filling an adsorbent into an adsorption column (the inner diameter is 4.6mm, the length is 150mm), introducing mixed gas containing 99 vol% of propylene and 1 vol% of propyne into the adsorption column at 20 ℃ at 0.50mL/min, obtaining propylene with extremely low propyne content (<1ppm) in the first 80min, and stopping adsorption. Helium is used for purging and desorbing the propyne at 50 ℃, and the adsorption column can be repeatedly used. The material still has stable adsorption performance after 5 times of adsorption-regeneration cycles.
Example 8
5g of 1,3, 5-tris (bromomethyl) -2,4, 6-triethyl and 7.94g of vinyldiphenylphosphine were weighed out, added to 400mL of acetonitrile, mixed and dissolved with stirring, and then heated to 55 ℃ for reaction for 48 hours. The resulting product was filtered and washed with acetonitrile and then vacuum dried at 65 ℃ for 24 hours to give a white solid, i.e. a hyperbranched ionic liquid, with a yield of about 80%.
1.0g of the obtained hyperbranched ionic liquid and 0.06g of azobisisobutyronitrile were weighed and added to a mixed solution of 10mL of N, N-dimethylformamide and 2mL of water, mixed and dissolved with stirring, and then heated to 90 ℃ for reaction for 24 hours. The resulting product was filtered, washed with water and methanolWashing and then vacuum drying at 65 ℃ for 24 hours gave a pale red solid powder with a yield of about 78%. CO at 195K2The adsorption isotherm results showed that the specific surface area of Langmuir was 212m2Per g, total pore volume of 0.110cm3Per g, pore diameter of
Figure BDA0002430754520000113
N at 77K2The adsorption result shows that the specific surface area of the material is only 14.6m2(ii) in terms of/g. The results show that the material is an ultra-microporous material.
Activating the ultramicropore material at 80 ℃, filling an adsorbent into an adsorption column (the inner diameter is 4.6mm, the length is 150mm), introducing mixed gas containing 99 vol% of ethylene and 1 vol% of acetylene into the adsorption column at 35 ℃ at 0.40mL/min, obtaining ethylene with extremely low acetylene content (<1ppm) in the first 70min, and stopping adsorption. The adsorption column can be repeatedly used when the acetylene is desorbed by helium purging at 50 ℃. The material still has stable adsorption performance after 4 times of adsorption-regeneration cycles.
Example 9
5g of 1,3, 5-tris (dichloroethyl) benzene and 5.85g of vinylimidazole were weighed out, added to 400mL of acetonitrile, mixed and dissolved with stirring, and then heated to 55 ℃ for reaction for 48 hours. The resulting product was filtered and washed with acetonitrile and then vacuum dried at 65 ℃ for 24 hours to give a white solid, i.e. a hyperbranched ionic liquid, with a yield of about 80%.
1.0g of the obtained hyperbranched ionic liquid and 0.06g of azobisisobutyronitrile were weighed and added to a mixed solution of 10mL of N, N-dimethylformamide and 2mL of water, mixed and dissolved with stirring, and then heated to 90 ℃ for reaction for 24 hours. The resulting product was filtered, washed with water and methanol, and then dried under vacuum at 65 ℃ for 24 hours to give a pale red solid powder with a yield of about 78%. CO at 195K2The adsorption isotherm results showed that the specific surface area of Langmuir was 112m2(ii)/g, total pore volume of 0.091cm3Per g, pore diameter of
Figure BDA0002430754520000121
N at 77K2The adsorption result shows that the specific surface area of the material is only 10.6m2(ii) in terms of/g. The results show that the materialIs an ultra-microporous material.
Activating the ultramicropore material at 60 ℃, filling an adsorbent into an adsorption column (the inner diameter is 4.6mm, the length is 150mm), introducing mixed gas containing 99 vol% of propylene and 1 vol% of propyne into the adsorption column at 30 ℃ at 0.40mL/min, obtaining propylene with extremely low propyne content (<1ppm) in the first 60min, and stopping adsorption. Helium is used for purging and desorbing the propyne at 50 ℃, and the adsorption column can be repeatedly used. The material still has stable adsorption performance after 4 times of adsorption-regeneration cycles.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.

Claims (10)

1. A kind of ultramicropore ionic polymer material is characterized in that the material is obtained by polymerization of hyperbranched ionic liquid; the hyperbranched ionic liquid consists of a hyperbranched benzene ring framework and a cation M+And the anion N-The structure of the three parts is shown in the following formulas (1) to (5):
Figure FDA0002430754510000011
wherein R is1～R8Each independently selected from one of H and alkyl;
the cation M+Is one of imidazole cation, quaternary ammonium cation and quaternary phosphine cation, and the structures are respectively shown in formulas (I) to (III) as follows:
Figure FDA0002430754510000012
wherein m is an integer of 0-3, R9Is a polymerizable group, R10～R12Are respectively and independently selected from one of H, alkyl and aromatic hydrocarbon group, and R10～R12At least one of the hyperbranched polymers is connected with the hyperbranched benzene ring skeleton through covalent bonds;
the anionN-The ion source is any one of halogen ion, thiocyanate ion, dicyanamide ion, tetrafluoroborate ion, hexafluorophosphate ion, hexafluorosilicate ion, bis (trifluoromethylsulfonyl) imide ion, trifluoromethanesulfonate ion, sulfate ion, formate ion and acetate ion.
2. The ultramicropore ionomer material according to claim 1, wherein R is9Is one of vinyl, styryl, acrylamide and acrylic groups, and the structures of the compounds are respectively shown in the following formulas (A) to (D):
Figure FDA0002430754510000013
wherein R is13And R14Each independently selected from H and alkyl.
3. The ultramicropore ionomer material according to claim 1 or 2, wherein the pore size distribution is within
Figure FDA0002430754510000021
4. The method for producing the ultramicropore ionomer material according to any one of claims 1 to 3, comprising the steps of:
(a) dissolving the hyperbranched ionic liquid in a mixed solution of a solvent A and water, carrying out polymerization reaction at 70-120 ℃, stirring for 12-48 hours, and filtering to obtain a solid precipitate product; the solvent A is one of N, N-dimethylformamide, methanol, ethanol, acetonitrile and acetone;
(b) and washing the obtained solid precipitate product with water and methanol in sequence to remove unreacted raw materials, and then carrying out vacuum drying at the temperature of 50-100 ℃ for 12-24 hours to obtain the ultramicropore ionic polymer material.
5. The preparation method according to claim 4, wherein in the mixed solution of the solvent A and water, the volume ratio of the solvent A to the water is 1-100: 2;
the polymerization reaction temperature is 60-100 ℃, and the stirring time is 12-24 hours.
6. The use of the ultramicropore ionic polymer material according to any one of claims 1 to 3 for selective adsorption separation of alkynes/alkenes, wherein the ultramicropore ionic polymer material is used as an adsorbent, and the adsorbent is contacted with a mixed gas containing alkynes/alkenes to realize selective separation of alkynes and alkenes;
the mixed gas is mixed gas containing acetylene/ethylene or mixed gas containing propyne/propylene.
7. The use according to claim 6, wherein the adsorbent is contacted with the mixed gas in any one of fixed bed adsorption, fluidized bed adsorption and moving bed adsorption.
8. The use of claim 6, wherein the temperature of the selective adsorption separation is-5 to 50 ℃, the total pressure of the mixed gas is 100 to 1000kPa, and the content of acetylene or propyne in the mixed gas is 50ppm to 70 vol%;
after selective adsorption and separation, the ultramicropore ionic polymer material adsorbed with alkyne is desorbed to obtain alkyne, and the regeneration of the ultramicropore ionic polymer material is realized; the temperature of desorption is 25-150 ℃.
9. Use according to claim 6, wherein the mixed gas further comprises one or more of carbon dioxide, methane, nitrogen, ethane and propane.
10. The use according to claim 6, wherein the content of acetylene or propyne after the selective adsorption separation of the mixed gas is not more than 1 ppm.
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