CN108499361A - A kind of preparation method of the adjustable nano-porous polymer film in aperture - Google Patents

A kind of preparation method of the adjustable nano-porous polymer film in aperture Download PDF

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CN108499361A
CN108499361A CN201810317098.1A CN201810317098A CN108499361A CN 108499361 A CN108499361 A CN 108499361A CN 201810317098 A CN201810317098 A CN 201810317098A CN 108499361 A CN108499361 A CN 108499361A
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polymer film
aperture
porous polymer
preparation
film
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CN108499361B (en
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李建荣
束伦
赵翠
王乃鑫
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Beijing University of Technology
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    • 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
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
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    • 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
    • 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
    • B01D61/002—Forward osmosis or direct osmosis
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    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
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    • 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
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
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    • 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
    • B01D61/145—Ultrafiltration
    • 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
    • B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
    • B01D61/362—Pervaporation
    • 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
    • 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
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0013—Casting processes
    • 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
    • B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
    • B01D67/003—Organic membrane manufacture by inducing porosity into non porous precursor membranes by selective elimination of components, e.g. by leaching
    • 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
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • 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
    • B01D71/08—Polysaccharides
    • B01D71/12—Cellulose derivatives
    • B01D71/14—Esters of organic acids
    • B01D71/16—Cellulose acetate
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D71/06—Organic material
    • B01D71/26—Polyalkenes
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D71/06—Organic material
    • B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
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    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • 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
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes

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Abstract

A kind of preparation method of the adjustable nano-porous polymer film in aperture, belongs to UF membrane field.The present invention uses molecule polymerization of olefin using catalyst compound molecule to prepare the seperation film with nano aperture as pore creating material.By using the molecule polymerization of olefin using catalyst compound of different molecular size, control the pore size of seperation film, it can be achieved that nano-porous polymer membrane aperture nanoscale adjusting.The present invention provides the preparation methods that nano-porous polymer film is adjusted in a kind of easy aperture, simple for process and cost is relatively low, material is easy to get convenient for extension production, and the separation membrane aperture prepared can be adjusted in nanoscale, therefore it has potential application prospect in terms of molecule screening.

Description

A kind of preparation method of the adjustable nano-porous polymer film in aperture
Technical field
The present invention relates to a kind of preparation methods of the adjustable nano-porous polymer film in aperture, belong to UF membrane field.
Background technology
Membrane separation technique is the mixture of different-grain diameter molecule on a molecular scale when passing through semi-permeable membrane, realizes selectivity The technology of separation has the characteristics that easy to operate, low energy consumption, good separating effect, non-secondary pollution, is more and more closed Note.Relative to processes such as traditional rectifying, absorption and extractions, membrane separation technique has efficient, energy-saving and environmental protection, molecular level filtering And filter process it is simple, easily controllable the advantages that.Membrane material used at present is mainly based on organic high molecular polymer, still The separation membrane aperture prepared with high molecular polymer this at present lacks the adjusting of nanoscale, exists simultaneously permeability and choosing " trade-off " effect between selecting property, therefore further increasing for the polymer film performance is limited, so that increasing film The cost of isolation technics.
The complexes such as metal-organic polyhedra (MOPs), metal cluster are a kind of nano materials of molecule base.It is not only With regular and uniform structure, can also its size be changed by using different metal ion and ligand, meanwhile, this material Material can be removed under water, acid and alkaline condition, therefore can be by using the molecule polymerization of olefin using catalyst chemical combination of different molecular size Object realizes that the aperture to polymer film separating layer in the adjusting of nanoscale, is prepared with adjustable nanometer as pore creating material The seperation film in aperture.The present invention provides a kind of preparation method of the nano-porous polymer film of easy adjustable aperture, works Skill is simple and cost is relatively low, and material, which is easy to get, is convenient for extension production, and the seperation film prepared is with preferable separating effect and surely It is qualitative, there is potential application prospect.
Invention content
The object of the present invention is to provide a kind of preparation methods of the adjustable nano-porous polymer film in aperture.
A kind of preparation method of the adjustable nano-porous polymer film in aperture, which is characterized in that include the following steps：
(1) in organic solvent by pore creating material dissolving, transparent solution is made；
(2) polymer is dissolved in step (1) prepared solution, obtains casting solution, stand at a certain temperature with Exclude the bubble in prepared casting solution；
(3) the prepared casting solution of step (2) is prepared into film forming, then gained film is dipped in appropriate solvent, will be polymerize Pore creating material in object film fully removes；The appropriate solvent is that can wash away pore creating material, while keeping polymer film structure Solvent；
(4) polymer film for obtaining step (3) is taken out from the appropriate solvent to get adjustable to a kind of aperture Seperation film.
Heretofore described pore creating material is molecule polymerization of olefin using catalyst compound, such as selected from metal-organic polyhedra (MOPs), first The molecule polymerization of olefin using catalyst compound of hydrochlorate, acetic acid salt.
Solvent in step (1) of the present invention can be methanol, ethyl alcohol, acetone, dichloromethane, n-hexane, N- methyl pyrroles One or more of pyrrolidone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide etc..
Selected polymer can be acetate fiber, aromatic polyamides, poly- piperazine acyl in heretofore described step (2) One kind in amine, sulfonated polyether sulfone, Kynoar polyether sulfone, polysulfones, polyvinyl chloride, polyvinyl alcohol, polyethylene, polypropylene etc. Or it is several.
A concentration of 0.01~20.00wt.% of pore creating material, polymer concentration 1.00 in heretofore described casting solution ~50.00wt.%.
Temperature used in heretofore described step (2) is 0~150 DEG C.
Time of repose is 0~5 day in heretofore described step (2).
It includes phase inversion, cladding process, interfacial polymerization, Dynamic Membrane to prepare film method in heretofore described step (3) Any means such as method.
Appropriate solvent described in heretofore described step (3) can be water, acid solution (such as sulfuric acid, hydrochloric acid, nitric acid acid Solution), aqueous slkali (such as hydroxide, ammonium hydroxide aqueous slkali).
The prepared adjustable nano-porous polymer film in aperture is for gas separation, infiltration vapour in the method for the present invention Separation in the fields such as change, reverse osmosis, positive infiltration, nanofiltration, ultrafiltration.
The technical principle of the present invention：It is dissolved molecule polymerization of olefin using catalyst compound as pore creating material in a solvent, it can be equal It is even to be dispersed in polymeric casting film liquid, and the mixing dispersion of Nano grade, the casting solution system that will then obtain again can also be reached Standby film forming, and pore creating material is removed by using appropriate solvent and is adjusted to get to a kind of aperture for Dye Removal nanofiltration Polymer film (can by adjusting concentration, pore creating material type etc. further to adjust aperture).Polymer film made from this method With larger porosity, small molecule flow channel is increased, considerably increases the permeation flux of seperation film, while by using The pore creating material of different molecular size obtains the polymer film with different pore size size separation layer.The system of seperation film in the present invention Preparation Method is simple, has excellent performance, of low cost, is easy to industrialize.
Specific implementation mode
With reference to embodiment further to the adjustable polymer nano filter membrane in aperture and its dyestuff rejection of the present invention It can be described in detail.However, the present invention is not limited to following embodiments.
Embodiment 1
Detach membrane preparation method：
(1) [the Cu of 161.5mg is weighed24(5-tBu-1,3-BDC)24(S)24] (tBu-MOP) powder, it is dissolved in the N- of 100mL In methyl pyrrolidone, it is stirred by ultrasonic to being completely dissolved, obtains the solution containing pore creating material tBu-MOP；
(2) it weighs in the solution that 25.84g Kynoar powder is added in step (1), and is stirred continuously to dissolving, Then obtained solution is placed in 60 DEG C of baking ovens, standing and defoaming 2 days, you can obtain Kynoar casting solution；
(3) the casting solution height obtained step (2) scratches for 150 microns of scraper on clean glass plate, so Be put into afterwards by tap water group at coagulating bath in film-forming, and regularly replace coagulating bath so that pore creating material can completely remove；
(4) NF membrane that step (3) obtains is taken out from coagulating bath, dries at room temperature, you can obtain a kind of for contaminating The polymer separation film of material removing nanofiltration.
Gained seperation film is subjected to Dye Removal performance test in nanofiltration device, test system is 0.1g/L methyl blues (MW=799.8) aqueous solution, test pressure 0.5MPa, test temperature are room temperature.
The seperation film measured is as follows to the removal performance of methyl blue：Flux is 13.45Lm-2·h-1·MPa-1, methyl blue Rejection be 97.81%.
Embodiment 2
Detach membrane preparation method：
(1) [the Cu of 323.5mg is weighed24(5-tBu-1,3-BDC)24(S)24] (tBu-MOP) powder, it is dissolved in the N- of 100mL In methyl pyrrolidone, it is stirred by ultrasonic to being completely dissolved, obtains the solution containing pore creating material tBu-MOP；
(2) it weighs in the solution that 25.88g Kynoar powder is added in step (1), and is stirred continuously to dissolving, Then obtained solution is placed in 60 DEG C of baking ovens, standing and defoaming 2 days, you can obtain Kynoar casting solution；
(3) the casting solution height obtained step (2) scratches for 150 microns of scraper on clean glass plate, so Be put into afterwards by tap water group at coagulating bath in film-forming, and regularly replace coagulating bath so that pore creating material can completely remove；
(4) NF membrane that step (3) obtains is taken out from coagulating bath, dries at room temperature, you can obtain a kind of for contaminating The polymer separation film of material removing nanofiltration.
Gained seperation film is subjected to Dye Removal performance test in nanofiltration device, test system is 0.1g/L methyl blues (MW=799.8) aqueous solution, test pressure 0.5MPa, test temperature are room temperature.
The seperation film measured is as follows to the removal performance of methyl blue：Flux is 41.27Lm-2·h-1·MPa-1, methyl blue Rejection be 97.01%.
Embodiment 3
Detach membrane preparation method：
(1) [the Cu of 486.1mg is weighed24(5-tBu-1,3-BDC)24(S)24] (tBu-MOP) powder, it is dissolved in the N- of 100mL In methyl pyrrolidone, it is stirred by ultrasonic to being completely dissolved, obtains the solution containing pore creating material tBu-MOP；
(2) it weighs in the solution that 25.92g Kynoar powder is added in step (1), and is stirred continuously to dissolving, Then obtained solution is placed in 60 DEG C of baking ovens, standing and defoaming 2 days, you can obtain Kynoar casting solution；
(3) the casting solution height obtained step (2) scratches for 150 microns of scraper on clean glass plate, so Be put into afterwards by tap water group at coagulating bath in film-forming, and regularly replace coagulating bath so that pore creating material can completely remove；
(4) NF membrane that step (3) obtains is taken out from coagulating bath, dries at room temperature, you can obtain a kind of for contaminating The polymer separation film of material removing nanofiltration.
Gained seperation film is subjected to Dye Removal performance test in nanofiltration device, test system is 0.1g/L methyl blues (MW=799.8) aqueous solution, test pressure 0.5MPa, test temperature are room temperature.
The seperation film measured is as follows to the removal performance of methyl blue：Flux is 52.72Lm-2·h-1·MPa-1, methyl blue Rejection be 95.77%.
Embodiment 4
Detach membrane preparation method：
(1) [the Cu of 315.6mg is weighed24(5-tBu-1,3-BDC)24(S)24] (tBu-MOP) powder, it is dissolved in the N- of 100mL In methyl pyrrolidone, it is stirred by ultrasonic to being completely dissolved, obtains the solution containing pore creating material tBu-MOP；
(2) it weighs in the solution that 22.72g Kynoar powder is added in step (1), and is stirred continuously to dissolving, Then obtained solution is placed in 60 DEG C of baking ovens, standing and defoaming 2 days, you can obtain Kynoar casting solution；
(3) the casting solution height obtained step (2) scratches for 150 microns of scraper on clean glass plate, so Be put into afterwards by tap water group at coagulating bath in film-forming, and regularly replace coagulating bath so that pore creating material can completely remove；
(4) NF membrane that step (3) obtains is taken out from coagulating bath, dries at room temperature, you can obtain a kind of for contaminating The polymer separation film of material removing nanofiltration.
Gained seperation film is subjected to Dye Removal performance test in nanofiltration device, test system is 0.1g/L methyl blues (MW=799.8) aqueous solution, test pressure 0.5MPa, test temperature are room temperature.
The seperation film measured is as follows to the removal performance of methyl blue：Flux is 203.92Lm-2·h-1·MPa-1, methyl Blue rejection is 97.82%.
Embodiment 5
Detach membrane preparation method：
(1) [the Fe of 315.6mg is weighed2Co(μ3-O)(CH3COO)6] (Fe2Co) powder, it is dissolved in the N- methyl pyrroles of 100mL In pyrrolidone, it is stirred by ultrasonic to being completely dissolved, obtains containing pore creating material Fe2The solution of Co；
(2) it weighs in the solution that 22.72g Kynoar powder is added in step (1), and is stirred continuously to dissolving, Then obtained solution is placed in 60 DEG C of baking ovens, standing and defoaming 2 days, you can obtain Kynoar casting solution；
(3) the casting solution height obtained step (2) scratches for 150 microns of scraper on clean glass plate, first Be put by tap water group at coagulating bath in film-forming, be then immersed in pH be 4 dilute hydrochloric acid solution form coagulating bath in, And regularly replace so that pore creating material can completely remove；
(4) NF membrane that step (3) obtains is taken out from coagulating bath, dries at room temperature, you can obtain a kind of for contaminating The polymer separation film of material removing nanofiltration.
Gained seperation film is subjected to Dye Removal performance test in nanofiltration device, test system is 0.1g/L methyl blues (MW=799.8) aqueous solution, test pressure 0.5MPa, test temperature are room temperature.
The seperation film measured is as follows to the removal performance of methyl blue：Flux is 94.61Lm-2·h-1·MPa-1, methyl blue Rejection be 99.38%.
Embodiment 6
Detach membrane preparation method：
(1) the acetic acid copper powders for weighing 315.6mg, are dissolved in the N-Methyl pyrrolidone of 100mL, are stirred by ultrasonic to complete Dissolving, obtains the solution containing pore creating material copper acetate；
(2) it weighs in the solution that 22.69g Kynoar powder is added in step (1), and is stirred continuously to dissolving, Then obtained solution is placed in 60 DEG C of baking ovens, standing and defoaming 2 days, you can obtain Kynoar casting solution；
(3) the casting solution height obtained step (2) scratches for 150 microns of scraper on clean glass plate, so Be put into afterwards by tap water group at coagulating bath in film-forming, and regularly replace coagulating bath so that pore creating material can completely remove；
(4) NF membrane that step (3) obtains is taken out from coagulating bath, dries at room temperature, you can obtain a kind of for contaminating The polymer separation film of material removing nanofiltration.
Gained seperation film is subjected to Dye Removal performance test in nanofiltration device, test system is 0.1g/L methyl blues (MW=799.8) aqueous solution, test pressure 0.5MPa, test temperature are room temperature.
The seperation film measured is as follows to the removal performance of methyl blue：Flux is 93.31Lm-2·h-1·MPa-1, methyl blue Rejection be 98.37%.

Claims (10)

1. a kind of preparation method of the adjustable nano-porous polymer film in aperture, which is characterized in that include the following steps：
(1) in organic solvent by pore creating material dissolving, transparent solution is made；
(2) polymer is dissolved in step (1) prepared solution, obtains casting solution, stood at a certain temperature to exclude Bubble in prepared casting solution；
(3) the prepared casting solution of step (2) is prepared into film forming, then gained film is dipped in appropriate solvent, by polymer film In pore creating material fully remove；The appropriate solvent is that can wash away pore creating material, while keeping the molten of polymer film structure Agent；
(4) polymer film for obtaining step (3) is taken out from the appropriate solvent to get to a kind of adjustable point of aperture From film.
2. a kind of preparation method of the adjustable nano-porous polymer film in aperture described in accordance with the claim 1, feature exist In the pore creating material is molecule polymerization of olefin using catalyst compound.
3. a kind of preparation method of the adjustable nano-porous polymer film in aperture described in accordance with the claim 1, feature exist In the pore creating material is the molecule polymerization of olefin using catalyst compound from metal-organic polyhedra (MOPs), formates, acetic acid salt.
4. a kind of preparation method of the adjustable nano-porous polymer film in aperture described in accordance with the claim 1, feature exist In the solvent in step (1) is methanol, ethyl alcohol, acetone, dichloromethane, n-hexane, N-Methyl pyrrolidone, N, N- dimethyl One or more of formamide, DMAC N,N' dimethyl acetamide；Appropriate solvent described in step (3) is water, acid solution or alkali Solution.
5. a kind of preparation method of the adjustable nano-porous polymer film in aperture described in accordance with the claim 1, feature exist In selected polymer can be acetate fiber, aromatic polyamides, polypiperazine-amide, sulfonated polyether sulfone, gather partially in step (2) One or more of vinyl fluoride, polyether sulfone, polysulfones, polyvinyl chloride, polyvinyl alcohol, polyethylene, polypropylene.
6. a kind of preparation method of the adjustable nano-porous polymer film in aperture described in accordance with the claim 1, feature exist In a concentration of 0.01~20.00wt.% of pore creating material in the casting solution, polymer concentration is 1.00~50.00wt.%.
7. a kind of preparation method of the adjustable nano-porous polymer film in aperture described in accordance with the claim 1, feature exist In the temperature used in step (2) is 0~150 DEG C, and time of repose is 0~5 day.
8. a kind of preparation method of the adjustable nano-porous polymer film in aperture described in accordance with the claim 1, feature exist In, prepared in step (3) film method be phase inversion, cladding process, interfacial polymerization, dynamic embrane method any means.
9. the adjustable nano-porous polymer film in aperture being prepared according to claim 1-8 any one of them methods.
10. the adjustable nano-porous polymer film in aperture being prepared according to claim 1-8 any one of them methods Application, for gas separation, infiltration evaporation, reverse osmosis, positive infiltration, nanofiltration, ultrafiltration.
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Cited By (4)

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