CN106674560A - Crown ether micropore containing polyimide intrinsic microporosity polymer membrane and preparation method thereof - Google Patents
Crown ether micropore containing polyimide intrinsic microporosity polymer membrane and preparation method thereof Download PDFInfo
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- CN106674560A CN106674560A CN201611147220.2A CN201611147220A CN106674560A CN 106674560 A CN106674560 A CN 106674560A CN 201611147220 A CN201611147220 A CN 201611147220A CN 106674560 A CN106674560 A CN 106674560A
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- 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
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- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
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- 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
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- 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
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- 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
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Abstract
The invention relates to a crown ether micropore containing polyimide intrinsic microporosity polymer membrane and a preparation method thereof. The preparation method comprises the following steps of: firstly, preparing a diamine solution from aromatic diamine; adding aromatic dianhydride into the diamine solution, and stirring for 9-13 hours at the room temperature; further adding a dehydration agent and a catalyst, stirring for 3-6 hours at 40-65 DEG C, removing the solvent, and drying, so as to obtain a crown ether micropore containing polyimide intrinsic microporosity polymer; and dissolving the polymer by using an organic solvent so as to obtain a membrane casting liquid, and performing membrane casting and drying, thereby obtaining the crown ether micropore containing polyimide intrinsic microporosity polymer membrane. As crown ether micropores are introduced into the polymer membrane provided by the invention, dense accumulation of polymer chain segments can be effectively prevented by virtue of steric hindrance of a cyclic structure of crown ether, an intrinsic microporosity polymer membrane material has a relatively large free volume, and in addition ether bonds of the crown ether have very good affinity with CO2, so that the prepared crown ether micropore containing polyimide intrinsic microporosity polymer membrane is relatively high in gas permeability coefficient and good in selectivity.
Description
【Technical field】
The present invention relates to polymeric membrane field, and in particular to a kind of polyimide containing crown ether micropore gathers from having micropore
Compound film and preparation method thereof.
【Background technology】
Common macromolecule member material can processing type it is relatively good, but there are high osmosis and high selectivity can not get both lacks
Point；The poromerics such as molecular sieve, metal-organic framework materials have higher permeability and selectivity, can break through common high score
" Robenson " upper limit of sub- membrane material, but it is difficult to the shortcomings of scale is amplified, ultra-thin film preparation is difficult, pliability is poor.Relatively
First two material, from tool capillary copolymer material (PIM), the microcellular structure with molecular sieve analog material, it is possible to achieve to difference
The screening of sized molecules, with high transmission selectivity, while also having, the pliability that has of polymeric material itself is good, Yi Cheng
The advantage that film, easy scale are amplified.Extensive concern is received recent years from having microporous polymer membrane material based on above feature.
But the pore size of such capillary copolymer material is difficult to control to, pore-size distribution width is unfavorable to gas-selectively.
For Membrane Gas Separation Processes it is typical from tool microporous polymer as based on phthalocyanine on-plane surface, twist structured
PIM-1 membrane materials, the PIM-EA-TB containing semicircular structure, on the strand of PIM-1 be grafted closed pore structure TZPIM, base
In triptycene structure polyimide type PIM membrane material.The studies above shows, from the pore size of tool microporous polymer membrane material and
Its pore-size distribution is to affect its selective key factor, and free volume is the key factor for affecting its gas permeability coefficient.
【The content of the invention】
This method aims to overcome that defect present in prior art, there is provided a kind of polyamides containing crown ether micropore is sub-
Amine obtains machinability by force and breaks through from having microporous polymer membranes and preparation method thereof by solution polycondensation and chemical imidization
Certainly the tool microporous polymer membrane material of Trade-off effects, finally prepares the polyamides containing crown ether micropore using solvent evaporated method
Imines have microporous polymer membranes certainly.
To reach above-mentioned purpose, the present invention is adopted the following technical scheme that：
Comprise the following steps：
(1) under protective atmosphere, organic solvent X, stirring and dissolving is added to obtain diamine solution aromatic diamine monomer；Press
Aromatic diamine is 1 with the mol ratio of aromatic dianhydride:(0.95~1.05), aromatic dianhydride is added in diamine solution,
Mixed solution A is configured to, mixed solution A is stirred at room temperature 9~13h；Dehydrant is added in mixed solution A again with catalysis
Agent, obtains mixed solution B, and mixed solution B desolvation and is dried to obtain micro- containing crown ether after stirring 3~6h at 40~65 DEG C
The polyimide in hole has microporous polymer certainly；Wherein, aromatic diamine using crown compound or crown compound and its
Its aromatic diamine monomer is in molar ratio (0.33~3)：1 mixture；
(2) polyimide containing crown ether micropore is dissolved from having microporous polymer organic solvent Y, obtains casting film
Liquid, by casting solution casting film and drying are carried out, and are obtained the polyimide containing crown ether micropore and are had microporous polymer membranes certainly.
Further, the crown compound in step (1) include diaminourea dibenzo -15- crown-s 5, diaminourea dibenzo -
18- crown-s 6 or diaminourea dibenzo -21- crown-s 7, other aromatic diamines include p-phenylenediamine, 4,4'- diaminodiphenyl ethers, 4,
Double [4- (4- amino-benzene oxygens) phenyl] propane of 4'- diaminodiphenyl-methanes, 2,2-, the double [4- (4- amino-benzene oxygens) of 2,2-
Phenyl] double (4- aminophenyls) HFC-236fa of HFC-236fa or 2,2-；Aromatic dianhydride includes 4,4'- hexafluoro isopropyls neighbour's benzene two
Formic anhydride, 3,3', 4,4'- benzophenone tetracarboxylic dianhydride (BTDA)s, 4,4'- oxygen diphthalic anhydrides, 4,4'- bibenzene tetracarboxylic dianhydrides,
Pyromellitic acid anhydride, 4,4'- (4,4'- isopropyl diphenoxies) two anhydride phthalic acids or 3,4,9,10- perylene tetracarboxylic acid dianhydrides.
Further, the preparation process of diaminourea dibenzo-18 crown-6 is specifically included：
A () is dissolved in dibenzo-18 crown-6 in the mixed solvent of chloroform and glacial acetic acid composition, obtain dibenzo -18- crown-s
6 solution；
B () is added dropwise to nitric acid and acetic anhydride mixed liquor in dibenzo-18 crown-6 solution, 10~25 DEG C reaction 1~
1.5h, is warming up to 40~80 DEG C and continues to react 5~6h, then through filtration, recrystallization and vacuum drying, 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 for (0.0125~
0.0153)mol：(95~115) mL：(70~80) mL：(3~4.5) mL：(13.5~15.5) mL；
C trans-dinitro the dibenzo-18 crown-6 for preparing is dissolved in ethylene glycol monomethyl ether by (), obtain concentration for 0.0222~
The reactant liquor of 0.0444mmol/mL, reactant liquor is added in reactor；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 heats up, and at 50~95 DEG C 2~3h is reacted；
Then be filtrated to get filtrate, in 60~85 DEG C of vacuum distillation filtrates, obtain red solid, sequentially pass through be dried, recrystallization and
Vacuum drying, obtains trans-diaminourea dibenzo-18 crown-6.
Further, recrystallization is carried out using DMF in 140~160 DEG C in step (b)；Step (c)
Middle recrystallization is carried out using the mixed solvent of ethanol and ethylene glycol monomethyl ether in 70~100 DEG C, wherein, ethanol and ethylene glycol monomethyl ether
Volume ratio is 0.3~0.7.
Further, the aromatic diamine and aromatic dianhydride total mass fraction in step (1) mixed solution A be 17~
20%.
Further, the dehydrant in step (1) is acetic anhydride, and catalyst is triethylamine；Aromatic diamine and acetic anhydride
Mol ratio be 1:(8~10), acetic anhydride is 2 with the mol ratio of triethylamine:(1~1.1).
Further, the organic solvent X of step (1) is DMF, N,N-dimethylacetamide or N- first
Base ketopyrrolidine；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 vacuum drying oven of casting solution in step (2), is then poured into again in mould
Carry out casting film；Drying is first to be vacuum dried 12h at 40~60 DEG C, is then vacuum dried 24h at 100~140 DEG C.
A kind of polyimide using containing crown ether micropore obtained in preparation method as above has microporous polymer certainly
Thing film.
Compared with prior art, the present invention has following beneficial technique effect：
Machinability is obtained by force and breakthrough Trade-off effects by solution polycondensation and chemical imidization in the method for the present invention
The tool microporous polymer certainly answered, crown ether compound has specific ring-type microcellular structure in the raw material for being adopted, and hole is big
It is little with crown ether species fromTo being more thanThis and H2、CO2It is suitable etc. gas-kinetic diameter；These crown ethers are introduced into film
Screening separation can be carried out to different size of gas molecule using crown ether duct after material, be obviously improved the screening choosing of membrane material
Selecting property.While the ehter bond and CO of crown ether2With good affinity, it is also possible to effectively increase CO2Dissolving selectivity.In segment
In structure, crown ether has big circulus, due to sterically hindered effect, can be effectively prevented segment dense packing, improves
The free volume of material；Be conducive to improving the permeability of membrane material；Polyimides are by its excellent mechanical performance and thermally-stabilised
Property be widely used in gaseous jet simulation field, can obtain high-performance polyimide by changing the chemical constitution of diamidogen or dianhydride
Gas separation membrane material.Both monomers compare with the monomer of numerous other heterocycle polymers, raw material sources extensively, synthesis also compared with
Easily.The obtained polyimide containing crown ether micropore of the invention is a kind of molecule interchain or intramolecular from having microporous polymer
Portion has the polymeric film material similar to molecular sieve or the microcellular structure of MOFs materials, and the present invention is introduced on PIM strands
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, with good processing characteristics, and can break through Trade-off effects；There is excellent heat stability, decomposition temperature simultaneously
More than 400 DEG C；Has micropore certainly by preparing a kind of new polyimide containing crown ether micropore using solvent evaporated method
Polymeric film, introduces crown ether micropore in Inventive polymers film, method is reliable, equipment is simple, controllability is strong.
Polyimide containing crown ether micropore of the invention introduces cyclic crown ether micropore from tool microporous polymer membranes, should
Micropore size is controllable, size uniformity, while the sterically hindered dense accumulation for effectively preventing polymer segment of crown ether circulus,
Ensure that there is higher free volume, and the ehter bond and CO of crown ether from tool microporous polymer membrane material2With affine well
Property, so as to ensure it is made there is high gas permeability coefficient and selectivity from tool microporous polymer membranes, its infiltration coefficient and selection
Performance enough respectively be up to 519barrer, 542.9.And the membrane material machinability is strong, gas separating property is excellent, application prospect
Extensively.
【Description of the drawings】
Fig. 1 is the trans-diaminourea dibenzo-18 crown-6 prepared by present example 11HNMR。
Fig. 2 is the heat stability testing figure of embodiment 1~3.
【Specific embodiment】
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 reality
Apply dibenzo-18 crown-6 used by example, 4,4'- diaminodiphenyl ethers, 4,4'- diaminodiphenyl-methanes and 4,4'- hexafluoros different
Propyl group phthalic anhydride is the production of Beijing lark prestige Science and Technology Ltd.；DMF, N, N- dimethyl second
Amide, N-Methyl pyrrolidone, nitric acid, glacial acetic acid, chloroform, triethylamine, ethanol, ethylene glycol monomethyl ether and Pd/C catalyst are
Chemical Reagent Co., Ltd., Sinopharm Group produces；Acetic anhydride is Xilong Chemical Co., Ltd's production.
DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone, ethylene glycol monomethyl ether use front addition
Appropriate molecular sieve is carried out except water process；4,4'- diaminodiphenyl ethers, the 80 DEG C of vacuum drying of 4,4'- diaminodiphenyl-methanes
48h；120 DEG C of vacuum drying 48h of 4,4'- hexafluoro isopropyls phthalic anhydride.
The inventive method 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 effects, most
Afterwards the polyimide containing crown ether micropore is prepared using solvent evaporated method and have microporous polymer membranes certainly；Specifically include following step
Suddenly：
(1) preparation of crown compound；Crown compound include diaminourea dibenzo -15- crown-s 5, diaminourea dibenzo -
18- crown-s 6 or diaminourea dibenzo -21- crown-s 7, below to prepare diaminourea dibenzo-18 crown-6 as a example by illustrate, prepare
During other crown compounds, the dibenzo-18 crown-6 in raw material is substituted for into dibenzo -15- crown-s 5 or dibenzo -21- crown-s 7
.
During dibenzo-18 crown-6 is dissolved in into chloroform, the mixed solvent of glacial acetic acid composition, dibenzo-18 crown-6 is obtained molten
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 and continue to react 5~6h, by yellow
Precipitation filtration, recrystallization, vacuum drying, you can obtain the trans-dinitro dibenzo-18 crown-6 containing crown ether structures.Will system
Standby trans-dinitro dibenzo-18 crown-6 is dissolved in ethylene glycol monomethyl ether, and it is 0.0222~0.0444mmol/mL's to obtain concentration
Reactant liquor, reactant liquor is added in reactor；Addition accounts for trans-dinitro dibenzo-18 crown-6 2~20wt%'s of quality
Pd/C catalyst, then fills H2To 0.3~0.4MPa, stirring heats up, and at 50~95 DEG C 2~3h is reacted；Solution in kettle is filtered,
60~85 DEG C of vacuum distillation filtrates, obtain red solid, successively drying, recrystallization, vacuum drying, you can obtain trans-diaminourea
Dibenzo-18 crown-6.
The recrystallization of the trans-dinitro dibenzo-18 crown-6 described in step (1) using N,N-dimethylformamide in
140~160 DEG C are carried out, and the recrystallization of trans-diaminourea dibenzo-18 crown-6 adopts the mixed solvent of ethanol/ethylene glycol monomethyl ether
Carry out in 70~100 DEG C, wherein, the volume ratio of ethanol and ethylene glycol monomethyl ether is 0.3~0.7.
(2) crown ether microporous polyamide imines are from the preparation for having microporous polymer
Under nitrogen protection, aromatic diamine monomer is added into organic solvent, organic solvent can be N, N- dimethyl formyls
In amine, N,N-dimethylacetamide, N-Methyl pyrrolidone any one, magnetic agitation dissolving obtain diamine solution；According to virtue
Fragrant race's diamidogen is 1 with the mol ratio of aromatic dianhydride:(0.95~1.05), is added directly into diamidogen molten by aromatic dianhydride solid
In liquid, aromatic diamine is configured to and solution that aromatic dianhydride total mass fraction is 17~20wt%, stirring 9 under room temperature~
13h；Add the mol ratio of the mixed liquor of acetic anhydride (dehydrant) and triethylamine (catalyst), aromatic diamine monomer and acetic anhydride
For 1:(8~10)；Acetic anhydride is 2 with the mol ratio of triethylamine:(1~1.1)；3~6h is stirred at 40~65 DEG C；It is cooled to room
Temperature, is added to desolventizing in ethanol in proper amount, using the multiple washing impurity-removing of ethanol, in 90~120 DEG C of vacuum by end reaction solution
It is dried 12~24h, you can obtain the polyimide containing crown ether micropore 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 in molar ratio (0.33~3)：1 mixture；Crown compound includes diaminourea dibenzo -15- crown-s 5, diaminourea two
Phendioxin 8- crown-s 6 or diaminourea dibenzo -21- crown-s 7, other aromatic diamines can be p-phenylenediamine, 4,4'- diaminourea hexichol
Double [4- (4- amino-benzene oxygens) phenyl] propane of ether, 4,4'- diaminodiphenyl-methanes, 2,2-, double [4- (the 4- aminobenzenes of 2,2-
Epoxide) phenyl] double (4- aminophenyls) HFC-236fa of HFC-236fa or 2,2-.
Aromatic dianhydride is 4,4'- hexafluoro isopropyl phthalic anhydrides, 3,3', 4,4'- benzophenone tetracarboxylic dianhydride (BTDA)s, 4,
4'- oxygen diphthalic anhydrides, 4,4'- bibenzene tetracarboxylic dianhydrides, pyromellitic acid anhydride, 4,4'- (4,4'- isopropyl diphenyls
Epoxide) two anhydride phthalic acids or 3,4,9,10- perylene tetracarboxylic acid dianhydrides.
Catalyst can also replace triethylamine with pyridine.
(3) crown ether microporous polyamide imines are from the preparation for having microporous polymer membranes
The membrane material N,N-dimethylacetamide of above-mentioned preparation or DMF are dissolved, making concentration is
The homogeneous solution of 15~30wt%, is placed in 2~4h of deaeration in vacuum drying oven, is then poured over casting solution and is fixed on glass plate
On circular die in, in 40~60 DEG C be vacuum dried 12h then again 100~140 DEG C vacuum drying 24h, you can contained
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 diaminourea dibenzo-18 crown-6
During 0.0142mol dibenzo-18 crown-6s are dissolved in into 105mL chloroforms, the mixed solvent of 75mL glacial acetic acids composition, will
3.6mL nitric acid and 14.25mL acetic anhydride mixed liquors are added dropwise in dibenzo-18 crown-6 solution, -17 DEG C of reaction 1.2h, are risen
Temperature continues to react 5.5h to 50 DEG C, by yellow mercury oxide filtration, 150 DEG C of recrystallization, vacuum drying, you can obtain containing crown ether structures
Trans-dinitro dibenzo-18 crown-6, its yield can reach 62.9mol%；Filtrate stands, almost without the analysis of Cis formulas product
Go out.
The 0.0037mol dinitro dibenzo-18 crown-6s of preparation are dissolved in into 100mL ethylene glycol monomethyl ether, prepared concentration is
The reactant liquor of 0.037mmol/mL, reactant liquor is added in reactor；Add dinitro dibenzo-18 crown-6 quality 4%
Pd/C catalyst, then fills H2To 0.35MPa, stirring heats up, and at 75 DEG C 2.5h is reacted；Solution in kettle is filtered, in 70 DEG C of decompressions
Distillation filtrate, obtains red solid, successively be dried, 80 DEG C adopt volume ratio and tie again for 0.3 ethanol/ethylene glycol monomethyl ether mixed solvent
Brilliant, vacuum drying, you can obtain trans-diaminourea dibenzo-18 crown-6.Shown in its reaction equation equation 1 below.
Equation 1：
(2) crown ether microporous polyamide imines are from the preparation for having microporous polymer
Under nitrogen protection, the diaminourea dibenzo-18 crown-6 for being prepared by step (1) and business 4,4'- diaminourea hexichol
Ether is in molar ratio 0.5 mixing as aromatic diamine monomer, adds N,N-dimethylacetamide, magnetic agitation dissolving to obtain two
Amine aqueous solution；It is 1 by the mol ratio of aromatic diamine and aromatic dianhydride：1,4,4'- hexafluoro isopropyls phthalic anhydride is solid
Body is added directly in diamine solution, is configured to the solution of aromatic diamine and aromatic dianhydride total mass fraction for 18wt%,
10h is stirred under room temperature；Mol ratio according to aromatic diamine monomer and acetic anhydride is 1：9, the mol ratio of acetic anhydride and triethylamine
For 2:1, the mixed liquor of acetic anhydride and triethylamine is added, stir 4.5h at 50 DEG C；Room temperature is cooled to, by end reaction solution precipitation
Agent, remove impurity, 100 DEG C of vacuum drying 23h, you can obtain the polyimide containing crown ether micropore and have microporous polymer certainly.Its is anti-
Answer shown in equation equation 2 below.
Equation 2：
(3) crown ether microporous polyamide imines are from the preparation for having microporous polymer membranes
By the membrane material of above-mentioned preparation with N,N-dimethylacetamide dissolve, make mass fraction be 20% it is uniform molten
Liquid, is placed in deaeration 3h in vacuum drying oven, is then poured over casting solution in the circular die being fixed on glass plate, in 50 DEG C
Vacuum drying 12h and then again 120 DEG C of vacuum drying 24h, you can obtain the polyimide containing crown ether micropore and gather from having micropore
Compound film.
Referring to Fig. 1, nuclear magnetic resonance, NMR test is carried out to trans-diaminourea dibenzo-18 crown-6, two phenyl ring are in symmetrical
Position, the characteristic peak ratio of the benzene ring hydrogen of diaminourea dibenzo-18 crown-6 is a:b:C=2:2:It is amino hydrogen at 2, f
Characteristic peak, its hydrogen number is exactly 4, further illustrates during nitration reaction each phenyl ring only one of which meta hydrogen by nitro
Replace, also illustrate that the nitro on two phenyl ring is reduced into amino by catalytic hydrogenation.
Embodiment 2
(1) preparation method of diaminourea dibenzo-18 crown-6 is with the step (1) in embodiment 1.
(2) crown ether microporous polyamide imines are from the preparation for having microporous polymer
Under nitrogen protection, by diaminourea dibenzo-18 crown-6 and business 4,4'- diaminodiphenyl-methanes by mole
Than mixing for 0.33, N,N-dimethylacetamide, magnetic agitation dissolving is added to obtain diamine solution；By aromatic diamine and fragrance
The mol ratio of race's dianhydride is 1：1,4,4'- hexafluoro isopropyl phthalic anhydride solids are added directly in diamine solution, match somebody with somebody
The solution of aromatic diamine and aromatic dianhydride total mass fraction for 18wt% is made, under room temperature 9h is stirred；According to aromatic series two
Amine monomers are 1 with the mol ratio of acetic anhydride：8, acetic anhydride is 2 with the mol ratio of triethylamine:1, acetic anhydride is added with triethylamine
Mixed liquor, at 50 DEG C 3h is stirred；Room temperature is cooled to, by end reaction solution desolventizing, remove impurity, 90 DEG C of vacuum drying 24h, you can
Obtain the polyimide containing crown ether micropore and have microporous polymer certainly.Shown in its reaction equation equation 3 below.
Equation 3：
(3) crown ether microporous polyamide imines are from the preparation for having microporous polymer membranes
By the membrane material of above-mentioned preparation with N,N-dimethylacetamide dissolve, make mass fraction be 15% it is uniform molten
Liquid, is placed in deaeration 2h in vacuum drying oven, is then poured over casting solution in the circular die being fixed on glass plate, in 40 DEG C
Vacuum drying 12h and then again 100 DEG C of vacuum drying 24h, you can obtain the polyimide containing crown ether micropore and gather from having micropore
Compound film.
Embodiment 3
(1) preparation method of diaminourea dibenzo-18 crown-6 is with the step (1) in embodiment 1.
(2) crown ether microporous polyamide imines are from the preparation for having microporous polymer
Under nitrogen protection, the trans-diaminourea dibenzo-18 crown-6 of step (1) preparation is weighed, N, N- diformazans is added
Yl acetamide, magnetic agitation dissolving；It is 1 by the mol ratio of aromatic diamine and aromatic dianhydride：1, by 4,4'- hexafluoro isopropyls
Phthalic anhydride solid is added directly in diamine solution, is configured to aromatic diamine and aromatic dianhydride total mass fraction is
11h is stirred under the solution of 20wt%, room temperature；Mol ratio according to aromatic diamine monomer and acetic anhydride is 1：8.5, acetic anhydride with
The mol ratio of triethylamine is 2:1, the mixed liquor of acetic anhydride and triethylamine is added, stir 4h at 40 DEG C；Room temperature is cooled to, will be final
Reaction solution desolventizing, remove impurity, 95 DEG C of vacuum drying 22h, you can obtain the polyimide containing crown ether micropore and have micropore certainly
Polymer.Shown in its reaction equation equation 4 below.
Equation 4：
(3) crown ether microporous polyamide imines are from the preparation for having microporous polymer membranes
By the membrane material of above-mentioned preparation with N,N-dimethylacetamide dissolve, make mass fraction be 30% it is uniform molten
Liquid, is placed in deaeration 4h in vacuum drying oven, is then poured over casting solution in the circular die being fixed on glass plate, in 60 DEG C
Vacuum drying 12h and then again 140 DEG C of vacuum drying 24h, you can obtain the polyimide containing crown ether micropore and gather from having micropore
Compound film.
The gas separating property of the embodiment 1~3 of table 1
| 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, made polyimide is from the gas for having microporous polymer membranes
Body separating property is as shown in table 1.For 3 maskings of embodiment, its infiltration coefficient and selectivity be up to respectively 519barrer,
542.9, due to crown ether pore size and CO2Kinetic diameter quite, while the ehter bond and CO of crown ether2With fine affinity.
Referring to Fig. 2, present the polyimide containing crown ether micropore prepared by embodiment 1-3 and have microporous polymer certainly
The heat stability of film, its initial decomposition temperature at 400~450 DEG C, shows good heat stability.
Embodiment 4
(1) preparation of diaminourea dibenzo-18 crown-6
During 0.0125mol dibenzo-18 crown-6s are dissolved in into 95mL chloroforms, the mixed solvent of 70mL glacial acetic acids composition, will
3.0mL nitric acid and 13.5mL acetic anhydride mixed liquors are added dropwise in dibenzo-18 crown-6 solution, 10 DEG C of reaction 1h, are warming up to
40 DEG C are continued to react 5h, by yellow mercury oxide filtration, 140 DEG C of recrystallization, vacuum drying, you can obtain containing the anti-of crown ether structures
Formula-dinitro dibenzo-18 crown-6.Trans-dinitro the dibenzo-18 crown-6 for preparing is dissolved in into 100mL ethylene glycol monomethyl ether,
Prepared concentration is the reactant liquor of 0.0222mmol/mL, and reactant liquor is added in reactor；Add dinitro dibenzo -18-
The Pd/C catalyst of the mass 2% of crown- 6, then fills H2To 0.3MPa, stirring heats up, and at 50 DEG C 2h is reacted；Solution in kettle is filtered,
In 60 DEG C of vacuum distillation filtrates, obtain red solid, successively be dried, 70 DEG C adopt volume ratio for 0.7 ethanol/ethylene glycol monomethyl ether mix
Bonding solvent recrystallization, vacuum drying, you can obtain trans-diaminourea dibenzo-18 crown-6.
(2) crown ether microporous polyamide imines are from the preparation for having microporous polymer
Under nitrogen protection, trans-diaminourea dibenzo-18 crown-6 and the p-phenylenediamine for being prepared by step (1) by mole
Than be 1.5 mixing as aromatic diamine monomer, add N,N-dimethylacetamide, magnetic agitation dissolving to obtain diamine solution；
It is 1 by the mol ratio of aromatic diamine and aromatic dianhydride：0.95, by 3,3', 4,4'- benzophenone tetracarboxylic dianhydride (BTDA)s are directly added into
To in diamine solution, the solution of aromatic diamine and aromatic dianhydride total mass fraction for 17wt% is configured to, is stirred under room temperature
12h；Mol ratio according to aromatic diamine monomer and acetic anhydride is 1：9.5, acetic anhydride is 2 with the mol ratio of triethylamine:1.1,
The mixed liquor of acetic anhydride and triethylamine is added, at 45 DEG C 5h is stirred；Be cooled to room temperature, by end reaction solution desolventizing, remove impurity,
110 DEG C of vacuum drying 20h, you can obtain the polyimide containing crown ether micropore and have microporous polymer certainly.
(3) crown ether microporous polyamide imines are from the preparation for having microporous polymer membranes
By the membrane material of above-mentioned preparation with N,N-dimethylacetamide dissolve, make mass fraction be 25% it is uniform molten
Liquid, is placed in deaeration 2.2h in vacuum drying oven, and then casting solution is poured in the circular die being fixed on glass plate, in 45
DEG C vacuum drying 12h and then again 110 DEG C of vacuum drying 24h, you can obtain the polyimide containing crown ether micropore from having micropore
Polymeric film.
Embodiment 5
(1) preparation of diaminourea dibenzo-18 crown-6
During 0.0153mol dibenzo-18 crown-6s are dissolved in into 115mL chloroforms, the mixed solvent of 80mL glacial acetic acids composition, will
3.5mL nitric acid and 15.5mL acetic anhydride mixed liquors are added dropwise in dibenzo-18 crown-6 solution, 25 DEG C of reaction 1.5h, are heated up
Continue to react 6h to 80 DEG C, by yellow mercury oxide filtration, 160 DEG C of recrystallization, vacuum drying, you can obtain containing the anti-of crown ether structures
Formula-dinitro dibenzo-18 crown-6.The dinitro dibenzo-18 crown-6 of preparation is dissolved in into 100mL ethylene glycol monomethyl ether, is obtained
Concentration is the reactant liquor of 0.0444mmol/mL, and reactant liquor is added in reactor；Add trans-dinitro dibenzo -18-
The Pd/C catalyst of the mass 20% of crown- 6, then fills H2To 0.4MPa, stirring heats up, and at 95 DEG C 3h is reacted；Solution in kettle is filtered,
In 85 DEG C of vacuum distillation filtrates, obtain red solid, successively be dried, 100 DEG C adopt volume ratio for 0.5 ethanol/ethylene glycol monomethyl ether
Mixed solvent recrystallization, vacuum drying, you can obtain trans-diaminourea dibenzo-18 crown-6.
(2) crown ether microporous polyamide imines are from the preparation for having microporous polymer
Under nitrogen protection, the diaminourea dibenzo-18 crown-6 for being prepared by step (1) and double [4- (the 4- aminobenzenes of 2,2-
Epoxide) phenyl] propane is in molar ratio 2 mixing as aromatic diamine monomer, adds DMF, magnetic agitation
Dissolving obtains diamine solution；It is 1 by the mol ratio of aromatic diamine and aromatic dianhydride：0.98, by the O-phthalic of 4,4'- oxygen two
Anhydride is added directly in diamine solution, is configured to aromatic diamine and aromatic dianhydride total mass fraction for the molten of 19wt%
13h is stirred under liquid, room temperature；Mol ratio according to aromatic diamine monomer and acetic anhydride is 1：10, acetic anhydride rubs with triethylamine
You are than being 2:1.1, the mixed liquor of acetic anhydride and triethylamine is added, stir 6h at 65 DEG C；Room temperature is cooled to, by end reaction solution
Desolventizing, remove impurity, 115 DEG C of vacuum drying 18h, you can obtain the polyimide containing crown ether micropore and have microporous polymer certainly.
(3) crown ether microporous polyamide imines are from the preparation for having microporous polymer membranes
By the membrane material of above-mentioned preparation with DMF dissolve, make mass fraction be 18% it is uniform molten
Liquid, is placed in deaeration 2.5h in vacuum drying oven, and then casting solution is poured in the circular die being fixed on glass plate, in 55
DEG C vacuum drying 12h and then again 130 DEG C of vacuum drying 24h, you can obtain the polyimide containing crown ether micropore from having micropore
Polymeric film.
Embodiment 6
(1) preparation of diaminourea dibenzo -21- crown-s 7
Dibenzo-18 crown-6 is substituted for into dibenzo -21- crown-s 7, other conditions are using identical with the step of embodiment 5 (1)
Condition, prepare trans-diaminourea dibenzo -21- crown-s 7.
(2) crown ether microporous polyamide imines are from the preparation for having microporous polymer
Under nitrogen protection, the diaminourea dibenzo -21- crown-s 7 for being prepared by step (1) and double [4- (the 4- aminobenzenes of 2,2-
Epoxide) phenyl] HFC-236fa is in molar ratio 3 mixing as aromatic diamine monomer, adds DMF, magnetic force
Stirring and dissolving obtains diamine solution；It is 1 by the mol ratio of aromatic diamine and aromatic dianhydride：1.02, by 4,4'- biphenyl tetracarboxylics
Acid dianhydride is added directly in diamine solution, is configured to aromatic diamine and aromatic dianhydride total mass fraction for 17.5wt%'s
9.5h is stirred under solution, room temperature；Mol ratio according to aromatic diamine monomer and acetic anhydride is 1：8.2, acetic anhydride and pyridine
Mol ratio is 2:1.1, the mixed liquor of acetic anhydride and pyridine is added, stir 3.5h at 60 DEG C；Room temperature is cooled to, end reaction is molten
Loss of thick fluid solvent, remove impurity, 120 DEG C of vacuum drying 12h, you can obtain the polyimide containing crown ether micropore and have microporous polymer certainly
Thing.
(3) crown ether microporous polyamide imines are from the preparation for having microporous polymer membranes
By the membrane material of above-mentioned preparation with DMF dissolve, make mass fraction be 22% it is uniform molten
Liquid, is placed in deaeration 2.8h in vacuum drying oven, and then casting solution is poured in the circular die being fixed on glass plate, in 41
DEG C vacuum drying 12h and then again 105 DEG C of vacuum drying 24h, you can obtain the polyimide containing crown ether micropore from having micropore
Polymeric film.
Embodiment 7
(1) preparation of diaminourea dibenzo -15- crown-s 5
Dibenzo-18 crown-6 is substituted for into dibenzo -15- crown-s 5, other conditions are using identical with the step of embodiment 5 (1)
Condition, prepare trans-diaminourea dibenzo -15- crown-s 5.
(2) crown ether microporous polyamide imines are from the preparation for having microporous polymer
Under nitrogen protection, the diaminourea dibenzo -15- crown-s 5 for being prepared by step (1) and 2,2- are double (4- aminophenyls)
HFC-236fa is in molar ratio 1 mixing as aromatic diamine monomer, adds N-Methyl pyrrolidone, magnetic agitation dissolving to obtain
Diamine solution；It is 1 by the mol ratio of aromatic diamine and aromatic dianhydride：1.04, pyromellitic acid anhydride is added directly into
In diamine solution, the solution of aromatic diamine and aromatic dianhydride total mass fraction for 18.5wt% is configured to, is stirred under room temperature
10.5h；Mol ratio according to aromatic diamine monomer and acetic anhydride is 1：9.6, acetic anhydride is 2 with the mol ratio of triethylamine:
1.05, the mixed liquor of acetic anhydride and triethylamine is added, stir 5.5h at 55 DEG C；Room temperature is cooled to, by end reaction solution precipitation
Agent, remove impurity, 105 DEG C of vacuum drying 23h, you can obtain the polyimide containing crown ether micropore and have microporous polymer certainly.
(3) crown ether microporous polyamide imines are from the preparation for having microporous polymer membranes
By the membrane material of above-mentioned preparation with DMF dissolve, make mass fraction be 26% it is uniform molten
Liquid, is placed in deaeration 3.2h in vacuum drying oven, and then casting solution is poured in the circular die being fixed on glass plate, in 54
DEG C vacuum drying 12h and then again 115 DEG C of vacuum drying 24h, you can obtain the polyimide containing crown ether micropore from having micropore
Polymeric film.
Embodiment 8
(1) preparation of diaminourea dibenzo-18 crown-6
During 0.0144mol dibenzo-18 crown-6s are dissolved in into 110mL chloroforms, the mixed solvent of 72mL glacial acetic acids composition, will
3.8mL nitric acid and 14mL acetic anhydride mixed liquors are added dropwise in dibenzo-18 crown-6 solution, 20 DEG C of reaction 1.4h, are warming up to
50 DEG C are continued to react 5.2h, by yellow mercury oxide filtration, 148 DEG C of recrystallization, vacuum drying, you can obtain containing the anti-of crown ether structures
Formula-dinitro dibenzo-18 crown-6.Trans-dinitro the dibenzo-18 crown-6 for preparing is dissolved in into 100mL ethylene glycol monomethyl ether,
Prepared concentration is the reactant liquor of 0.0333mmol/mL, and reactant liquor is added in reactor；Add dinitro dibenzo -18-
The Pd/C catalyst of the mass 10% of crown- 6, then fills H2To 0.38MPa, stirring heats up, and at 80 DEG C 2.2h is reacted；Filter molten in kettle
Liquid, in 85 DEG C of vacuum distillation filtrates, obtains red solid, successively be dried, 90 DEG C adopt volume ratio for 0.6 ethanol/ethylene glycol first
Ether mixed solvent recrystallization, vacuum drying, you can obtain trans-diaminourea dibenzo-18 crown-6.
(2) crown ether microporous polyamide imines are from the preparation for having microporous polymer
Under nitrogen protection, using the diaminourea dibenzo-18 crown-6 of step (1) preparation as aromatic diamine monomer, plus
Enter N-Methyl pyrrolidone, magnetic agitation dissolving obtains diamine solution；It is with the mol ratio of aromatic dianhydride by aromatic diamine
1：1.05,4,4'- (4,4'- isopropyl diphenoxy) two anhydride phthalic acids are added directly in diamine solution, it is configured to aromatic series
Diamidogen and aromatic dianhydride total mass fraction are the solution of 19.5wt%, and under room temperature 11.5h is stirred；According to aromatic diamine monomer
It is 1 with the mol ratio of acetic anhydride：9.3, acetic anhydride is 2 with the mol ratio of triethylamine:1.05, add acetic anhydride mixed with triethylamine
Liquid is closed, at 48 DEG C 3.2h is stirred；Room temperature is cooled to, end reaction solution desolventizing, remove impurity, 100 DEG C 23h is vacuum dried into, i.e.,
The polyimide containing crown ether micropore can be obtained and have microporous polymer certainly.
(3) crown ether microporous polyamide imines are from the preparation for having microporous polymer membranes
By the membrane material of above-mentioned preparation with DMF dissolve, make mass fraction be 28% it is uniform molten
Liquid, is placed in deaeration 3.5h in vacuum drying oven, and then casting solution is poured in the circular die being fixed on glass plate, in 59
DEG C vacuum drying 12h and then again 125 DEG C of vacuum drying 24h, you can obtain the polyimide containing crown ether micropore from having micropore
Polymeric film.
The present invention relates to a kind of polyimide containing crown ether micropore is from tool microporous polymer membranes and preparation method thereof.This
Invention passes sequentially through nitration reaction, catalytic hydrogenation synthesizing diamino and takes with crown compounds such as dibenzo-18 crown-6s as raw material
For crown ether；Then replace crown ether as raw material with dicarboxylic anhydride and diaminourea, pass sequentially through solution polycondensation and chemical imidization method, make
Must be containing the polyimide of crown ether micropore from tool microporous polymer membrane material；Finally prepared using solvent evaporated method and contain crown ether
The polyimide of micropore has microporous polymer membranes certainly.
Claims (10)
1. a kind of polyimide containing crown ether micropore is from the preparation method for having microporous polymer membranes, it is characterised in that：Including
Following steps：
(1) under protective atmosphere, organic solvent X, stirring and dissolving is added to obtain diamine solution aromatic diamine monomer；By fragrance
Race's diamidogen is 1 with the mol ratio of aromatic dianhydride:(0.95~1.05), aromatic dianhydride is added in diamine solution, is prepared
Into mixed solution A, mixed solution A is stirred at room temperature 9~13h；Add dehydrant and catalyst in mixed solution A again, obtain
To mixed solution B, mixed solution B desolvation and is dried to obtain containing crown ether micropore after stirring 3~6h at 40~65 DEG C
Polyimide has microporous polymer certainly；Wherein, aromatic diamine is using crown compound or crown compound and other virtues
Fragrant race's diamine monomer is in molar ratio (0.33~3)：1 mixture；
(2) polyimide containing crown ether micropore is dissolved from having microporous polymer organic solvent Y, obtains casting solution, will
Casting solution carries out casting film and drying, obtains the polyimide containing crown ether micropore and has microporous polymer membranes certainly.
2. a kind of polyimide containing crown ether micropore according to claim 1 is from the preparation side for having microporous polymer membranes
Method, it is characterised in that：Crown compound in step (1) includes diaminourea dibenzo -15- crown-s 5, diaminourea dibenzo -18-
Crown- 6 or diaminourea dibenzo -21- crown-s 7, other aromatic diamines include p-phenylenediamine, 4,4'- diaminodiphenyl ethers, 4,4'-
Double [4- (4- amino-benzene oxygens) phenyl] propane of diaminodiphenyl-methane, 2,2-, double [4- (4- amino-benzene oxygens) benzene of 2,2-
Base] double (4- aminophenyls) HFC-236fa of HFC-236fa or 2,2-；Aromatic dianhydride includes 4,4'- hexafluoro isopropyl O-phthalics
Anhydride, 3,3', 4,4'- benzophenone tetracarboxylic dianhydride (BTDA)s, 4,4'- oxygen diphthalic anhydrides, 4,4'- bibenzene tetracarboxylic dianhydrides,
PMDA, 4,4'- (4,4'- isopropyl diphenoxies) two anhydride phthalic acids or 3,4,9,10- perylene tetracarboxylic acid dianhydrides.
3. a kind of polyimide containing crown ether micropore according to claim 2 is from the preparation side for having microporous polymer membranes
Method, it is characterised in that：The preparation process of diaminourea dibenzo-18 crown-6 is specifically included：
A () is dissolved in dibenzo-18 crown-6 in the mixed solvent of chloroform and glacial acetic acid composition, obtain dibenzo-18 crown-6 molten
Liquid；
B () is added dropwise to nitric acid and acetic anhydride mixed liquor in dibenzo-18 crown-6 solution, 10~25 DEG C reaction 1~
1.5h, is warming up to 40~80 DEG C and continues to react 5~6h, then through filtration, recrystallization and vacuum drying, 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 for (0.0125~
0.0153)mol：(95~115) mL：(70~80) mL：(3~4.5) mL：(13.5~15.5) mL；
C trans-dinitro the dibenzo-18 crown-6 for preparing is dissolved in ethylene glycol monomethyl ether by (), obtain concentration for 0.0222~
The reactant liquor of 0.0444mmol/mL, reactant liquor is added in reactor；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 heats up, and at 50~95 DEG C 2~3h is reacted；
Then be filtrated to get filtrate, in 60~85 DEG C of vacuum distillation filtrates, obtain red solid, sequentially pass through be dried, recrystallization and
Vacuum drying, obtains trans-diaminourea dibenzo-18 crown-6.
4. a kind of polyimide containing crown ether micropore according to claim 3 is from the preparation side for having microporous polymer membranes
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 the mixed solvent of ethanol and ethylene glycol monomethyl ether in 70~100 DEG C, wherein, the volume of ethanol and ethylene glycol monomethyl ether
Than for 0.3~0.7.
5. a kind of polyimide containing crown ether micropore according to claim 1 is from the preparation side for having microporous polymer membranes
Method, it is characterised in that：Aromatic diamine and aromatic dianhydride total mass fraction in step (1) mixed solution A is 17~20%.
6. a kind of polyimide containing crown ether micropore according to claim 1 is from the preparation side for having microporous polymer membranes
Method, it is characterised in that：Dehydrant in step (1) is acetic anhydride, and catalyst is triethylamine；Aromatic diamine rubs with acetic anhydride
You are than being 1:(8~10), acetic anhydride is 2 with the mol ratio of triethylamine:(1~1.1).
7. a kind of polyimide containing crown ether micropore according to claim 1 is from the preparation side for having microporous polymer membranes
Method, it is characterised in that：The organic solvent X of step (1) is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or N- methyl pyrroles
Pyrrolidone；The organic solvent Y of step (2) is DMAC N,N' dimethyl acetamide or N,N-dimethylformamide.
8. a kind of polyimide containing crown ether micropore according to claim 1 is from the preparation side for having microporous polymer membranes
Method, it is characterised in that：Casting solution concentration in step (2) is 15wt%~30wt%.
9. a kind of polyimide containing crown ether micropore according to claim 1 is from the preparation side for having microporous polymer membranes
Method, it is characterised in that：First 2~the 4h of deaeration in vacuum drying oven of casting solution in step (2), being then poured into again in mould is carried out
Casting film；Drying is first to be vacuum dried 12h at 40~60 DEG C, is then vacuum dried 24h at 100~140 DEG C.
10. a kind of polyimide using containing crown ether micropore obtained in preparation method as claimed in claim 1 is micro- from having
Pore polymer film.
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