CN110433668A - A kind of MOF and PIM-1 are cross-linked in situ matrix membrane and preparation method thereof - Google Patents
A kind of MOF and PIM-1 are cross-linked in situ matrix membrane and preparation method thereof Download PDFInfo
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- CN110433668A CN110433668A CN201910573001.8A CN201910573001A CN110433668A CN 110433668 A CN110433668 A CN 110433668A CN 201910573001 A CN201910573001 A CN 201910573001A CN 110433668 A CN110433668 A CN 110433668A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
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Abstract
The invention discloses a kind of MOF and PIM-1 to be cross-linked in situ matrix membrane and preparation method thereof, the MOF and PIM-1 be cross-linked in situ matrix membrane the preparation method comprises the following steps: by UIO-66-NH2, Isosorbide-5-Nitrae-dicyano phenyl tetrafluoride, 5,5', 6,6' tetrahydroxy -3,3,3', 3'- tetramethyl -1,10- spiral shell diacid, potassium carbonate and DMF mixed dissolution react 12~72h under conditions of 70~80 DEG C, obtain that reaction solution A is post-treated to obtain cross-linking products；Obtained cross-linking products are dissolved in chloroform and obtain viscosity solution, then being layered on the viscosity solution uniform ground in film forming utensil, is dried at room temperature for 24~36h, and obtaining forming a film post-treated obtains target product MOF and PIM-1 is cross-linked in situ matrix membrane.MOF of the present invention and PIM-1 is cross-linked in situ the CO of composite base plasma membrane2Flux improves by about one time, and CO2/CH4The selective 12.3 and UiO-66-NH by PIM-1 film2The 12.5 of/PIM-1 blend film are increased to 31.9, CO2/N2Selectivity is increased to 54.2 by 18.7 and 17.3.
Description
(1) technical field
The present invention relates to polymer separation film technology, specifically introducing MOF is made by being cross-linked in situ to react with PIM-1
Make the technology of mixed substrate membrane containing nano-grade molecular sieve.
(2) background technique
Compared with conventional isolation techniques, membrane separation technique is high, energy-efficient with separative efficiency, loss is small, takes up little area, grasps
Make the advantages that simple.2004, Peter Budd successfully had developed PIM (from tool microporous polymer) material containing spirane structure
Material, film has the characteristics that high osmosis to the PIM being concerned (from tool microporous polymer), but its selectivity is general, at present
There are a variety of fillers and PIM-1 production composite membrane to improve selectivity, but influenced by trade-off, is improved selective
Permeability reduces simultaneously.
(3) summary of the invention
The object of the present invention is to provide a kind of MOF and PIM-1 to be cross-linked in situ matrix membrane and preparation method thereof, and this method solves
Between conventional composite film filler and polymer the problem of poor compatibility, prepared composite membrane has high permeability and selection
Property.
Technical scheme is as follows:
MOF of the present invention and PIM-1 is cross-linked in situ matrix membrane and passes through UiO-66-NH2In situ hand over occurs with PIM-1
Connection, then prepared by phase inversion.
Further, the MOF and PIM-1 is cross-linked in situ matrix membrane and specifically follows the steps below preparation:
(1) by UIO-66-NH2, 1,4- dicyano phenyl tetrafluoride, 5,5', tetramethyl -1 6,6' tetrahydroxy -3,3,3', 3'-,
10- spiral shell diacid, potassium carbonate and DMF mixed dissolution react 12~72h under conditions of 70~80 DEG C, obtain reaction solution A after
Reason obtains cross-linking products；The UIO-66-NH2, 1,4- dicyano phenyl tetrafluoride, 5,5', 6,6' tetrahydroxy -3,3,3', 3'- tetra-
Methyl-1, the ratio between 10- spiral shell diacid, amount of substance of potassium carbonate are 1:1~2:1~2:2~4；
(2) cross-linking products that step (1) obtains are dissolved in chloroform and obtain viscosity solution, it is then that the viscosity is molten
Being layered in film forming utensil for liquid uniform ground, is dried at room temperature for 24~36h, and obtaining forming a film post-treated obtains target product
MOF and PIM-1 are cross-linked in situ matrix membrane.
Further, in step (1), the additional amount of the DMF is with the UIO-66-NH2The amount of substance be calculated as 10
~20ml/mmol.
Further, in step (1), the post-processing approach of the reaction solution A are as follows: reaction solution A filtering, obtained filter will be obtained
Cake uses methanol and acetone washing 2~3 times respectively, to remove any remaining catalyst and unreacted monomer, obtains crosslinking and produces
Object.
Further, in step (2), cross-linking products dissolution of the additional amount of the chloroform just obtain step (1)
Subject to.
Further, in step (2), the post-processing approach of the film forming are as follows: obtained film forming is placed in methanol solution and is soaked
Bubble 12~remove remaining solvent for 24 hours, then it is placed in 90~110 DEG C of vacuum drying ovens dry 12~for 24 hours, obtain target product
MOF and PIM-1 are cross-linked in situ matrix membrane.
UiO-66-NH of the present invention2It is prepared as follows:
By 2- amino terephthalic acid (TPA), ZrCl4, formic acid and DMF mixed dissolution, 3~4h is stirred under room temperature, then by solution
It is transferred in reaction kettle, is put into 120 DEG C of baking oven and heats 24 hours, obtain reaction mixture B, it is post-treated to obtain UiO-
66-NH2；The 2- amino terephthalic acid (TPA) and ZrCl4The ratio between the amount of substance be 1:1；The additional amount of the formic acid is with institute
The amount of the substance for the 2- amino terephthalic acid (TPA) stated is calculated as 1.11mL/mol.
Further, the additional amount of the DMF be calculated as 10 with the amount of the substance of the 2- amino terephthalic acid (TPA)~
50mL/mol。
Further, the post-processing approach of the reaction solution B are as follows: be centrifuged obtained reaction solution B, obtained centrifugation product
It is washed 3~6 times with methanol, activates 24 hours in 120 DEG C of vacuum drying oven then to get UiO-66-NH2。
MOF of the present invention is cross-linked in situ matrix membrane with PIM-1 and separates applied to gas.
Further, the gas is preferably CO2/CH4Or CO2/N2。
Compared with prior art, the beneficial effects of the present invention are: the preparation of traditional mixed substrate membrane containing nano-grade molecular sieve is exactly simply
Polymer and filler are mixed, can not usually solve the problems, such as that poor compatibility between polymer and filler, the present invention mention
Mixed substrate membrane containing nano-grade molecular sieve of new generation is gone out, wherein filler and polymer substrate have synthesized flawless film by being covalently keyed.Relatively
In original PIM-1 film or simple UiO-66-NH2/ PIM-1 blend film, MOF and PIM-1 are cross-linked in situ composite base plasma membrane
CO2Flux improves by about one time, and CO2/CH4The selective 12.3 and UiO-66-NH by PIM-1 film2/ PIM-1 blend film
12.5 are increased to 31.9, CO2/N2Selectivity is increased to 54.2 by 18.7 and 17.3.
(4) Detailed description of the invention
Fig. 1 is the UiO-66-NH in the embodiment of the present invention 22/ PIM-1 is cross-linked in situ the SEM electromicroscopic photograph of matrix membrane.
(5) specific embodiment
Combined with specific embodiments below, the present invention is described in detail, but the present invention is not limited to the following embodiments, In
It does not depart from the content of present invention and range, change all should be comprising within the technical scope of the present invention.
Embodiment 1: putting up the reflux unit containing three-necked flask, in nitrogen atmosphere, by 3.4gTTSBI, 2gDCTB
With 4.14g anhydrous K2CO3It is added in three-necked flask, 20ml NMP is added, stirs 3min under room temperature, 10ml toluene is then added,
It is put into 160 DEG C of oil bath pans at once and reacts 40min, the solution obtained after reaction is poured into 200ml methanol, stirred 2h, use hole
The nylon membrane that diameter is 0.45 μm filters, and obtained filter cake is dried 6h, the powder that then will be dried to obtain under conditions of 60 DEG C
It is dissolved in 100ml chloroform, stirs 2h, bottom sediment is dissolved in 400ml methanol by centrifugation, stirs 2h, and suction filtration obtains
PIM-1 powder is finally successively respectively washed 2 times with deionized water, acetone, dioxane, and fluorescent yellow PIM-1 powder is dried to obtain.
It takes 0.72gPIM-1 powder to be dissolved in 10ml chloroform ultrasonic half an hour and obtains thick solution, solution has entirely been poured into
In the culture dish of lid, at room temperature after drying for 24 hours, resulting film is put into ethyl alcohol and is impregnated for 24 hours, then in a vacuum drying oven
For 24 hours, what is obtained is pure PIM-1 film, and the gas separating property of the film is as shown in table 1 for 100 DEG C of dryings:
The gas separating property of the pure PIM-1 film of table 1
Pure PIM-1 film CO as can be seen from Table 12/N2Selective highest is 18.7, CO2/CH4Gas to selectivity be
12.3 CO2Flux is 6576.
Embodiment 2: putting up the reflux unit containing three-necked flask, in nitrogen atmosphere, by 3.4gTTSBI, 2gDCTB
With 4.14g anhydrous K2CO3It is added in three-necked flask, 20ml NMP is added, stirs 3min under room temperature, 10ml toluene is then added,
It is put into 160 DEG C of oil bath pans at once and reacts 40min, the solution obtained after reaction is poured into 200ml methanol, stirred 2h, use hole
The nylon membrane that diameter is 0.45 μm filters, and obtained filter cake is dried 6h, the powder that then will be dried to obtain under conditions of 60 DEG C
It is dissolved in 100ml chloroform, stirs 2h, bottom sediment is dissolved in 400ml methanol by centrifugation, stirs 2h, and suction filtration obtains
PIM-1 powder is finally successively respectively washed 2 times with deionized water, acetone, dioxane, and fluorescent yellow PIM-1 powder is dried to obtain.
By 0.81g2- amino terephthalic acid (TPA), 1.06gZrCl4, 5ml formic acid and 50mlDMF mixed dissolution, stir 3h under room temperature, then
It transfers the solution into reaction kettle, is put into 120 DEG C of baking oven and heats 24 hours, obtain reaction mixture B, it is centrifuged
Bottom centrifugation product is washed 4 times with methanol, is then activated 24 hours in 120 DEG C of vacuum drying oven, is obtained UiO-66-NH2.It takes
0.7g UiO-66-NH2It is put into 50ml small beaker with 1.12gPIM-1,10ml chloroform is then added, ultrasonic half an hour obtains
Thick solution, solution is poured into culture dish, at room temperature after drying for 24 hours, resulting film is put into ethyl alcohol and is impregnated for 24 hours,
Then 100 DEG C of dryings obtain film for 24 hours in a vacuum drying oven.
Obtained film is non-crosslinked composite membrane, by simple gas test, the gas separating property of the film such as 2 institute of table
Show: this example is also comparative example,
The non-crosslinked composite membrane gas separating property of table 2
As shown in Table 2, relative to pure PIM-1 film, obtained blending UiO-66-NH2Four kinds of gases of/PIM-1 film lead to
Amount is somewhat promoted, however CO2/CH4And CO2/N2The selectivity of gas pair declines, respectively 12.0 and 16.5, it is comprehensive for
It is equally matched with the separating property of pure PIM-1 film, be not suitable for industrial applications.
Embodiment 3: by 0.81g2- amino terephthalic acid (TPA), 1.06gZrCl4, 5ml formic acid and 50mlDMF mixed dissolution,
3h is stirred under room temperature, is then transferred the solution into reaction kettle, is put into 120 DEG C of baking oven and heats 24 hours, and it is mixed to obtain reaction
Liquid is closed, centrifuged bottom centrifugation product is washed 4 times with methanol, is then activated 24 hours in 120 DEG C of vacuum drying oven,
Obtain UiO-66-NH2.Take 0.7 gram of UiO-66-NH2Be put into DMF (50mL), then be added for PIM-1 polymerization monomer and
Catalyst, including DCTB (1.0g, 5.0mmol), TTSBI (1.7g, 5.0mmol) and K2CO3(2.1g, 10.0mmol).Reaction exists
It carries out, is reacted for 24 hours, by the UiO-66-NH comprising crosslinking at 70 DEG C2With the yellow mixture in drag precipitating of PIM-1
It filters and is washed with methanol (twice) and acetone (twice) to remove any remaining catalyst and unreacted monomer.By product
It is dispersed in chloroform to obtain viscous slurry, equally viscous liquid is poured into culture dish and is dried for 24 hours at room temperature, obtained film is put
It impregnates in ethanol solution for 24 hours, is then dried in vacuo for 24 hours for 100 DEG C.
This obtained film is crosslinking mixed substrate membrane containing nano-grade molecular sieve, and the separating property of the film is as shown in table 3:
3 MOF of table and PIM-1 are cross-linked in situ composite base plasma membrane
As can be seen from Table 3, MOF of the present invention and PIM-1 is cross-linked in situ the CO of composite base plasma membrane2Flux increases nearly one
Times, reach 12498, and CO2/CH4And CO2/N2The selectivity of gas pair is greatly promoted, and has respectively reached 31.9 Hes
54.2, it is expected to be applied to industrialization gas separation, and treatment effeciency can be greatlyd improve, reduces energy consumption.
Claims (10)
1. a kind of MOF and PIM-1 are cross-linked in situ matrix membrane, it is characterised in that: the MOF and PIM-1 is cross-linked in situ matrix membrane
Specifically prepared in accordance with the following methods:
(1) by UIO-66-NH2, 1,4- dicyano phenyl tetrafluoride, 5,5', 6,6' tetrahydroxy -3,3,3', 3'- tetramethyl -1,10- spiral shell
Diacid, potassium carbonate and DMF mixed dissolution react 12~72h 70~80 DEG C under conditions of, and it is post-treated to obtain reaction solution A
To cross-linking products；The UIO-66-NH2, 1,4- dicyano phenyl tetrafluoride, 5,5', 6,6' tetrahydroxy -3,3,3', 3'- tetramethyl
The ratio between amount of substance of base -1,10- spiral shell diacid, potassium carbonate is 1:1~2:1~2:2~4；
(2) cross-linking products that step (1) obtains are dissolved in chloroform and obtain viscosity solution, it is then that the viscosity solution is equal
It is even it is smooth be layered in film forming utensil, be dried at room temperature for 24~36h, obtain forming a film it is post-treated obtain target product MOF with
PIM-1 is cross-linked in situ matrix membrane.
2. MOF as described in claim 1 and PIM-1 are cross-linked in situ matrix membrane, it is characterised in that: described in step (1)
The additional amount of DMF is with the UIO-66-NH2The amount of substance be calculated as 10~20ml/mmol.
3. MOF as described in claim 1 and PIM-1 are cross-linked in situ matrix membrane, it is characterised in that: in step (1), the reaction
The post-processing approach of liquid A are as follows: reaction solution A filtering will be obtained, obtained filter cake uses methanol and acetone washing 2~3 times respectively, to remove
Any remaining catalyst and unreacted monomer are removed, cross-linking products are obtained.
4. MOF as described in claim 1 and PIM-1 are cross-linked in situ matrix membrane, it is characterised in that: in step (2), the chlorine
Imitative additional amount be subject to just obtain step (1) cross-linking products dissolution.
5. MOF as described in claim 1 and PIM-1 are cross-linked in situ matrix membrane, it is characterised in that: in step (2), the film forming
Post-processing approach are as follows: by obtained film forming be placed in methanol solution impregnate 12~remove remaining solvent for 24 hours, be then placed on 90
Dry 12 in~110 DEG C of vacuum drying ovens~for 24 hours, it obtains target product MOF and PIM-1 is cross-linked in situ matrix membrane.
6. MOF as described in claim 1 and PIM-1 are cross-linked in situ matrix membrane, it is characterised in that: the UIO-66-NH2It presses
It is prepared according to following method:
By 2- amino terephthalic acid (TPA), ZrCl4, formic acid and DMF mixed dissolution, stir 3~4h under room temperature, then shift solution
Into reaction kettle, it is put into 120 DEG C of baking oven and heats 24 hours, obtain reaction solution B, it is post-treated to obtain UiO-66-NH2；Institute
The 2- amino terephthalic acid (TPA) and ZrCl stated4The ratio between the amount of substance be 1:1；The additional amount of the formic acid is with the 2- ammonia
The amount of the substance of base terephthalic acid (TPA) is calculated as 1.11mL/mol.
7. MOF as claimed in claim 6 and PIM-1 are cross-linked in situ matrix membrane, it is characterised in that: the additional amount of the DMF
10~50mL/mol is calculated as with the amount of the substance of the 2- amino terephthalic acid (TPA).
8. MOF as claimed in claim 6 and PIM-1 are cross-linked in situ matrix membrane, it is characterised in that: after the reaction solution B
Processing method are as follows: be centrifuged obtained reaction solution B, obtained centrifugation product washs 3~6 times with methanol, then true at 120 DEG C
24 hours are activated in empty baking oven to get UiO-66-NH2。
9. a kind of MOF as described in claim 1 is cross-linked in situ matrix membrane with PIM-1 and separates applied to gas.
10. application as claimed in claim 9, it is characterised in that: the gas is CO2/CH4Or CO2/N2Gas.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112007527A (en) * | 2020-09-11 | 2020-12-01 | 长春工业大学 | Gas separation membrane containing MOF composite material and preparation method thereof |
| CN113713636A (en) * | 2021-08-27 | 2021-11-30 | 中国石油大学(华东) | Mixed matrix membrane based on PIM-1 and preparation method thereof |
| CN115228311A (en) * | 2022-07-08 | 2022-10-25 | 大连理工大学 | Preparation method of PIM-1 mixed matrix membrane based on amidoxime group modified UiO-66 material |
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| CN105792919A (en) * | 2013-12-16 | 2016-07-20 | 沙特基础工业全球技术公司 | Treated mixed matrix polymeric membranes |
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| CN105792919A (en) * | 2013-12-16 | 2016-07-20 | 沙特基础工业全球技术公司 | Treated mixed matrix polymeric membranes |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112007527A (en) * | 2020-09-11 | 2020-12-01 | 长春工业大学 | Gas separation membrane containing MOF composite material and preparation method thereof |
| CN113713636A (en) * | 2021-08-27 | 2021-11-30 | 中国石油大学(华东) | Mixed matrix membrane based on PIM-1 and preparation method thereof |
| CN115228311A (en) * | 2022-07-08 | 2022-10-25 | 大连理工大学 | Preparation method of PIM-1 mixed matrix membrane based on amidoxime group modified UiO-66 material |
| CN115228311B (en) * | 2022-07-08 | 2024-02-02 | 大连理工大学 | Preparation method of PIM-1 mixed matrix membrane based on amidoxime group modified UiO-66 material |
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Application publication date: 20191112 |