CN110141977A - Graft type ionic liquid polyimide film and preparation method and applications - Google Patents
Graft type ionic liquid polyimide film and preparation method and applications Download PDFInfo
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- CN110141977A CN110141977A CN201910520807.0A CN201910520807A CN110141977A CN 110141977 A CN110141977 A CN 110141977A CN 201910520807 A CN201910520807 A CN 201910520807A CN 110141977 A CN110141977 A CN 110141977A
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- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
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Abstract
The invention belongs to UF membrane fields, in particular to graft type ionic liquid polyimide film and preparation method and applications.The present invention utilizes aminated functional ion liquid, first carries out polyimide grafted, then prepares graft type ionic liquid polyimide film, the graft type ionic liquid polyimide film prepared is in carbon dioxide gas separation.The present invention proposes that one kind, can be by ionic liquid supported in the method on polyimides main chain by schiff base structure, and carbon dioxide permeability flux not only can be improved in the Modified Membrane of acquisition, additionally it is possible to significantly improve the selectivity of carbon dioxide gas.
Description
Technical field:
The invention belongs to UF membrane field, in particular to graft type ionic liquid polyimide film and preparation method and its answer
With.
Background technique:
The fast development of industry produces a large amount of carbon dioxide gas, in numerous carbon dioxide recovery techniques, film point
Have energy consumption small from process, environmental-friendly, the advantages that equipment is simple, to show one's talent.The core original part of membrane separating process is just
It is membrane material, being commonly used in and preparing the material of gas separation membrane includes cellulose acetate, polysulfones, polydimethylsiloxane, polyamides
Imines etc., wherein polyimides is since with excellent mechanical performance, hot property, chemical stability etc. becomes gas instantly
The research hotspot of separation membrane material.But there is the common problems of other gas separation membranes, i.e. permeability and choosing for polyimides
The relationship mutually restricted between selecting property.The plasticizing problem of the polyimides of carbon dioxide at high pressure induction simultaneously also limits its development
Prospect.So the modification that scholars have been devoted to polyimides is probed into, disadvantage as above is overcome with this.
Ionic liquid is made of organic cation and inorganic or organic anion, and the feature that ionic liquid structure is adjustable makes it
With designability, the functional group with property can be introduced, to design the ionic liquid that synthesis has certain specific function
Body, that is, functionalized ion liquid.Currently used is the functionalized ion liquid of amido, has height to the absorption of carbon dioxide
Selectivity.But ionic liquid also has certain limitation to the modification of gas separation membrane, such as supported ionic liquid liquid
For film, when pressure difference reaches a certain level, film liquid can rupture, so that the performance of ionic liquid supporting liquid sheet declines；For gather from
For sub- liquid film, not only the peculiar group of ionic liquid is required strictly, and synthesis process very complicated；For ionic liquid
For body blend film, due to being physical blending mostly between material and ionic liquid, so dissolving each other to ionic liquid and material
Property is more demanding, and stability of the ionic liquid in film is difficult to ensure, while the raising degree of blend film physical property
It is limited.
Therefore, it is required to that ionic liquid is overcome to be easy to run off in film at present, film liquid is easy to rupture, with dissolving each other for polymer
Property it is bad the problems such as, while remaining ionic liquid itself to the advantage of the highly dissoluble of carbon dioxide, improve gas separation membrane
Separating property polyimide film.
Summary of the invention:
Goal of the invention:
The purpose of the present invention is deficiencies in view of the above technology, provide graft type ionic liquid polyimide film and preparation side
Method and its application.It is intended to prepare the modified gas seperation film that aminated functional ionic liquids graft on polyimides, passes through
Schiff bases feature structure realizes that ionic liquid is immobilized logical in the infiltration on polymer chain, improving carbon dioxide in the form of side group
Amount improves the selectivity of carbon dioxide gas, improves plasticizing pressure point.Compared with prior art, which overcomes ionic liquid
Body is easy to run off in film, and film liquid is easy to rupture, the bad problem with the intersolubility of polymer, while improving the plasticizing of polymer film
Pressure.
Technical solution:
Graft type ionic liquid polyimide film, the graft type ionic liquid polyimides membrane structure are as follows:
Wherein, n range is 100~200；R1Indicate methylimidazole, butyl imidazole or octylimidazole；
R2It indicates
Graft type ionic liquid polyimides membrane preparation method, method includes the following steps:
(1) polyimide grafted: aminated functional ion liquid to be added in the casting solution of polyimides formation, water-bath
Heating stirring, aminated functional ion liquid are grafted on main polymer chain with pendant manner, are obtained by the feature structure of schiff bases
To aminated casting solution；
(2) it prepares graft type ionic liquid polyimide film: the aminated casting solution blade coating in step (1) is formed a film,
Modified Membrane is obtained using solvent evaporated method, drying solidifies film, then takes off film after being freezed, and obtains graft type ionic liquid polyamides
Imines film.
Further, the preparation method of step (1) aminated functional ion liquid are as follows: by N- methylimidazole, N- butyl miaow
One of azoles, N- octylimidazole or it is a variety of heated with bromine ethylamine hydrobromide, alcohol reflux obtains centre after dry
Body, adds potassium hydroxide, removes KBr, then with KPF6Ion-exchange reactions is carried out, heating water bath is carried out after ethyl alcohol dissolution, goes
Except ethyl alcohol, aminated functional ion liquid is obtained.
Further, the polyimides in step (1) and aminated functional ionic liquid body mass ratio be 1:(0.02~
0.2)；Condition of water bath heating is 60 DEG C~80 DEG C, and stirring in water bath heats 8~16 hours.
Further, the aminated functional ion liquid in step (1) is 1- (amine ethyl) -3- methylimidazole hexafluorophosphoric acid
Salt, 1- (amine ethyl) -3- butyl imidazole hexafluorophosphate, one of 1- (amine ethyl) -3- octylimidazole hexafluorophosphate or
It is a variety of.
Further, the aminated functional ion liquid in step (1) is 1- (amine ethyl) -3- butyl imidazole hexafluorophosphoric acid
Salt.
Further, Grafting Structure is the schiff bases feature structure of C=N double bond, and condition of cure is 40~60 in step (2)
DEG C, it is -4 DEG C~-15 DEG C that film condition is taken off after freezing, which is cryogenic temperature, and cooling time is 15~30min.
Graft type ionic liquid polyimide film is applied in carbon dioxide gas separation.
Further, graft type ionic liquid polyimide film is used to separate titanium dioxide carbon/nitrogen gas, carbon dioxide/first
Alkane, carbon dioxide/oxygen mixed gas system.
It further, is 0.1MPa~1.6MPa, operation temperature in transmembrane pressure by graft type ionic liquid polyimide film
Under conditions of degree is 30 DEG C~70 DEG C, the separation of carbon dioxide gas is carried out.
Advantage and effect:
The present invention proposes that one kind, can be by ionic liquid supported in the side on polyimides main chain by schiff base structure
Method, filming technology is simple, overcomes the complicated processes of traditional chemical graft modification, while ionic liquid being overcome easily to flow in film
Lose, it is bad with polymer compatibility the disadvantages of, and the weak interaction and ion having between schiff bases and carbon dioxide
Liquid both contributes to mass transport process of the carbon dioxide in film to the high-dissolvability of carbon dioxide, the superposition of the two effect.Simultaneously
After ionic liquid is grafted on main polymer chain as side group, so that the rigidity of polymer obviously increases, so that nitrogen is in film
Interior osmotic resistance increases, and selectively significantly improves.So carbon dioxide permeability flux had not only can be improved in the Modified Membrane obtained, but also
The selectivity that carbon dioxide gas can be significantly improved overcomes the restricting relation between permeation flux and selectivity.
Preparation method of the invention can change the form of polymer chain from molecular structure, improve the durability of film, improve
Rigidity improves plasticizing pressure point and service life while guaranteeing good separating effect and excellent stability.
Detailed description of the invention:
Fig. 1 is that the reaction by taking 1- (amine ethyl) -3- butyl imidazole hexafluorophosphate grafts on polyimides side chain as an example is former
Reason figure.
Fig. 2 is the experiment flow of carbon dioxide gas separation in the present invention.
Description of symbols:
1- dioxide bottle, 2- nitrogen gas cylinder, 3- methane gas cylinder, 4- oxygen gas cylinder, 5- pressure reducing valve, 6- needle valve, 7-
Control valve, 8- digital display manometer, 9- insulating box, 10- diaphragm, 11- relief valve, 12- soap bubble flowmeter.
Specific embodiment:
The present invention uses simple graft-modification method, and ionic liquid is immobilized in polymer chain in the form of chemical bond
On, so as to overcome ionic liquid to be easy to run off in film, film liquid is easy to rupture, it is bad with the intersolubility of polymer the problems such as,
Ionic liquid itself is remained simultaneously to the advantage of the highly dissoluble of carbon dioxide, largely improves point of gas separation membrane
From performance.Schiff bases compound and its metal complex have important application in the fields such as medicine, catalysis, photochromic.Wherein
The interaction of schiff bases and carbon dioxide is always the research hotspot of catalytic field.By the graft modification of schiff base structure,
Ionic liquid itself can not only be retained to the high-dissolvability of carbon dioxide, and ionic liquid can be overcome easily to flow in film
Lose, it is bad with polymer compatibility the disadvantages of, ensure that stability of the ionic liquid in film, at the same time again can change it is poly-
The structure of object chain is closed to improve selectivity, improves plasticizing pressure point.These advantages have all shown ionic liquid graft modification gas
The huge applications potentiality of body seperation film.
Ionic liquid and polyimides are grafted on main chain with schiff base structure, schiff base structure itself and carbon dioxide it
Between the weak interaction that just has, while after ionic liquid is grafted, preferably remain ionic liquid to carbon dioxide
The superposition of high-dissolvability, the two effect both contributes to mass transport process of the carbon dioxide in film.Ionic liquid is as side group simultaneously
After being grafted on main polymer chain, so that the rigidity of polymer obviously increases, so that osmotic resistance of the nitrogen in film increases,
Selectivity significantly improves.So carbon dioxide permeability flux had not only can be improved in the Modified Membrane obtained, but also dioxy can be significantly improved
The selectivity for changing carbon gas, overcomes the restricting relation between permeation flux and selectivity.
Graft type ionic liquid polyimide film, as follows comprising graft type ionic liquid polyimides membrane structure:
Wherein, n range is 100~200；R1Indicate methylimidazole, butyl imidazole or octylimidazole；
R2It indicates
Graft type ionic liquid polyimides membrane preparation method, method includes the following steps:
(1) polyimide grafted: aminated functional ion liquid to be added in the casting solution of polyimides formation, water-bath
Heating stirring, aminated functional ion liquid are grafted on main polymer chain with pendant manner, are obtained by the feature structure of schiff bases
To aminated casting solution；
(2) it prepares graft type ionic liquid polyimide film: the aminated casting solution blade coating in step (1) is formed a film,
Modified Membrane is obtained using solvent evaporated method, drying solidifies film, then takes off film after being freezed, and obtains graft type ionic liquid polyamides
Imines film.
Generally film thickness is controlled in 25 μm of ± 4 μ ms when blade coating film forming.
Wherein, the preparation method of step (1) aminated functional ion liquid are as follows: by N- methylimidazole, N- butyl imidazole, N-
One of octylimidazole or it is a variety of heated with bromine ethylamine hydrobromide, alcohol reflux obtains intermediate after dry, then plus
Enter potassium hydroxide, remove KBr, then with KPF6Ion-exchange reactions is carried out, heating water bath is carried out after ethyl alcohol dissolution, removes ethyl alcohol,
Obtain aminated functional ion liquid.
The concrete configuration method of aminated functional ion liquid is:
The three neck round bottom flask for taking 250mL or 500mL weighs bromine ethylamine hydrobromide and N- first in the ratio of 1:1.125
Base imidazoles (N- butyl imidazole, N- octylimidazole), oil bath heating, alcohol reflux 22~for 24 hours, obtained product is evaporated and is removed
Ethyl alcohol obtains thick liquid, puts after pouring into boiling flask in a vacuum drying oven, and dry 4~6h, obtains at 80 DEG C
Intermediate [equimolar KOH is added in 1- (2- amine ethyl) -3- methylimidazole bromide, 1- (2- amine ethyl) in the intermediate,
Product is put into vacuum oven 12h~suitable ethyl alcohol is added afterwards for 24 hours, stirring and dissolving generates a large amount of white solid KBr, removes
Decontamination KBr obtains the higher amine ethylmethylimidazolium hydrobromate of purity (amine ethyl-butyl imidazoles hydrobromate, amine ethyl
Octylimidazole hydrobromate).Finally by products obtained therefrom and KPF6Carry out ion-exchange reactions.After the two is dissolved with ethyl alcohol,
It is taken out after 18~20h of successive reaction in 66 DEG C of water-bath.Ethyl alcohol is evaporated off in the impurity back spin that generation is removed by suction filtration under vacuum, and obtains mesh
Mark functional ionic liquids.
Polyimides and aminated functional ionic liquid body mass ratio in step (1) are 1:(0.02~0.2)；Heating water bath
Condition is 60 DEG C~80 DEG C, and stirring in water bath heats 8~16 hours.
Aminated functional ion liquid in step (1) is 1- (amine ethyl) -3- methylimidazole hexafluorophosphate, 1- (amine
Ethyl) -3- butyl imidazole hexafluorophosphate or 1- (amine ethyl) -3- octylimidazole hexafluorophosphate.
Aminated functional ion liquid in step (1) is 1- (amine ethyl) -3- methylimidazole hexafluorophosphate.
Grafting Structure is the schiff bases feature structure of C=N double bond.Condition of cure is 40~60 DEG C of progress low-temperature settings, directly
It is evaporated to solvent, freezing conditions are -15 DEG C~-4 DEG C 15~30min of freezing chamber.
Graft type ionic liquid polyimide film is applied in carbon dioxide gas separation.
Graft type ionic liquid polyimide film is used to separate titanium dioxide carbon/nitrogen gas, carbon dioxide/methane, titanium dioxide
Carbon/oxygen mixed gas system.
By graft type ionic liquid polyimide film transmembrane pressure be 0.1MPa~1.6MPa, operation temperature be 30 DEG C~
Under conditions of 70 DEG C, the separation of carbon dioxide gas is carried out.
As shown in Fig. 2, dioxide bottle 1, nitrogen gas cylinder 2, methane gas cylinder 3, oxygen gas cylinder 4 respectively successively with pressure reducing valve
5 and needle valve 6 connection formed four parallel pipelines, parallel pipeline is again successively and in control valve 7, digital display manometer 8, insulating box 9
Diaphragm 10 connect, insulating box 9 is additionally provided with relief valve 11, and 10 lower section of diaphragm is connect with soap bubble flowmeter 12.
Carbon dioxide gas separating experiment concrete operations process are as follows: Modified Membrane is placed in diaphragm, adjustment insulating box is extremely
Required temperature is tested, temperature range may be selected 30 DEG C~70 DEG C, and adjustment pressure pressure to needed for testing, pressure limit may be selected
0.1MPa~1.6MPa, the control valve for being first turned on nitrogen gas cylinder carries out precompressed 30~60 minutes, until pressure gauge registration is steady
It is fixed, the value added of film downstream soap bubble flowmeter registration is observed within the unit time, the permeation flux of nitrogen is calculated with this, then
It opens methane gas cylinder to carry out precompressed 40 minutes, after guaranteeing the exclusion of nitrogen whole and the precompressed to film of methane, in unit
The value added of interior observation film downstream soap bubble flowmeter registration, the permeation flux of methane is calculated with this.Secondly oxygen gas is opened
Bottle carries out precompressed 50 minutes, and after guaranteeing the exclusion of methane whole and the precompressed to film of oxygen, film is observed within the unit time
The value added of downstream soap bubble flowmeter registration, the permeation flux of oxygen is calculated with this.Dioxide bottle is finally opened to carry out
It precompressed 60 minutes, after guaranteeing the exclusion of oxygen whole and the precompressed to film of carbon dioxide, is observed under film within the unit time
The value added for swimming soap bubble flowmeter registration, the permeation flux of carbon dioxide is calculated with this.It is logical in the infiltration for measuring every kind of gas
After amount, and then titanium dioxide carbon/nitrogen gas is acquired, carbon dioxide/methane, carbon dioxide/oxygen selectivity.
Existing polyimide film material is at 0.1MPa, 30 DEG C of experimental conditions, the permeation flux of carbon dioxide
5.28Barrer CO2/N2Selectivity 21.9, CO2/CH4Selectivity 24.1, CO2/O2Selectivity 12.6.
At 0.2MPa, 30 DEG C of experimental conditions, the permeation flux of carbon dioxide is reduced to from 5.28Barrer
4.89Barrer CO2/N2Selectivity is increased to 22.5, CO from 21.92/CH4Selectivity is increased to 25.8, CO from 24.12/O2Choosing
Selecting property is increased to 13.2 from 12.6.
At 0.6MPa, 30 DEG C of experimental conditions, the permeation flux of carbon dioxide is reduced to from 5.28Barrer
3.32Barrer CO2/N2Selectivity is increased to 26.1, CO from 21.92/CH4Selectivity is increased to 27.8, CO from 24.12/O2Choosing
Selecting property is increased to 18.2 from 12.6.
At 1.2MPa, 30 DEG C of experimental conditions, the permeation flux of carbon dioxide is increased to by original 6.01Barrer
53.83Barrer CO2/N2Selectivity is reduced to 13.6, CO by 21.92/CH4Selectivity is reduced to 16.5, CO by 24.12/O2Choosing
Selecting property is reduced to 8.3 by 12.6.Illustrate that plasticizing phenomenon occurs for polyimide gas separating film at this time, plasticizing pressure is
1.2MPa.Selectivity is greatly lowered at this time, and application value reduces.
Embodiment 1
The three neck round bottom flask for taking 250mL or 500mL weighs bromine ethylamine hydrobromide and N- fourth in the ratio of 1:1.125
Base imidazoles, oil bath heating, alcohol reflux 22~for 24 hours, by obtained product evaporating ethanol, thick liquid is obtained,
It is put after pouring into boiling flask in a vacuum drying oven, dry 4~6h, obtains intermediate 1- (2- amine ethyl) -3- at 80 DEG C
Butyl imidazole bromide.Then, equimolar KOH is added in the intermediate, after product is put into vacuum oven 12h~for 24 hours
Suitable ethyl alcohol is added, stirring and dissolving generates a large amount of white solid KBr, removes impurity KBr, obtains the higher amine ethyl of purity
Butyl imidazole hydrobromate.Products obtained therefrom and KPF6 are finally subjected to ion-exchange reactions.After the two is dissolved with ethyl alcohol, 66
DEG C water-bath in take out after 18~20h of successive reaction.Ethyl alcohol is evaporated off in the impurity back spin that generation is removed by suction filtration under vacuum, and obtains target
Functional ionic liquids.
As shown in Figure 1, first 10g polyimides is dissolved in 90g N-Methyl pyrrolidone solvent, 60 DEG C of heating stirrings
Then the aminated functional ion liquid 1- amine ethyl -3- butyl imidazole hexafluorophosphate of 0.2g is added in 8h, continue heating stirring
Casting solution is cast in horizontal glass plate and scratches after the casting solution of formation to be carried out to deaeration processing 12h at room temperature by 12h
Film forming.Glass plate is put into vacuum oven, solvent flashing and moisture, solidify film under the conditions of 60 DEG C, and -4 are placed on after taking-up
DEG C 15~30min of freezing chamber, careful scrapes the film, obtains graft type ionic liquid polyimide film.
At 0.1MPa, 30 DEG C of experimental conditions, the permeation flux of carbon dioxide is by original 5.28Barrer (1Barrer
=10-10cm3(STP)cm/cm2S cmHg) rise to 6.56Barrer, CO2/N2Selectivity increases to 28.5, CO by 21.92/
CH4Selectivity increases to 32.5, CO by 24.12/CH4, CO2/O2Selectivity increases to 20.5 by 12.6.
Embodiment 2
The aminated functional ion liquid prepared using embodiment 1.
First 10g polyimides is dissolved in 90g N-Methyl pyrrolidone solvent, then 60 DEG C of heating stirring 8h are added
0.8g 1- amine ethyl -3- butyl imidazole hexafluorophosphate continues heating stirring 12h, the casting solution of formation is carried out at room temperature
After deaeration handles 12h, casting solution is cast in horizontal glass plate and scratches film forming.Glass plate is put into vacuum oven,
Solvent flashing and moisture, solidify film under the conditions of 60 DEG C, and -4 DEG C of 15~30min of freezing chamber are placed on after taking-up, and careful scrapes this
Film obtains graft type ionic liquid polyimide film.
At 0.1MPa, 30 DEG C of experimental conditions, the permeation flux of carbon dioxide is risen to by original 5.28Barrer
10.01Barrer CO2/N2Selectivity increases to 84.9, CO by 21.92/CH4Selectivity increases to 44.5, CO by 24.12/O2Choosing
Selecting property increases to 39.5 by 12.6.
Embodiment 3
The aminated functional ion liquid prepared using embodiment 1.
First 10g polyimides is dissolved in 90g N-Methyl pyrrolidone solvent, then 60 DEG C of heating stirring 8h are added
2g 1- amine ethyl 3- butyl imidazole hexafluorophosphate continues heating stirring 12h, the casting solution of formation is taken off at room temperature
After bubble processing 12h, casting solution is cast in horizontal glass plate and scratches film forming.Glass plate is put into vacuum oven, 60
Solvent flashing and moisture, solidify film under the conditions of DEG C, and -4 DEG C of 15~30min of freezing chamber are placed on after taking-up, and careful scrapes the film,
Obtain graft type ionic liquid polyimide film.
At 0.1MPa, 30 DEG C of experimental conditions, the permeation flux of carbon dioxide is reduced to by original 5.28Barrer
2.13Barrer CO2/N2Selectivity increases to 49.2, CO by 21.92/CH4Selectivity increases to 29.5, CO by 24.12/O2Choosing
Selecting property increases to 31.2 by 12.6.
Embodiment 4
The aminated functional ion liquid prepared using embodiment 1.
First 10g polyimides is dissolved in 90g N-Methyl pyrrolidone solvent, then 60 DEG C of heating stirring 8h are added
0.8g 1- amine ethyl 3- butyl imidazole hexafluorophosphate continues heating stirring 12h, the casting solution of formation is carried out at room temperature
After deaeration handles 12h, casting solution is cast in horizontal glass plate and scratches film forming.Glass plate is put into vacuum oven,
Solvent flashing and moisture, solidify film under the conditions of 60 DEG C, and -4 DEG C of 15~30min of freezing chamber are placed on after taking-up, and careful scrapes this
Film obtains graft type ionic liquid polyimide film.
At 0.1MPa~1MPa, 30 DEG C of experimental conditions, compared with Example 2, the permeation flux of carbon dioxide is by implementing
The 10.01Barrer of example 2 is reduced to 9.83Barrer, CO2/N2Selectivity increases to 180.2, CO by 21.92/CH4Selectivity by
24.1 increase to 86.5, CO2/O2Selectivity increases to 49.3 by 12.6.
Embodiment 5
The aminated functional ion liquid prepared using embodiment 1.
First 10g polyimides is dissolved in 90g N-Methyl pyrrolidone solvent, 60 DEG C of heating stirring 8h, by formation
After casting solution carries out deaeration processing 12h at room temperature, casting solution is cast in horizontal glass plate and scratches film forming.By glass plate
Be put into vacuum oven, solvent flashing and moisture, solidify film under the conditions of 60 DEG C, be placed on after taking-up -4 DEG C of freezing chambers 15~
30min, careful scrapes the film, obtains the pure film of polyimides.
At 1.2MPa, 30 DEG C of experimental conditions, the permeation flux of carbon dioxide is increased to by original 6.01Barrer
53.83Barrer CO2/N2Selectivity is reduced to 13.6, CO by 21.92/CH4Selectivity is reduced to 16.5, CO by 24.12/O2Choosing
Selecting property is reduced to 8.3 by 12.6.Illustrate that plasticizing phenomenon occurs for polyimide gas separating film at this time, plasticizing pressure is
1.2MPa。
Embodiment 6
The aminated functional ion liquid prepared using embodiment 1.
First 10g polyimides is dissolved in 90g N-Methyl pyrrolidone solvent, then 60 DEG C of heating stirring 8h are added
0.8g 1- amine ethyl 3- butyl imidazole hexafluorophosphate continues heating stirring 12h, the casting solution of formation is carried out at room temperature
After deaeration handles 12h, casting solution is cast in horizontal glass plate and scratches film forming.Glass plate is put into vacuum oven,
Solvent flashing and moisture, solidify film under the conditions of 60 DEG C, and -4 DEG C of 15~30min of freezing chamber are placed on after taking-up, and careful scrapes this
Film obtains graft type ionic liquid polyimide film.
At 1.2MPa, 30 DEG C of experimental conditions, the permeation flux of carbon dioxide is reduced to by original 9.01Barrer
7.63Barrer CO2/N2Selectivity increases to 202.2, CO by 21.92/CH4Selectivity increases to 96.5, CO by 24.12/O2Choosing
Selecting property increases to 59.3 by 12.6.Illustrate that there is no being plasticized phenomenon for Modified Membrane at this time.
By embodiment 5 and embodiment 6 it is found that pressure significantly affects membrane flux presence, mainly due to pressure increase pair
The interaction of molecule segment has an impact in film, and segment spacing reduces, and flux is caused to reduce, and selectivity increases.
Embodiment 7
The aminated functional ion liquid prepared using embodiment 1.
First 10g polyimides is dissolved in 90g N-Methyl pyrrolidone solvent, then 60 DEG C of heating stirring 8h are added
0.8g 1- amine ethyl 3- butyl imidazole hexafluorophosphate continues heating stirring 12h, the casting solution of formation is carried out at room temperature
After deaeration handles 12h, casting solution is cast in horizontal glass plate and scratches film forming.Glass plate is put into vacuum oven,
Solvent flashing and moisture, solidify film under the conditions of 60 DEG C, and -4 DEG C of 15~30min of freezing chamber are placed on after taking-up, and careful scrapes this
Film obtains graft type ionic liquid polyimide film.
At 1.6MPa, 30 DEG C of experimental conditions, the permeation flux of carbon dioxide is increased to by original 8.59Barrer
49.52Barrer CO2/N2Selectivity is reduced to 18.6, CO by 21.92/CH4Selectivity is reduced to 16.5, CO by 24.12/O2Choosing
Selecting property is reduced to 9.9 by 12.6.Plasticizing pressure 1.6MPa.Illustrate that there is no plasticizing phenomenons for Modified Membrane at this time, compared to poly-
The pure film of acid imide, plasticizing pressure are enhanced.
Embodiment 8
The aminated functional ion liquid prepared using embodiment 1.
First 10g polyimides is dissolved in 90g N-Methyl pyrrolidone solvent, then 60 DEG C of heating stirring 8h are added
0.8g 1- amine ethyl 3- butyl imidazole hexafluorophosphate continues heating stirring 12h, the casting solution of formation is carried out at room temperature
After deaeration handles 12h, casting solution is cast in horizontal glass plate and scratches film forming.Glass plate is put into vacuum oven,
Solvent flashing and moisture, solidify film under the conditions of 60 DEG C, and -4 DEG C of 15~30min of freezing chamber are placed on after taking-up, and careful scrapes this
Film obtains graft type ionic liquid polyimide film.
At 0.2MPa, 30 DEG C~70 DEG C experimental conditions, the permeation flux of carbon dioxide is by original 10.01Barrer liter
Height arrives 11.13Barrer, CO2/N2Selectivity is reduced to 30.4, CO by 38.12/CH4Selectivity is reduced to 28.5, CO by 34.12/
O2Selectivity is reduced to 10.9 by 12.6.
Embodiment 9
The three neck round bottom flask for taking 250mL or 500mL weighs bromine ethylamine hydrobromide and N- first in the ratio of 1:1.125
Base imidazoles, oil bath heating, alcohol reflux 22~for 24 hours, by obtained product evaporating ethanol, thick liquid is obtained,
It is put after pouring into boiling flask in a vacuum drying oven, dry 4~6h, obtains intermediate 1- (2- amine ethyl) -3- at 80 DEG C
Methylimidazole bromide.Then, equimolar KOH is added in the intermediate, after product is put into vacuum oven 12h~for 24 hours
Suitable ethyl alcohol is added, stirring and dissolving generates a large amount of white solid KBr, removes impurity KBr, obtains the higher amine ethyl of purity
Methylimidazole hydrobromate.Finally by products obtained therefrom and KPF6Carry out ion-exchange reactions.After the two is dissolved with ethyl alcohol, 66
DEG C water-bath in take out after 18~20h of successive reaction.Ethyl alcohol is evaporated off in the impurity back spin that generation is removed by suction filtration under vacuum, and obtains target
Functional ionic liquids.
First 10g polyimides is dissolved in 90g N-Methyl pyrrolidone solvent, then 60 DEG C of heating stirring 8h are added
0.8g 1- amine ethyl 3- methylimidazole hexafluorophosphate continues heating stirring 12h, the casting solution of formation is carried out at room temperature
After deaeration handles 12h, casting solution is cast in horizontal glass plate and scratches film forming.Glass plate is put into vacuum oven,
Solvent flashing and moisture, solidify film under the conditions of 60 DEG C, and -4 DEG C of 15~30min of freezing chamber are placed on after taking-up, and careful scrapes this
Film obtains graft type ionic liquid polyimide film.
At 0.1MPa, 30 DEG C of experimental conditions, the permeation flux of carbon dioxide is risen to by original 5.28Barrer
10.96Barrer CO2/N2Selectivity increases to 69.3, CO by 21.92/CH4Selectivity increases to 40.5, CO by 24.12/O2Choosing
Selecting property increases to 28.6 by 12.6.
Embodiment 10
The three neck round bottom flask for taking 250mL or 500mL weighs bromine ethylamine hydrobromide in the ratio of 1:1.125 and N- is pungent
Base imidazoles, oil bath heating, alcohol reflux 22~for 24 hours, by obtained product evaporating ethanol, thick liquid is obtained,
It is put after pouring into boiling flask in a vacuum drying oven, dry 4~6h, obtains intermediate 1- (2- amine ethyl) -3- at 80 DEG C
Octylimidazole bromide.Then, equimolar KOH is added in the intermediate, after product is put into vacuum oven 12h~for 24 hours
Suitable ethyl alcohol is added, stirring and dissolving generates a large amount of white solid KBr, removes impurity KBr, obtains the higher amine ethyl of purity
Octylimidazole hydrobromate.Finally by products obtained therefrom and KPF6Carry out ion-exchange reactions.After the two is dissolved with ethyl alcohol, 66
DEG C water-bath in take out after 18~20h of successive reaction.Ethyl alcohol is evaporated off in the impurity back spin that generation is removed by suction filtration under vacuum, and obtains target
Functional ionic liquids.
First 10g polyimides is dissolved in 90g N-Methyl pyrrolidone solvent, then 60 DEG C of heating stirring 8h are added
0.8g 1- amine ethyl 3- octylimidazole hexafluorophosphate continues heating stirring 12h, the casting solution of formation is carried out at room temperature
After deaeration handles 12h, casting solution is cast in horizontal glass plate and scratches film forming.Glass plate is put into vacuum oven,
Solvent flashing and moisture, solidify film under the conditions of 60 DEG C, and -4 DEG C of 15~30min of freezing chamber are placed on after taking-up, and careful scrapes this
Film obtains graft type ionic liquid polyimide film.
At 0.1MPa, 30 DEG C of experimental conditions, the permeation flux of carbon dioxide is risen to by original 5.28Barrer
7.26Barrer CO2/N2Selectivity increases to 61.9, CO by 21.92/CH4Selectivity increases to 32.5, CO by 24.12/O2Choosing
Selecting property increases to 22.6 by 12.6.
Embodiment 11
Aminated functional ion liquid mixing prepared by Example 1 and embodiment 9, mass ratio 1:1 are mixed equal
It is even.
First 10g polyimides is dissolved in 90g N-Methyl pyrrolidone solvent, then 60 DEG C of heating stirring 8h are added
0.2g 1- amine ethyl 3- butyl imidazole hexafluorophosphate and 1- amine ethyl 3- methylimidazole hexafluorophosphate mixing liquid continue
Casting solution is cast to horizontal glass after the casting solution of formation to be carried out to deaeration processing 12h at room temperature by heating stirring 12h
Film forming is scratched on plate.Glass plate is put into vacuum oven, solvent flashing and moisture, solidify film under the conditions of 60 DEG C, take out
After be placed on -4 DEG C of 15~30min of freezing chamber, careful scrapes the film, obtains graft type ionic liquid polyimide film.
At 0.1MPa, 30 DEG C of experimental conditions, the permeation flux of carbon dioxide is risen to by original 5.28Barrer
9.86Barrer CO2/N2Selectivity increases to 73.4, CO by 21.92/CH4Selectivity increases to 38.1, CO by 24.12/O2Choosing
Selecting property increases to 29.2 by 12.6.
Embodiment 12
Aminated functional ion liquid mixing prepared by Example 1 and embodiment 10, mass ratio 1:2 are mixed
Uniformly.
First 10g polyimides is dissolved in 90g N-Methyl pyrrolidone solvent, 60 DEG C of heating stirring 16h, then plus
Enter 2.0g1- amine ethyl -3- butyl imidazole hexafluorophosphate and 1- amine ethyl 3- octylimidazole hexafluorophosphate mixing liquid, after
Casting solution is cast to horizontal glass after the casting solution of formation to be carried out to deaeration processing 12h at room temperature by continuous heating stirring 12h
Film forming is scratched in glass plate.Glass plate is put into vacuum oven, solvent flashing and moisture, solidify film under the conditions of 60 DEG C, take
- 4 DEG C of 15~30min of freezing chamber are placed on after out, careful scrapes the film, obtains graft type ionic liquid polyimide film.
At 0.1MPa, 30 DEG C of experimental conditions, the permeation flux of carbon dioxide is risen to by original 5.28Barrer
9.92Barrer CO2/N2Selectivity increases to 76.3, CO by 21.92/CH4Selectivity increases to 38.1, CO by 24.12/O2Choosing
Selecting property increases to 29.9 by 12.6.
Embodiment 13
Aminated functional ion liquid mixing prepared by Example 1, embodiment 9 and embodiment 10, mass ratio 1:1:
1, it is mixed evenly.
First 10g polyimides is dissolved in 90g N-Methyl pyrrolidone solvent, 60 DEG C of heating stirring 10h, then plus
Enter 1.0g 1- amine ethyl 3- methylimidazole hexafluorophosphate, 1- amine ethyl -3- butyl imidazole hexafluorophosphate and 1- amine ethyl 3-
Octylimidazole hexafluorophosphate mixing liquid continues heating stirring 12h, the casting solution of formation is carried out deaeration processing at room temperature
After 12h, casting solution is cast in horizontal glass plate and scratches film forming.Glass plate is put into vacuum oven, 60 DEG C of conditions
Lower solvent flashing and moisture, solidify film, and -4 DEG C of 15~30min of freezing chamber are placed on after taking-up, and careful scrapes the film, are connect
Branch type ionic liquid polyimide film.
At 0.1MPa, 30 DEG C of experimental conditions, the permeation flux of carbon dioxide is risen to by original 5.28Barrer
10.0Barrer CO2/N2Selectivity increases to 71.5, CO by 21.92/CH4Selectivity increases to 41.1, CO by 24.12/O2Choosing
Selecting property increases to 29.5 by 12.6.
Claims (10)
1. graft type ionic liquid polyimide film, it is characterised in that: the graft type ionic liquid polyimides membrane structure is as follows:
Wherein, n range is 100~200；R1Indicate methylimidazole, butyl imidazole or octylimidazole；
R2It indicates
2. graft type ionic liquid polyimides membrane preparation method, it is characterised in that: method includes the following steps:
(1) polyimide grafted: aminated functional ion liquid to be added in the casting solution of polyimides formation, heating water bath
Stirring, aminated functional ion liquid graft on main polymer chain with pendant manner, obtain amine by the feature structure of schiff bases
The casting solution of base；
(2) it prepares graft type ionic liquid polyimide film: the aminated casting solution blade coating film forming in step (1) utilizes
Solvent evaporated method obtains Modified Membrane, and drying solidifies film, then takes off film after being freezed, and obtains graft type ionic liquid polyimides
Film.
3. graft type ionic liquid polyimides membrane preparation method according to claim 2, it is characterised in that: step (1)
The preparation method of aminated functional ion liquid are as follows: by one of N- methylimidazole, N- butyl imidazole, N- octylimidazole or more
Kind is heated with bromine ethylamine hydrobromide, alcohol reflux, obtains intermediate after dry, adds potassium hydroxide, removes KBr,
Again with KPF6Ion-exchange reactions is carried out, heating water bath is carried out after ethyl alcohol dissolution, removes ethyl alcohol, obtain aminated functional ionic liquid
Body.
4. graft type ionic liquid polyimides membrane preparation method according to claim 2 or 3, it is characterised in that: step
(1) polyimides and aminated functional ionic liquid body mass ratio in are 1:(0.02~0.2)；Condition of water bath heating is 60 DEG C~
80 DEG C, stirring in water bath heats 8~16 hours.
5. graft type ionic liquid polyimides membrane preparation method according to claim 2 or 3, it is characterised in that: step
(1) the aminated functional ion liquid in is 1- (amine ethyl) -3- methylimidazole hexafluorophosphate, 1- (amine ethyl) -3- butyl
Limidazolium hexafluorophosphate, one of 1- (amine ethyl) -3- octylimidazole hexafluorophosphate or a variety of.
6. graft type ionic liquid polyimides membrane preparation method according to claim 2 or 3, it is characterised in that: step
(1) the aminated functional ion liquid in is 1- (amine ethyl) -3- butyl imidazole hexafluorophosphate.
7. graft type ionic liquid polyimides membrane preparation method according to claim 2, it is characterised in that: Grafting Structure
For the schiff bases feature structure of C=N double bond, condition of cure is 40~60 DEG C in step (2), and it is freezing temperature that film condition is taken off after freezing
Degree is -4 DEG C~-15 DEG C, and cooling time is 15~30min.
8. graft type ionic liquid polyimide film application, it is characterised in that: such as the graft type ionic liquid of claim 1~6
Polyimide film is applied in carbon dioxide gas separation.
9. graft type ionic liquid polyimide film application according to claim 8, it is characterised in that: by graft type ion
Liquid polyimide film is for separating titanium dioxide carbon/nitrogen gas, carbon dioxide/methane, carbon dioxide/oxygen mixed gas body
System.
10. graft type ionic liquid polyimide film application according to claim 8, it is characterised in that: by graft type from
Sub- liquid polyimide film is that 0.1MPa~1.6MPa is carried out under conditions of operation temperature is 30 DEG C~70 DEG C in transmembrane pressure
The separation of carbon dioxide gas.
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| CN110898681A (en) * | 2019-09-26 | 2020-03-24 | 上海稀点新材料科技有限公司 | Flat membrane with nano porous structure and preparation method thereof |
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| US20060049102A1 (en) * | 2004-09-03 | 2006-03-09 | Miller Jeffrey T | Ionic polymer membranes |
| US7943543B1 (en) * | 2006-09-29 | 2011-05-17 | Uop Llc | Ionic liquid-solid-polymer mixed matrix membranes for gas separations |
| CA2704634A1 (en) * | 2007-11-05 | 2009-05-14 | Co2Crc Technologies Pty Ltd | Gas separation membranes and processes for the manufacture thereof |
| KR101920716B1 (en) * | 2012-05-17 | 2019-02-13 | 삼성전자주식회사 | Gas separation membrane and method for preparing the same |
| US11007487B2 (en) * | 2015-12-08 | 2021-05-18 | King Abdullah University Of Science And Technology | Fabrication of green polymeric membranes |
| CN105854634A (en) * | 2016-04-05 | 2016-08-17 | 中国科学院过程工程研究所 | Ionic liquid/cellulose acetate blended membrane for gas separation |
| CN105749769B (en) * | 2016-04-13 | 2019-01-11 | 天津大学 | A kind of preparation and application of ionic liquid blend film |
| CN105664737A (en) * | 2016-04-22 | 2016-06-15 | 浙江工业大学 | Preparation method of electrostatic self-assembly modified polyamide reverse osmosis membrane |
| CN105964155B (en) * | 2016-05-13 | 2019-05-14 | 天津工业大学 | Supermolecular beta-cyclodextrin-ionic liquid-polyimides CO2The design and preparation of gas separation membrane material |
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| CN108619921B (en) * | 2017-03-16 | 2021-06-04 | 同济大学 | Ionic liquid modified graphene oxide/polymer composite membrane and preparation and application thereof |
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| CN107875867B (en) * | 2017-11-09 | 2020-02-07 | 石河子大学 | Transfer-promoting membrane based on amino acid ionic liquid and preparation method and application thereof |
| CN108837715B (en) * | 2018-05-24 | 2020-10-16 | 南京工业大学 | Solvent-resistant polyimide film, preparation method and application |
| CN108993180B (en) * | 2018-08-22 | 2020-11-13 | 大连理工大学 | Grafted polyion liquid polyimide membrane and preparation method thereof |
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| CN110404424B (en) | 2021-12-14 |
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