CN106674560B - A kind of polyimide containing crown ether micropore is from tool microporous polymer membranes and preparation method thereof - Google Patents
A kind of polyimide containing crown ether micropore is from tool microporous polymer membranes and preparation method thereof Download PDFInfo
- Publication number
- CN106674560B CN106674560B CN201611147220.2A CN201611147220A CN106674560B CN 106674560 B CN106674560 B CN 106674560B CN 201611147220 A CN201611147220 A CN 201611147220A CN 106674560 B CN106674560 B CN 106674560B
- Authority
- CN
- China
- Prior art keywords
- crown
- micropore
- dibenzo
- microporous polymer
- crown ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The present invention relates to a kind of polyimides containing crown ether micropore from tool microporous polymer membranes and preparation method thereof, prepares diamine solution using aromatic diamine first；Aromatic dianhydride is added in diamine solution, 9~13h is stirred at room temperature；Dehydrating agent and catalyst are added, remove solvent after 3~6h is stirred at 40~65 DEG C and is dried to obtain the polyimide containing crown ether micropore from having a microporous polymer；The polymer is dissolved with organic solvent, obtains casting solution, carries out casting film and drying, the polyimide containing crown ether micropore is obtained and has microporous polymer membranes certainly.Crown ether micropore is introduced in Inventive polymers film, the steric hindrance of crown ether cyclic structure effectively prevent the dense accumulation of polymer segment, guarantees from tool microporous polymer membrane material free volume with higher, and the ehter bond and CO of crown ether2With good compatibility, to guarantee that the made microporous polymer membranes of tool certainly have high gas permeability coefficient and selectivity.
Description
[technical field]
The present invention relates to polymeric membrane fields, and in particular to a kind of polyimide containing crown ether micropore is poly- from tool micropore
Compound film and preparation method thereof.
[background technique]
Common macromolecule member material can be processed that type is relatively good, but there are high osmosis and it is highly selective cannot get both lack
Point；The poromerics such as molecular sieve, metal-organic framework materials permeability with higher and selectivity, can break through common high score
" Robenson " upper limit of sub- membrane material, but it is difficult to the disadvantages of scale is amplified, ultra-thin film preparation is difficult, flexibility is poor.Relatively
First two material, from having capillary copolymer material (PIM), the microcellular structure with molecular sieve analog material be may be implemented to difference
The screening of sized molecules has high transmission selectivity, while the also good, Yi Cheng with flexibility possessed by polymer material itself
The advantages of film, easy scale amplification.It is had received widespread attention recent years based on the above feature from tool microporous polymer membrane material.
But the pore size of such capillary copolymer material is difficult to control, pore-size distribution is wide, unfavorable to gas-selectively.
It is non-planar, twist structured that the typical microporous polymer of tool certainly for Membrane Gas Separation Processes is such as based on phthalocyanine
PIM-1 membrane material, the PIM-EA-TB of the structure containing semicircular, on the strand of PIM-1 be grafted closed pore structure TZPIM, base
In triptycene structure polyimide type PIM membrane material.The studies above show from have microporous polymer membrane material pore size and
Its pore-size distribution is the key factor for influencing its selectivity, and free volume is to influence the key factor of its gas permeability coefficient.
[summary of the invention]
This method aims to overcome that defect existing in the prior art, and it is sub- to provide a kind of polyamides containing crown ether micropore
Amine obtains machinability by force by solution polycondensation and chemical imidization and breaks through from tool microporous polymer membranes and preparation method thereof
The tool microporous polymer membrane material certainly of Trade-off effect, finally prepares the polyamides containing crown ether micropore using solvent evaporated method
Imines have microporous polymer membranes certainly.
In order to achieve the above objectives, the present invention adopts the following technical scheme that:
The following steps are included:
(1) under protective atmosphere, organic solvent X is added in aromatic diamine monomer, stirring and dissolving obtains diamine solution；It presses
The molar ratio of aromatic diamine and aromatic dianhydride is 1:(0.95~1.05), aromatic dianhydride is added in diamine solution,
It is configured to mixed solution A, 9~13h is stirred at room temperature in mixed solution A；Dehydrating agent and catalysis is added into mixed solution A again
Agent, obtains mixed solution B, and mixed solution B removes solvent after stirring 3~6h at 40~65 DEG C and is dried to obtain micro- containing crown ether
The polyimide in hole has microporous polymer certainly；Wherein, aromatic diamine is using crown compound or crown compound and its
Its aromatic diamine monomer is (0.33~3) in molar ratio: 1 mixture；
(2) polyimide containing crown ether micropore is dissolved from tool microporous polymer organic solvent Y, obtains casting film
Casting solution is carried out casting film and drying by liquid, obtains the polyimide containing crown ether micropore and has microporous polymer membranes certainly.
Further, the crown compound in step (1) includes diamino dibenzo -15- crown- 5, diamino dibenzo -
18- crown- 6 or diamino dibenzo -21- crown- 7, other aromatic diamines include p-phenylenediamine, 4,4'- diaminodiphenyl ether, 4,
Bis- [4- (4- amino-benzene oxygen) phenyl] propane of 4'- diaminodiphenyl-methane, 2,2-, the bis- [4- (4- amino-benzene oxygen) of 2,2-
Phenyl] hexafluoropropane or bis- (4- aminophenyl) hexafluoropropane of 2,2-；Aromatic dianhydride includes 4,4'- hexafluoro isopropyl neighbour benzene two
Formic anhydride, 3,3', 4,4'- benzophenone tetracarboxylic dianhydride (BTDA), 4,4'- oxygen diphthalic anhydrides, 4,4'- bibenzene tetracarboxylic dianhydride,
Pyromellitic acid anhydride, 4,4'- (4,4'- isopropyl diphenoxy) two anhydride phthalic acids or 3,4,9,10- tetracarboxylic acid dianhydride.
Further, the preparation step of diamino dibenzo-18 crown-6 specifically includes:
(a) dibenzo-18 crown-6 is dissolved in the in the mixed solvent of chloroform and glacial acetic acid composition, obtains dibenzo -18- crown-
6 solution；
(b) nitric acid and acetic anhydride mixed liquor are added dropwise in dibenzo-18 crown-6 solution, 10~25 DEG C of reactions 1~
1.5h is warming up to 40~80 DEG C the reaction was continued 5~6h then by filtering, recrystallization and vacuum drying and obtains trans--dinitro
Base dibenzo-18 crown-6；Wherein, the ratio of dibenzo-18 crown-6, chloroform, glacial acetic acid, nitric acid and acetic anhydride be (0.0125~
0.0153) mol:(95~115) mL:(70~80) mL:(3~4.5) mL:(13.5~15.5) mL；
(c) trans--dinitro dibenzo-18 crown-6 of preparation is dissolved in ethylene glycol monomethyl ether, obtain concentration be 0.0222~
The reaction solution of 0.0444mmol/mL, reaction solution is added in reaction kettle；Addition accounts for trans--dinitro dibenzo-18 crown-6
The Pd/C catalyst of 2~20wt% of quality, then fills H2To 0.3~0.4MPa, stirring heating, in 50~95 DEG C of 2~3h of reaction；
Then filtrate is obtained by filtration, in 60~85 DEG C of vacuum distillation filtrates, obtains red solid, successively by dry, recrystallization and
Vacuum drying, obtains trans--diamino dibenzo-18 crown-6.
Further, recrystallization is carried out using n,N-Dimethylformamide in 140~160 DEG C in step (b)；Step (c)
Middle recrystallization is carried out using the mixed solvent of ethyl alcohol and ethylene glycol monomethyl ether in 70~100 DEG C, wherein ethyl alcohol and ethylene glycol monomethyl ether
Volume ratio is 0.3~0.7.
Further, the aromatic diamine in step (1) mixed solution A and aromatic dianhydride total mass fraction be 17~
20%.
Further, the dehydrating agent in step (1) is acetic anhydride, and catalyst is triethylamine；Aromatic diamine and acetic anhydride
Molar ratio be 1:(8~10), the molar ratio of acetic anhydride and triethylamine is 2:(1~1.1).
Further, the organic solvent X of step (1) is n,N-Dimethylformamide, n,N-dimethylacetamide or N- first
Base pyrrolidones；The organic solvent Y of step (2) is DMAC N,N' dimethyl acetamide or N,N-dimethylformamide.
Further, the casting solution concentration in step (2) is 15wt%~30wt%.
Further, the first 2~4h of deaeration in a vacuum drying oven of casting solution in step (2), is then poured into mold again
Carry out casting film；Drying is then dried in vacuo for 24 hours at 100~140 DEG C in 40~60 DEG C of vacuum drying 12h.
A kind of polyimide using containing crown ether micropore made from preparation method as described above is from having microporous polymer
Object film.
Compared with prior art, the invention has the following beneficial technical effects:
Machinability is obtained by force by solution polycondensation and chemical imidization in method of the invention and breaks through Trade-off effect
That answers has specific cyclic annular microcellular structure from crown ether compound in tool microporous polymer, used raw material, and hole is big
It is small with crown ether type fromTo being greater thanThis and H2、CO2Etc. gas-kinetic diameters it is suitable；These crown ethers are introduced into film
It can use crown ether duct after material and screening separation carried out to different size of gas molecule, be obviously improved the screening choosing of membrane material
Selecting property.The ehter bond and CO of crown ether simultaneously2With good compatibility, CO can also be effectively increased2Dissolution selectivity.In segment
In structure, crown ether has big cyclic structure, since steric hindrance acts on, can be effectively prevented segment dense packing, improve
The free volume of material；Be conducive to improve the permeability of membrane material；Polyimides relies on its excellent mechanical performance and thermostabilization
Property be widely used in gaseous jet simulation field, pass through and change the chemical structure of diamines or dianhydride and can get high-performance polyimide
Gas separation membrane material.For both monomers compared with the monomer of numerous other heterocycle polymers, raw material sources are extensive, synthesis also compared with
It is easy.Polyimide produced by the present invention containing crown ether micropore from tool microporous polymer be a kind of molecule interchain or intramolecular
Portion has the polymeric film material of the microcellular structure similar to molecular sieve or MOFs material, and the present invention introduces on PIM strand
The crown ether cycle of specific closure pore size can significantly improve the screening selectivity of membrane material；It is closed at microcellular structure and three
Dimension stereochemical structure introduces the dense accumulation that can prevent strand, obtains higher free volume, improves film gas permeability coefficient, because
This, the processing performance having had, and can break through Trade-off effect；There is excellent thermal stability, decomposition temperature simultaneously
At 400 DEG C or more；The new polyimide containing crown ether micropore of one kind, which is prepared, by using solvent evaporated method has micropore certainly
Polymer film introduces crown ether micropore in Inventive polymers film, and method is reliable, equipment is simple, controllability is strong.
The polyimide that the present invention contains crown ether micropore introduces cyclic crown ether micropore from tool microporous polymer membranes, should
Micropore size is controllable, size uniformity, while the steric hindrance of crown ether cyclic structure effectively prevent the dense accumulation of polymer segment,
Guarantee from tool microporous polymer membrane material free volume with higher, and the ehter bond and CO of crown ether2With affine well
Property, to guarantee that the made microporous polymer membranes of tool certainly have high gas permeability coefficient and selectivity, infiltration coefficient and selection
Performance is enough to be up to 519barrer, 542.9 respectively.And the membrane material machinability is strong, gas separating property is excellent, application prospect
Extensively.
[Detailed description of the invention]
Fig. 1 is trans--diamino dibenzo-18 crown-6 prepared by present example 11HNMR。
Fig. 2 is the heat stability testing figure of Examples 1 to 3.
[specific embodiment]
Below with reference to embodiment, the present invention is further described.
The present invention prepares the polyimide containing crown ether microcellular structure from having microporous polymer membranes by polycondensation, below it is real
It is different to apply dibenzo-18 crown-6 used in example, 4,4'- diaminodiphenyl ether, 4,4'- diaminodiphenyl-methane and 4,4'- hexafluoro
Propyl phthalic anhydride is the production of Beijing lark prestige Science and Technology Ltd.；N,N-Dimethylformamide, N, N- dimethyl second
Amide, N-Methyl pyrrolidone, nitric acid, glacial acetic acid, chloroform, triethylamine, ethyl alcohol, ethylene glycol monomethyl ether and Pd/C catalyst are
Sinopharm Chemical Reagent Co., Ltd.'s production；Acetic anhydride is Xilong Chemical Co., Ltd's production.
N,N-Dimethylformamide, n,N-dimethylacetamide, N-Methyl pyrrolidone, ethylene glycol monomethyl ether use preceding addition
Suitable molecular sieve is carried out except water process；4,4'- diaminodiphenyl ether, 80 DEG C of 4,4'- diaminodiphenyl-methane vacuum drying
48h；120 DEG C of vacuum drying 48h of 4,4'- hexafluoro isopropyl phthalic anhydride.
The method of the present invention synthesizes the aromatic diamine containing crown ether structures by nitration reaction and catalytic hydrogenation, then by molten
Liquid polycondensation and chemical imidization obtain machinability by force and break through the tool microporous polymer membrane material certainly of Trade-off effect, most
Have microporous polymer membranes certainly using polyimide of the solvent evaporated method preparation containing crown ether micropore afterwards；Specifically include following step
It is rapid:
(1) preparation of crown compound；Crown compound includes diamino dibenzo -15- crown- 5, diamino dibenzo -
18- crown- 6 or diamino dibenzo -21- crown- 7, are illustrated for preparing diamino dibenzo-18 crown-6 below, preparation
When other crown compounds, the dibenzo-18 crown-6 in raw material is substituted for dibenzo -15- crown- 5 or dibenzo -21- crown- 7
.
Dibenzo-18 crown-6 is dissolved in the in the mixed solvent of chloroform, glacial acetic acid composition, it is molten to obtain dibenzo-18 crown-6
Liquid；Nitric acid and acetic anhydride mixed liquor are added dropwise in dibenzo-18 crown-6 solution, wherein dibenzo-18 crown-6, chlorine
The ratio of imitative, glacial acetic acid, nitric acid and acetic anhydride is (0.0125~0.0153) mol:(95~115) mL:(70~80) mL:(3~
4.5) mL:(13.5~15.5) mL；10~25 DEG C of 1~1.5h of reaction are warming up to 40~80 DEG C the reaction was continued 5~6h, by yellow
Precipitating filtering, recrystallization, vacuum drying, can be obtained trans--dinitro dibenzo-18 crown-6 containing crown ether structures.It will system
Standby trans--dinitro dibenzo-18 crown-6 is dissolved in ethylene glycol monomethyl ether, and obtaining concentration is 0.0222~0.0444mmol/mL's
Reaction solution is added in reaction kettle by reaction solution；Addition accounts for trans- -2~20wt%'s of dinitro dibenzo-18 crown-6 quality
Pd/C catalyst, then fills H2To 0.3~0.4MPa, stirring heating, in 50~95 DEG C of 2~3h of reaction；Filter solution in kettle, In
60~85 DEG C of vacuum distillation filtrates, obtain red solid, and trans--diamino can be obtained in successively dry, recrystallization, vacuum drying
Dibenzo-18 crown-6.
The recrystallization of trans--dinitro dibenzo-18 crown-6 described in step (1) using N,N-dimethylformamide in
The recrystallization of 140~160 DEG C of progress, trans--diamino dibenzo-18 crown-6 uses ethyl alcohol/ethylene glycol monomethyl ether mixed solvent
It is carried out in 70~100 DEG C, wherein the volume ratio of ethyl alcohol and ethylene glycol monomethyl ether is 0.3~0.7.
(2) preparation of the crown ether microporous polyamide imines from tool microporous polymer
Under nitrogen protection, organic solvent is added in aromatic diamine monomer, organic solvent can be N, N- dimethyl formyl
Amine, n,N-dimethylacetamide, any one in N-Methyl pyrrolidone, magnetic agitation dissolves to obtain diamine solution；According to virtue
The molar ratio of fragrant race's diamines and aromatic dianhydride is 1:(0.95~1.05), it is molten that aromatic dianhydride solid is added directly into diamines
In liquid, it is configured to the solution that aromatic diamine and aromatic dianhydride total mass fraction are 17~20wt%, stir 9 at room temperature~
13h；The mixed liquor of acetic anhydride (dehydrating agent) and triethylamine (catalyst), the molar ratio of aromatic diamine monomer and acetic anhydride is added
For 1:(8~10)；The molar ratio of acetic anhydride and triethylamine is 2:(1~1.1)；3~6h is stirred at 40~65 DEG C；It is cooled to room
Temperature, by end reaction solution be added to desolventizing in ethanol in proper amount, using the multiple washing impurity-removing of ethyl alcohol, in 90~120 DEG C of vacuum
Dry 12~for 24 hours, the polyimide containing crown ether micropore can be obtained and have microporous polymer certainly.
Wherein, aromatic diamine is crown compound prepared by the present invention or crown compound and other aromatic diamines
Monomer is (0.33~3) in molar ratio: 1 mixture；Crown compound includes diamino dibenzo -15- crown- 5, diamino two
Phendioxin 8- crown- 6 or diamino dibenzo -21- crown- 7, other aromatic diamines can be p-phenylenediamine, 4,4'- diamino hexichol
Bis- [4- (4- amino-benzene oxygen) phenyl] propane of ether, 4,4'- diaminodiphenyl-methane, 2,2-, bis- [4- (the 4- aminobenzenes of 2,2-
Oxygroup) phenyl] hexafluoropropane or bis- (4- aminophenyl) hexafluoropropane of 2,2-.
Aromatic dianhydride be 4,4'- hexafluoro isopropyl phthalic anhydride, 3,3', 4,4'- benzophenone tetracarboxylic dianhydride (BTDA), 4,
4'- oxygen diphthalic anhydrides, 4,4'- bibenzene tetracarboxylic dianhydride, pyromellitic acid anhydride, 4,4'- (4,4'- isopropyl diphenyl
Oxygroup) two anhydride phthalic acids or 3,4,9,10- tetracarboxylic acid dianhydride.
Catalyst can also replace triethylamine with pyridine.
(3) preparation of the crown ether microporous polyamide imines from tool microporous polymer membranes
The membrane material n,N-dimethylacetamide or n,N-Dimethylformamide of above-mentioned preparation are dissolved, concentration, which is made, is
The homogeneous solution of 15~30wt% is placed in a vacuum drying oven 2~4h of deaeration, is then poured over casting solution and is fixed on glass plate
On circular die in, in 40~60 DEG C of vacuum drying 12h, then again 100~140 DEG C vacuum drying for 24 hours, can be obtained containing
The polyimide of crown ether micropore has microporous polymer membranes certainly.
The present invention is described in further details below by specific embodiment.
Embodiment 1
(1) preparation of diamino dibenzo-18 crown-6
0.0142mol dibenzo-18 crown-6 is dissolved in the in the mixed solvent of 105mL chloroform, 75mL glacial acetic acid composition, it will
3.6mL nitric acid and 14.25mL acetic anhydride mixed liquor are added dropwise in dibenzo-18 crown-6 solution, -17 DEG C of reaction 1.2h, are risen
Yellow mercury oxide filtering, 150 DEG C of recrystallizations, vacuum drying can be obtained containing crown ether structures to 50 DEG C of the reaction was continued 5.5h for temperature
Trans--dinitro dibenzo-18 crown-6, yield can reach 62.9mol%；Filtrate stands, and analyses almost without cis-product
Out.
The 0.0037mol dinitro dibenzo-18 crown-6 of preparation is dissolved in 100mL ethylene glycol monomethyl ether, obtained concentration is
The reaction solution of 0.037mmol/mL, reaction solution is added in reaction kettle；Dinitro dibenzo-18 crown-6 quality 4% is added
Pd/C catalyst, then fills H2To 0.35MPa, stirring heating, in 75 DEG C of reaction 2.5h；Solution in kettle is filtered, is depressurized at 70 DEG C
Distillation filtrate obtains red solid, it is successively dry, 80 DEG C use volume ratio to tie again for 0.3 ethyl alcohol/ethylene glycol monomethyl ether mixed solvent
Brilliant, vacuum drying, can be obtained trans--diamino dibenzo-18 crown-6.Shown in its reaction equation following equation 1.
Equation 1:
(2) preparation of the crown ether microporous polyamide imines from tool microporous polymer
Under nitrogen protection, by the diamino dibenzo-18 crown-6 of step (1) preparation and business 4,4'- diamino hexichol
Ether is 0.5 mixing as aromatic diamine monomer in molar ratio, n,N-dimethylacetamide is added, magnetic agitation dissolves to obtain two
Amine aqueous solution；It is 1:1 by the molar ratio of aromatic diamine and aromatic dianhydride, 4,4'- hexafluoro isopropyl phthalic anhydride is solid
Body is added directly into diamine solution, is configured to the solution that aromatic diamine and aromatic dianhydride total mass fraction are 18wt%,
10h is stirred at room temperature；It is 1:9, the molar ratio of acetic anhydride and triethylamine according to aromatic diamine monomer and the molar ratio of acetic anhydride
For 2:1, the mixed liquor of acetic anhydride and triethylamine is added, stirs 4.5h at 50 DEG C；It is cooled to room temperature, by end reaction solution precipitation
Agent, removal of impurities, 100 DEG C of vacuum drying 23h can be obtained the polyimide containing crown ether micropore and have microporous polymer certainly.It is anti-
It answers shown in equation following equation 2.
Equation 2:
(3) preparation of the crown ether microporous polyamide imines from tool microporous polymer membranes
The membrane material of above-mentioned preparation is dissolved with n,N-dimethylacetamide, be made mass fraction be 20% it is uniform molten
Liquid is placed in a vacuum drying oven deaeration 3h, is then poured over casting solution and is fixed in the circular die on glass plate, in 50 DEG C
It is dried in vacuo 12h, then for 24 hours, it is poly- from tool micropore that the polyimide containing crown ether micropore can be obtained in 120 DEG C of vacuum drying again
Compound film.
Referring to Fig. 1, nuclear magnetic resonance test is carried out to trans--diamino dibenzo-18 crown-6, two phenyl ring are in symmetrical
Position, the characteristic peak ratio of the hydrogen on the phenyl ring of diamino dibenzo-18 crown-6 are a:b:c=2:2:2, and the place f is amino hydrogen
Characteristic peak, hydrogen number are exactly 4, further illustrate that only one meta position hydrogen of each phenyl ring is by nitro during nitration reaction
Replace, also illustrates that the nitro on two phenyl ring is reduced into amino by catalytic hydrogenation.
Embodiment 2
(1) step (1) of the diamino dibenzo-18 crown-6 during the preparation method is the same as that of Example 1.
(2) preparation of the crown ether microporous polyamide imines from tool microporous polymer
Under nitrogen protection, by diamino dibenzo-18 crown-6 and business 4,4'- diaminodiphenyl-methane by mole
Than mixing for 0.33, n,N-dimethylacetamide is added, magnetic agitation dissolves to obtain diamine solution；By aromatic diamine and fragrance
The molar ratio of race's dianhydride is 1:1, and 4,4'- hexafluoro isopropyl phthalic anhydride solid is added directly into diamine solution, is matched
Aromatic diamine and aromatic dianhydride total mass fraction is made as the solution of 18wt%, stirs 9h at room temperature；According to aromatic series two
The molar ratio of amine monomers and acetic anhydride is 1:8, and the molar ratio of acetic anhydride and triethylamine is 2:1, and acetic anhydride and triethylamine is added
Mixed liquor stirs 3h at 50 DEG C；It is cooled to room temperature, for 24 hours by end reaction solution desolventizing, removal of impurities, 90 DEG C of vacuum drying
It obtains the polyimide containing crown ether micropore and has microporous polymer certainly.Shown in its reaction equation following equation 3.
Equation 3:
(3) preparation of the crown ether microporous polyamide imines from tool microporous polymer membranes
The membrane material of above-mentioned preparation is dissolved with n,N-dimethylacetamide, be made mass fraction be 15% it is uniform molten
Liquid is placed in a vacuum drying oven deaeration 2h, is then poured over casting solution and is fixed in the circular die on glass plate, in 40 DEG C
It is dried in vacuo 12h, then for 24 hours, it is poly- from tool micropore that the polyimide containing crown ether micropore can be obtained in 100 DEG C of vacuum drying again
Compound film.
Embodiment 3
(1) step (1) of the diamino dibenzo-18 crown-6 during the preparation method is the same as that of Example 1.
(2) preparation of the crown ether microporous polyamide imines from tool microporous polymer
Under nitrogen protection, trans--diamino dibenzo-18 crown-6 of step (1) preparation is weighed, N, N- diformazan is added
Yl acetamide, magnetic agitation dissolution；It is 1:1 by the molar ratio of aromatic diamine and aromatic dianhydride, by 4,4'- hexafluoro isopropyl
Phthalic anhydride solid is added directly into diamine solution, is configured to aromatic diamine and aromatic dianhydride total mass fraction is
The solution of 20wt%, stirs 11h at room temperature；Be 1:8.5 according to aromatic diamine monomer and the molar ratio of acetic anhydride, acetic anhydride with
The molar ratio of triethylamine is 2:1, and the mixed liquor of acetic anhydride and triethylamine is added, stirs 4h at 40 DEG C；It is cooled to room temperature, it will be final
Reaction solution desolventizing, removal of impurities, 95 DEG C of vacuum drying 22h can be obtained the polyimide containing crown ether micropore and have micropore certainly
Polymer.Shown in its reaction equation following equation 4.
Equation 4:
(3) preparation of the crown ether microporous polyamide imines from tool microporous polymer membranes
The membrane material of above-mentioned preparation is dissolved with n,N-dimethylacetamide, be made mass fraction be 30% it is uniform molten
Liquid is placed in a vacuum drying oven deaeration 4h, is then poured over casting solution and is fixed in the circular die on glass plate, in 60 DEG C
It is dried in vacuo 12h, then for 24 hours, it is poly- from tool micropore that the polyimide containing crown ether micropore can be obtained in 140 DEG C of vacuum drying again
Compound film.
The gas separating property of 1 Examples 1 to 3 of table
| Title | Infiltration coefficient/barrer | Selectivity |
| Embodiment 1 | 238.6 | 149.1 |
| Embodiment 2 | 408.6 | 412.51 |
| Embodiment 3 | 519.4 | 542.91 |
With CO2/N2To separate object, in 0.2MPa, 30 DEG C, gas of the made polyimide from tool microporous polymer membranes
Body separating property is as shown in table 1.Embodiment 3 is film-made, infiltration coefficient and selectivity respectively be up to 519barrer,
542.9, due to crown ether pore size and CO2Kinetic diameter it is suitable, while the ehter bond and CO of crown ether2With fine compatibility.
Referring to fig. 2, it presents the polyimide containing crown ether micropore prepared by embodiment 1-3 and has microporous polymer certainly
The thermal stability of film, initial decomposition temperature at 400~450 DEG C, show good thermal stability.
Embodiment 4
(1) preparation of diamino dibenzo-18 crown-6
0.0125mol dibenzo-18 crown-6 is dissolved in the in the mixed solvent of 95mL chloroform, 70mL glacial acetic acid composition, it will
3.0mL nitric acid and 13.5mL acetic anhydride mixed liquor are added dropwise in dibenzo-18 crown-6 solution, and 10 DEG C of reaction 1h are warming up to
Yellow mercury oxide filtering, 140 DEG C of recrystallizations, vacuum drying can be obtained containing the anti-of crown ether structures 40 DEG C of the reaction was continued 5h
Formula-dinitro dibenzo-18 crown-6.Trans--dinitro dibenzo-18 crown-6 of preparation is dissolved in 100mL ethylene glycol monomethyl ether,
The reaction solution that concentration is 0.0222mmol/mL is made, reaction solution is added in reaction kettle；Dinitro dibenzo -18- is added
The Pd/C catalyst of 6 mass 2% of crown-, then fills H2To 0.3MPa, stirring heating, in 50 DEG C of reaction 2h；Solution in kettle is filtered,
In 60 DEG C of vacuum distillation filtrates, obtain red solid, it is successively dry, 70 DEG C use volume ratio to mix for 0.7 ethyl alcohol/ethylene glycol monomethyl ether
Bonding solvent recrystallization, vacuum drying, can be obtained trans--diamino dibenzo-18 crown-6.
(2) preparation of the crown ether microporous polyamide imines from tool microporous polymer
Under nitrogen protection, by step (1) preparation trans--diamino dibenzo-18 crown-6 and p-phenylenediamine by mole
Than being used as aromatic diamine monomer for 1.5 mixing, n,N-dimethylacetamide is added, magnetic agitation dissolves to obtain diamine solution；
It is 1:0.95 by the molar ratio of aromatic diamine and aromatic dianhydride, 3,3', 4,4'- benzophenone tetracarboxylic dianhydride (BTDA)s is directly added into
Into diamine solution, aromatic diamine and aromatic dianhydride total mass fraction are configured to as the solution of 17wt%, is stirred at room temperature
12h；It is 1:9.5 according to aromatic diamine monomer and the molar ratio of acetic anhydride, the molar ratio of acetic anhydride and triethylamine is 2:1.1,
The mixed liquor of acetic anhydride and triethylamine is added, stirs 5h at 45 DEG C；Be cooled to room temperature, by end reaction solution desolventizing, removal of impurities,
110 DEG C of vacuum drying 20h can be obtained the polyimide containing crown ether micropore and have microporous polymer certainly.
(3) preparation of the crown ether microporous polyamide imines from tool microporous polymer membranes
The membrane material of above-mentioned preparation is dissolved with n,N-dimethylacetamide, be made mass fraction be 25% it is uniform molten
Liquid is placed in a vacuum drying oven deaeration 2.2h, is then poured over casting solution and is fixed in the circular die on glass plate, in 45
DEG C vacuum drying 12h, then for 24 hours, the polyimide containing crown ether micropore can be obtained from having a micropore in 110 DEG C of vacuum drying again
Polymer film.
Embodiment 5
(1) preparation of diamino dibenzo-18 crown-6
0.0153mol dibenzo-18 crown-6 is dissolved in the in the mixed solvent of 115mL chloroform, 80mL glacial acetic acid composition, it will
3.5mL nitric acid and 15.5mL acetic anhydride mixed liquor are added dropwise in dibenzo-18 crown-6 solution, 25 DEG C of reaction 1.5h, heating
Yellow mercury oxide filtering, 160 DEG C of recrystallizations, vacuum drying can be obtained containing the anti-of crown ether structures to 80 DEG C of the reaction was continued 6h
Formula-dinitro dibenzo-18 crown-6.The dinitro dibenzo-18 crown-6 of preparation is dissolved in 100mL ethylene glycol monomethyl ether, is made
Concentration is the reaction solution of 0.0444mmol/mL, and reaction solution is added in reaction kettle；Trans--dinitro dibenzo -18- is added
The Pd/C catalyst of 6 mass 20% of crown-, then fills H2To 0.4MPa, stirring heating, in 95 DEG C of reaction 3h；Solution in kettle is filtered,
In 85 DEG C of vacuum distillation filtrates, obtain red solid, it is successively dry, 100 DEG C use volume ratio for 0.5 ethyl alcohol/ethylene glycol monomethyl ether
Mixed solvent recrystallization, vacuum drying, can be obtained trans--diamino dibenzo-18 crown-6.
(2) preparation of the crown ether microporous polyamide imines from tool microporous polymer
Under nitrogen protection, the diamino dibenzo-18 crown-6 and 2 prepared by step (1), bis- [4- (the 4- aminobenzenes of 2-
Oxygroup) phenyl] propane is 2 mixing as aromatic diamine monomer in molar ratio, n,N-Dimethylformamide, magnetic agitation is added
Dissolution obtains diamine solution；It is 1:0.98 by the molar ratio of aromatic diamine and aromatic dianhydride, by 4,4'- oxygen, two O-phthalic
Acid anhydrides is added directly into diamine solution, is configured to aromatic diamine and aromatic dianhydride total mass fraction is the molten of 19wt%
Liquid stirs 13h at room temperature；It is 1:10 according to aromatic diamine monomer and the molar ratio of acetic anhydride, acetic anhydride and triethylamine rub
You are added the mixed liquor of acetic anhydride and triethylamine, stir 6h at 65 DEG C than being 2:1.1；It is cooled to room temperature, by end reaction solution
Desolventizing, removal of impurities, 115 DEG C of vacuum drying 18h can be obtained the polyimide containing crown ether micropore and have microporous polymer certainly.
(3) preparation of the crown ether microporous polyamide imines from tool microporous polymer membranes
The membrane material of above-mentioned preparation is dissolved with n,N-Dimethylformamide, be made mass fraction be 18% it is uniform molten
Liquid is placed in a vacuum drying oven deaeration 2.5h, is then poured over casting solution and is fixed in the circular die on glass plate, in 55
DEG C vacuum drying 12h, then for 24 hours, the polyimide containing crown ether micropore can be obtained from having a micropore in 130 DEG C of vacuum drying again
Polymer film.
Embodiment 6
(1) preparation of diamino dibenzo -21- crown- 7
Dibenzo-18 crown-6 is substituted for dibenzo -21- crown- 7, other conditions are using identical as embodiment 5 step (1)
Condition, trans--diamino dibenzo -21- crown- 7 is prepared.
(2) preparation of the crown ether microporous polyamide imines from tool microporous polymer
Under nitrogen protection, the diamino dibenzo -21- crown- 7 and 2 prepared by step (1), bis- [4- (the 4- aminobenzenes of 2-
Oxygroup) phenyl] hexafluoropropane is 3 mixing as aromatic diamine monomer in molar ratio, n,N-Dimethylformamide, magnetic force is added
Stirring and dissolving obtains diamine solution；It is 1:1.02 by the molar ratio of aromatic diamine and aromatic dianhydride, by 4,4'- biphenyl tetracarboxylic
Acid dianhydride is added directly into diamine solution, is configured to aromatic diamine and aromatic dianhydride total mass fraction is 17.5wt%'s
Solution stirs 9.5h at room temperature；It is 1:8.2 according to aromatic diamine monomer and the molar ratio of acetic anhydride, acetic anhydride and pyridine
Molar ratio is 2:1.1, and the mixed liquor of acetic anhydride and pyridine is added, stirs 3.5h at 60 DEG C；It is cooled to room temperature, end reaction is molten
Liquid desolventizing, removal of impurities, 120 DEG C of vacuum drying 12h can be obtained the polyimide containing crown ether micropore and have microporous polymer certainly
Object.
(3) preparation of the crown ether microporous polyamide imines from tool microporous polymer membranes
The membrane material of above-mentioned preparation is dissolved with n,N-Dimethylformamide, be made mass fraction be 22% it is uniform molten
Liquid is placed in a vacuum drying oven deaeration 2.8h, is then poured over casting solution and is fixed in the circular die on glass plate, in 41
DEG C vacuum drying 12h, then for 24 hours, the polyimide containing crown ether micropore can be obtained from having a micropore in 105 DEG C of vacuum drying again
Polymer film.
Embodiment 7
(1) preparation of diamino dibenzo -15- crown- 5
Dibenzo-18 crown-6 is substituted for dibenzo -15- crown- 5, other conditions are using identical as embodiment 5 step (1)
Condition, trans--diamino dibenzo -15- crown- 5 is prepared.
(2) preparation of the crown ether microporous polyamide imines from tool microporous polymer
Under nitrogen protection, the diamino dibenzo -15- crown- 5 and 2 prepared by step (1), 2- bis- (4- aminophenyls)
Hexafluoropropane is 1 mixing as aromatic diamine monomer in molar ratio, N-Methyl pyrrolidone is added, magnetic agitation dissolves to obtain
Diamine solution；It is 1:1.04 by the molar ratio of aromatic diamine and aromatic dianhydride, pyromellitic acid anhydride is added directly into
In diamine solution, aromatic diamine and aromatic dianhydride total mass fraction are configured to as the solution of 18.5wt%, is stirred at room temperature
10.5h；It is 1:9.6 according to aromatic diamine monomer and the molar ratio of acetic anhydride, the molar ratio of acetic anhydride and triethylamine is 2:
1.05, the mixed liquor of acetic anhydride and triethylamine is added, stirs 5.5h at 55 DEG C；It is cooled to room temperature, by end reaction solution precipitation
Agent, removal of impurities, 105 DEG C of vacuum drying 23h can be obtained the polyimide containing crown ether micropore and have microporous polymer certainly.
(3) preparation of the crown ether microporous polyamide imines from tool microporous polymer membranes
The membrane material of above-mentioned preparation is dissolved with n,N-Dimethylformamide, be made mass fraction be 26% it is uniform molten
Liquid is placed in a vacuum drying oven deaeration 3.2h, is then poured over casting solution and is fixed in the circular die on glass plate, in 54
DEG C vacuum drying 12h, then for 24 hours, the polyimide containing crown ether micropore can be obtained from having a micropore in 115 DEG C of vacuum drying again
Polymer film.
Embodiment 8
(1) preparation of diamino dibenzo-18 crown-6
0.0144mol dibenzo-18 crown-6 is dissolved in the in the mixed solvent of 110mL chloroform, 72mL glacial acetic acid composition, it will
3.8mL nitric acid and 14mL acetic anhydride mixed liquor are added dropwise in dibenzo-18 crown-6 solution, and 20 DEG C of reaction 1.4h are warming up to
Yellow mercury oxide filtering, 148 DEG C of recrystallizations, vacuum drying can be obtained containing the anti-of crown ether structures 50 DEG C of the reaction was continued 5.2h
Formula-dinitro dibenzo-18 crown-6.Trans--dinitro dibenzo-18 crown-6 of preparation is dissolved in 100mL ethylene glycol monomethyl ether,
The reaction solution that concentration is 0.0333mmol/mL is made, reaction solution is added in reaction kettle；Dinitro dibenzo -18- is added
The Pd/C catalyst of 6 mass 10% of crown-, then fills H2To 0.38MPa, stirring heating, in 80 DEG C of reaction 2.2h；It filters molten in kettle
Liquid obtains red solid in 85 DEG C of vacuum distillation filtrates, it is successively dry, 90 DEG C use volume ratio for 0.6 ethyl alcohol/ethylene glycol first
Ether mixed solvent recrystallization, vacuum drying, can be obtained trans--diamino dibenzo-18 crown-6.
(2) preparation of the crown ether microporous polyamide imines from tool microporous polymer
Under nitrogen protection, using the diamino dibenzo-18 crown-6 of step (1) preparation as aromatic diamine monomer, add
Enter N-Methyl pyrrolidone, magnetic agitation dissolves to obtain diamine solution；Molar ratio by aromatic diamine and aromatic dianhydride is
4,4'- (4,4'- isopropyl diphenoxy) two anhydride phthalic acids are added directly into diamine solution, are configured to aromatic series by 1:1.05
The solution that diamines and aromatic dianhydride total mass fraction are 19.5wt%, stirs 11.5h at room temperature；According to aromatic diamine monomer
It is 1:9.3 with the molar ratio of acetic anhydride, the molar ratio of acetic anhydride and triethylamine is 2:1.05, and the mixed of acetic anhydride and triethylamine is added
Liquid is closed, stirs 3.2h at 48 DEG C；It is cooled to room temperature, by end reaction solution desolventizing, removal of impurities, 100 DEG C of vacuum drying 23h, i.e.,
It can obtain the polyimide containing crown ether micropore and have microporous polymer certainly.
(3) preparation of the crown ether microporous polyamide imines from tool microporous polymer membranes
The membrane material of above-mentioned preparation is dissolved with n,N-Dimethylformamide, be made mass fraction be 28% it is uniform molten
Liquid is placed in a vacuum drying oven deaeration 3.5h, is then poured over casting solution and is fixed in the circular die on glass plate, in 59
DEG C vacuum drying 12h, then for 24 hours, the polyimide containing crown ether micropore can be obtained from having a micropore in 125 DEG C of vacuum drying again
Polymer film.
The present invention relates to a kind of polyimides containing crown ether micropore to have microporous polymer membranes and preparation method thereof certainly.This
Invention passes sequentially through nitration reaction, catalytic hydrogenation synthesizing diamino takes using crown compounds such as dibenzo-18 crown-6s as raw material
For crown ether；Then replace crown ether as raw material using dicarboxylic anhydride and diamino, pass sequentially through solution polycondensation and chemical imidization method, make
The polyimide containing crown ether micropore is obtained from tool microporous polymer membrane material；Crown ether is finally contained using solvent evaporated method preparation
The polyimide of micropore has microporous polymer membranes certainly.
Claims (8)
1. the preparation method that a kind of polyimide containing crown ether micropore has microporous polymer membranes certainly, it is characterised in that: including
Following steps:
(1) under protective atmosphere, organic solvent X is added in aromatic diamine monomer, stirring and dissolving obtains diamine solution；By fragrance
The molar ratio of race's diamines and aromatic dianhydride is 1:(0.95~1.05), aromatic dianhydride is added in diamine solution, is prepared
At mixed solution A, 9~13h is stirred at room temperature in mixed solution A；Dehydrating agent and catalyst is added into mixed solution A again, obtains
Solvent is removed after stirring 3~6h at 40~65 DEG C to mixed solution B, mixed solution B and is dried to obtain containing crown ether micropore
Polyimide has microporous polymer certainly；Wherein, aromatic diamine is using crown compound or crown compound and other virtues
Fragrant race's diamine monomer is (0.33~3) in molar ratio: 1 mixture；
(2) polyimide containing crown ether micropore is dissolved from tool microporous polymer organic solvent Y, obtains casting solution, it will
Casting solution carries out casting film and drying, obtains the polyimide containing crown ether micropore and has microporous polymer membranes certainly；
Crown compound in step (1) includes diamino dibenzo -15- crown- 5, diamino dibenzo-18 crown-6 or diamino
Base dibenzo -21- crown- 7, other aromatic diamines include p-phenylenediamine, 4,4'- diaminodiphenyl ether, 4,4'- diamino hexichol
Bis- [4- (4- amino-benzene oxygen) phenyl] propane of methylmethane, 2,2-, bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane of 2,2-
Or bis- (4- aminophenyl) hexafluoropropane of 2,2-；Aromatic dianhydride includes 4,4'- hexafluoro isopropyl phthalic anhydride, 3,3',
4,4'- benzophenone tetracarboxylic dianhydride (BTDA), 4,4'- oxygen diphthalic anhydrides, 4,4'- bibenzene tetracarboxylic dianhydride, Pyromellitic Acid two
Acid anhydride, 4,4'- (4,4'- isopropyl diphenoxy) two anhydride phthalic acids or 3,4,9,10- tetracarboxylic acid dianhydride；
The preparation step of diamino dibenzo-18 crown-6 specifically includes:
(a) dibenzo-18 crown-6 is dissolved in the in the mixed solvent of chloroform and glacial acetic acid composition, it is molten to obtain dibenzo-18 crown-6
Liquid；
(b) nitric acid and acetic anhydride mixed liquor are added dropwise in dibenzo-18 crown-6 solution, 10~25 DEG C of reactions 1~
1.5h is warming up to 40~80 DEG C the reaction was continued 5~6h then by filtering, recrystallization and vacuum drying and obtains trans--dinitro
Base dibenzo-18 crown-6；Wherein, the ratio of dibenzo-18 crown-6, chloroform, glacial acetic acid, nitric acid and acetic anhydride be (0.0125~
0.0153) mol:(95~115) mL:(70~80) mL:(3~4.5) mL:(13.5~15.5) mL；
(c) trans--dinitro dibenzo-18 crown-6 of preparation is dissolved in ethylene glycol monomethyl ether, obtain concentration be 0.0222~
The reaction solution of 0.0444mmol/mL, reaction solution is added in reaction kettle；Addition accounts for trans--dinitro dibenzo-18 crown-6
The Pd/C catalyst of 2~20wt% of quality, then fills H2To 0.3~0.4MPa, stirring heating, in 50~95 DEG C of 2~3h of reaction；
Then filtrate is obtained by filtration, in 60~85 DEG C of vacuum distillation filtrates, obtains red solid, successively by dry, recrystallization and
Vacuum drying, obtains trans--diamino dibenzo-18 crown-6.
2. the preparation side that a kind of polyimide containing crown ether micropore according to claim 1 has microporous polymer membranes certainly
Method, it is characterised in that: recrystallization is carried out using n,N-Dimethylformamide in 140~160 DEG C in step (b)；Weight in step (c)
Crystallization is carried out using ethyl alcohol and the mixed solvent of ethylene glycol monomethyl ether in 70~100 DEG C, wherein the volume of ethyl alcohol and ethylene glycol monomethyl ether
Than being 0.3~0.7.
3. the preparation side that a kind of polyimide containing crown ether micropore according to claim 1 has microporous polymer membranes certainly
Method, it is characterised in that: aromatic diamine and aromatic dianhydride total mass fraction in step (1) mixed solution A are 17~20%.
4. the preparation side that a kind of polyimide containing crown ether micropore according to claim 1 has microporous polymer membranes certainly
Method, it is characterised in that: the dehydrating agent in step (1) is acetic anhydride, and catalyst is triethylamine；Aromatic diamine and acetic anhydride rub
You are than being 1:(8~10), the molar ratio of acetic anhydride and triethylamine is 2:(1~1.1).
5. the preparation side that a kind of polyimide containing crown ether micropore according to claim 1 has microporous polymer membranes certainly
Method, it is characterised in that: the organic solvent X of step (1) is n,N-Dimethylformamide, n,N-dimethylacetamide or N- methyl pyrrole
Pyrrolidone；The organic solvent Y of step (2) is DMAC N,N' dimethyl acetamide or N,N-dimethylformamide.
6. the preparation side that a kind of polyimide containing crown ether micropore according to claim 1 has microporous polymer membranes certainly
Method, it is characterised in that: the casting solution concentration in step (2) is 15wt%~30wt%.
7. the preparation side that a kind of polyimide containing crown ether micropore according to claim 1 has microporous polymer membranes certainly
Method, it is characterised in that: the first 2~4h of deaeration in a vacuum drying oven of casting solution in step (2) is then poured into mold again and carries out
Casting film；Drying is then dried in vacuo for 24 hours at 100~140 DEG C in 40~60 DEG C of vacuum drying 12h.
8. a kind of polyimide using containing crown ether micropore made from preparation method as described in claim 1 has micropore certainly
Polymer film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611147220.2A CN106674560B (en) | 2016-12-13 | 2016-12-13 | A kind of polyimide containing crown ether micropore is from tool microporous polymer membranes and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611147220.2A CN106674560B (en) | 2016-12-13 | 2016-12-13 | A kind of polyimide containing crown ether micropore is from tool microporous polymer membranes and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106674560A CN106674560A (en) | 2017-05-17 |
| CN106674560B true CN106674560B (en) | 2019-11-08 |
Family
ID=58867891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611147220.2A Active CN106674560B (en) | 2016-12-13 | 2016-12-13 | A kind of polyimide containing crown ether micropore is from tool microporous polymer membranes and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106674560B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107189432B (en) * | 2017-06-27 | 2019-10-18 | 华南理工大学 | A kind of composite modified polyimide film of graphene oxide/crown ether and preparation method thereof |
| CN107519849B (en) * | 2017-10-18 | 2019-04-05 | 福州大学 | A kind of amination tool microporous polymer adsorbent and its application certainly |
| CN107774140B (en) * | 2017-12-04 | 2020-12-01 | 中国石油大学(华东) | Preparation of PIMs (particle implanted membranes) with hinge structure and application of PIMs in field of gas separation |
| CN110643374B (en) * | 2019-09-27 | 2023-01-13 | 江苏三月科技股份有限公司 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
| CN110787641B (en) * | 2019-11-04 | 2021-12-03 | 陕西省膜分离技术研究院有限公司 | Method for quickly separating and extracting rubidium/potassium/sodium ions |
| CN110862537B (en) * | 2019-11-08 | 2020-11-24 | 华中科技大学 | Anthracene main chain type self-possessed microporous polymer and synthesis method and application thereof |
| CN111111459B (en) * | 2019-12-24 | 2021-07-13 | 西安交通大学 | Polyimide/surface modified metal organic framework mixed matrix membrane and preparation method and application thereof |
| CN111253571B (en) * | 2020-01-22 | 2023-01-03 | 天津工业大学 | Dibenzo crown ether polyimide polymer and preparation method and application thereof |
| CN112275147B (en) * | 2020-09-01 | 2021-08-13 | 中国科学院山西煤炭化学研究所 | Self-polymerization microporous polyimide gas separation membrane and preparation method and application thereof |
| CN113321807B (en) * | 2021-06-15 | 2022-10-14 | 中国科学院过程工程研究所 | Preparation method of crown ether-containing copolymer polyimide and phosphoric acid-doped proton exchange membrane thereof |
| CN113477235B (en) * | 2021-07-21 | 2023-04-14 | 大连理工大学 | Coimide aerogel block adsorbing material with micropores and preparation method thereof |
| CN113663540B (en) * | 2021-10-20 | 2022-01-18 | 湖南叶之能科技有限公司 | Carbon dioxide separation membrane and application thereof |
| CN115055066B (en) * | 2022-05-12 | 2023-07-07 | 南京工业大学 | Microporous polymer particle/polymer mixed matrix membrane and preparation method and application thereof |
| CN116640305B (en) * | 2023-07-26 | 2023-10-27 | 北京建工环境修复股份有限公司 | Polyimide sulfinate and preparation method and application thereof |
| CN116655915B (en) * | 2023-07-26 | 2023-11-03 | 北京建工环境修复股份有限公司 | Polyimide compound and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356647A (en) * | 2014-10-31 | 2015-02-18 | 华南理工大学 | Crown ether modified polyimide hybrid membrane and preparation method thereof |
| CN105924361A (en) * | 2016-06-20 | 2016-09-07 | 吉林大学 | Diamine monomer containing 4-dimethylamine-substituted tetraphenyl-p-phenylenediamine structure and preparation method and application of diamine monomer containing 4-dimethylamine-substituted tetraphenyl-p-phenylenediamine structure |
-
2016
- 2016-12-13 CN CN201611147220.2A patent/CN106674560B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356647A (en) * | 2014-10-31 | 2015-02-18 | 华南理工大学 | Crown ether modified polyimide hybrid membrane and preparation method thereof |
| CN105924361A (en) * | 2016-06-20 | 2016-09-07 | 吉林大学 | Diamine monomer containing 4-dimethylamine-substituted tetraphenyl-p-phenylenediamine structure and preparation method and application of diamine monomer containing 4-dimethylamine-substituted tetraphenyl-p-phenylenediamine structure |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106674560A (en) | 2017-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106674560B (en) | A kind of polyimide containing crown ether micropore is from tool microporous polymer membranes and preparation method thereof | |
| CN104829853B (en) | A kind of polyimide gas separating film and preparation method and application | |
| CN105289337B (en) | A kind of crosslinkable polyimide gas separation membrane and preparation method | |
| CN107551835B (en) | Preparation method of high-flux graphene oxide/polyimide mixed matrix membrane material | |
| CN106139936B (en) | Polyimide gas separating film and its preparation method and application | |
| CN101837254B (en) | Method for preparing solvent-resistant polyimide nanofiltration membrane | |
| JPS6153103B2 (en) | ||
| CN103846022A (en) | Preparation method of copolyimide hollow fiber gas separation membrane | |
| CN103846023A (en) | Copolymerization polyimide gas separation membrane material, preparation method and application of copolymerization polyimide gas separation membrane material | |
| CN106279685A (en) | Polyimide material, its preparation method and application of based on Teller lattice alkali structure | |
| CN108114615A (en) | A kind of polyimide gas separating film material and preparation and application | |
| CN114591503B (en) | Soluble poly (benzimidazole-co-imide) polymer and preparation and application thereof | |
| CN109821426A (en) | A kind of Preparation method and use containing binaphthyl structure Kapton | |
| Deng et al. | Molecular design and characterization of new polyimides based on binaphthyl-ether diamines for gas separation | |
| CN106866997A (en) | A kind of preparation method of nanoporous polyimides aeroge | |
| CN109833784A (en) | A kind of Silicone Containing Polyimides gas separation membrane and preparation method | |
| CN104817707A (en) | High-throughput polyimide nano-filtration membrane preparation method | |
| CN102824857A (en) | Preparation method of gas separation carbon membrane | |
| CN108440754A (en) | One kind is containing tertiary butyl substitution m-Terphenyl structure polyimide film material and preparation method thereof | |
| CN108745006A (en) | Fluorinated polyimide hollow-fibre membrane and preparation method thereof | |
| KR20200066446A (en) | BCDA-based semi-alicyclic polyimide membrane materials for gas separation and the preparation method thereof | |
| CN113244788A (en) | Synthetic method and application of polyimide gas separation membrane material | |
| CN105921037B (en) | A kind of preparation method of the porous gas separation membrane material with thermic rigid structure | |
| CN115501758B (en) | Polyimide copolymers and membranes, methods for their preparation and use, and systems and methods for purifying helium | |
| CN118437170B (en) | Preparation method of hyperbranched polyimide separation membrane for carbon dioxide separation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |