CN101077798A - Polyimide copolymer infiltration vaporization separation film for treating phenols-containing waste water and preparing method thereof - Google Patents
Polyimide copolymer infiltration vaporization separation film for treating phenols-containing waste water and preparing method thereof Download PDFInfo
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Abstract
The present invention belongs to the field of permeating and vaporizing film separation technology, and is especially permeating and vaporizing film of polyimide copolymer for treating phenol containing waste water and its preparation process. The permeating and vaporizing film is prepared through dissolving polyimide copolymer with fluoric malaic anhydride, fluoric diamine and carboxyl diamine in solvent, adding proper additives, phase transferring to prepare asymmetrical polyimide copolymer film, treating with cross-linking agent, coating, room temperature curing, stoving in a vacuum oven at 80-120 deg.c. The permeating and vaporizing film possesses a very thin compact surface separating layer and a porous supporting layer below the surface separating layer, and has thickness of 20-60 micron. In waste water treating test, it can separate phenol containing waste water into retained water with low phenol content and permeated water with high phenol content.
Description
Technical field
The invention belongs to the infiltrating and vaporizing membrane separation technology field, particularly be used for polyimide copolymer infiltration vaporization separation film of phenolic wastewater processing and preparation method thereof.
Background technology
Phenolic wastewater is a kind of one of wide, that the water yield is big, harm is very serious trade effluent of originating.Phenolic compound is a kind of strong neurotoxic substance and local corrosion is arranged, to all toxic effect of all bionts.The seriousness of phenols in water pollutes mainly due to them to the high toxicity of aquatic life be difficult to biological degradation, in recent years, increase in demand and production-scale continuous expansion along with phenolic compound, the discharging that contains the phenol trade effluent has caused severe contamination to environment, and Phenol-Containing Wastewater Treatment has become a great problem of water treatment at present.
Treatment of phenolic waste water such as extraction process, absorption method, biochemical process, electrolytic process and liquid-film method etc. all have certain treatment effect to phenolic wastewater at present, but exist and easily cause secondary pollution, shortcomings such as adsorptive capacity is limited, energy consumption is high, processing costs is high, technical process complexity, be difficult to large-scale industrial application.Therefore continue to seek that new to remove the phenol technology very necessary.
Membrane separation technique is a novel chemical separation technology, and infiltration evaporation is a kind of of membrane separation technique.The infiltration evaporation membrane separation technique can have very high selectivity under certain condition, separates with conventional separation method for those and has any problem or system that expense is high, as the separation of nearly boiling point, constant boiling point aqueous organopolysiloxane; Recovery to high value organic constituent in the separation of a small amount of organic pollutant in the removing of minor amount of water in organic solvent and the mixed solvent, the waste water and the aqueous solution has advantage significantly technical and economically.With respect to traditional phenol method that removes, the processing that this invention use infiltration evaporation membrane separation technique is carried out phenolic wastewater has less investment, process cost is low, separation efficiency is high, be easy to mass-producing, expandability is good, be convenient to remarkable advantage such as control.
The core of infiltration evaporation is the selection of mould material, and according to the selection principle of mould materials such as theory of solubility parameter and similar compatibility, polyimide is a kind of suitable one of phenol material that removes.Polyimide (PI) is a class high performance polymer material that has grown up since nineteen sixties, owing to have good thermotolerance, mechanical property and chemical resistance, has obtained application widely in fields such as machinery, chemical industry, electronics.In the membrane sepn field, the aromatic heterocycle polymer of polyimide has very high ventilative selectivity, is the outstanding gas separation membrane material of a class performance.Polyimide is again a kind of very potential infiltration vaporization separation film material simultaneously, in ethanol dehydration, cyclic hydrocarbon/fields such as aromatic hydrocarbons separation applied research is arranged.Germany F.Pithan etc. is used for the infiltration evaporation phenol recovery with the fluorinated polyimide multipolymer, when feed concentration is 7.8wt%, total permeation flux is 140g/ (m2h-1), phenol concentration reaches 40wt% in the penetrating fluid, good effect (F.Pithan and C.Staudt-Bickel, ChemPhysChem, 2003 have been received, 4,967～773).Because polyimide is a very big family, can select monomer dianhydride and diamines within a large range, so just can make the polyimide film of making satisfy different service requirementss.
Gordian technique of the present invention is the good asymmetric polyimide copolymer infiltration vaporization film of processability.Asymmetrical polyimide copolymer infiltration vaporization film is to be made of ultrafine fine and close separating layer and porous supporting layer, and the key for preparing good asymmetric membrane is that the separating layer that how to make ultra-thin densification does not influence permeation flux again.
The modification by copolymerization of superpolymer is macromolecule modified method commonly used, has become one of field active in polymer material science and the engineering, is easy to obtain to have the novel material of special construction, and exploitation has the important channel of brand-new performance type material especially.
Summary of the invention
One of purpose of the present invention is to be provided for the polyimide copolymer infiltration vaporization asymmetric membrane that phenolic wastewater is handled at above-mentioned technical problem, this film can be when keeping the original separation performance of polyimide film material, permeation flux increases considerably, to overcome the low shortcoming of dense film material self permeation flux.So-called permeation flux improves, and is meant with the comparison between the asymmetric membrane of method gained of the present invention and the common dense film.
Two of purpose of the present invention provides a kind of preparation method who is used for the polyimide copolymer infiltration vaporization separation film of phenolic wastewater processing.
The polyimide copolymer infiltration vaporization separation film that is used for the phenolic wastewater processing of the present invention is asymmetrical polyimide copolymer infiltration vaporization film (described polyimide copolymer is meant that macromolecular main chain contains the polyimide copolymer of a large amount of fluoro-containing groups), constitute by ultrafine fine and close separating layer and porous supporting layer, the epidermal area of this film is ultrafine fine and close separating layer, passive short texture is the porous supporting layer below the epidermal area, and the thickness of described film is between 20～60 μ m.
Described polyimide copolymer is formed by fluorine-containing dianhydride and the copolymerization of two kinds of diamines termonomer, wherein two kinds of diamines are respectively fluorinated diamines and contain the carboxyl diamines, fluorinated diamine and the mol ratio that contains the carboxyl diamines are between 1: 1～5: 1, and the total mol ratio of dianhydride and diamines is 1: 1.
Described fluorine-containing dianhydride is 4,4 '-hexafluoroisopropyli,ene-Tetra hydro Phthalic anhydride (6FDA).
Described fluorinated diamine is 2, two [4, (4-amino-benzene oxygen) phenyl] HFC-236fa (BAPOFP) of 2-.
The described carboxyl diamines that contains is 3,5-diaminobenzoic acid (DABA).
The preparation method who is used for the polyimide copolymer infiltration vaporization separation film of phenolic wastewater processing of the present invention is, at first the polyimide copolymer with fluorine-containing dianhydride and two kinds of diamines termonomer is dissolved in the solvent, after adding suitable non-solvent and additive, make the asymmetric membrane of polyimide copolymer by phase inversion process, and carry out after the crosslinking Treatment it standby.
The preparation method who is used for the polyimide copolymer infiltration vaporization separation film of phenolic wastewater processing of the present invention adopts phase inversion process, may further comprise the steps:
(1). the film-casting liquid preparation
With fluorine-containing dianhydride, fluorinated diamine and the polyimide copolymer that contains the carboxyl diamines by mass percentage concentration be 8～20% to be dissolved in the solvent, wherein, fluorinated diamine and the mol ratio that contains the carboxyl diamines are between 1: 1～5: 1, and the total mol ratio of dianhydride and diamines is 1: 1; Add non-solvent and additive then, wherein, non-solvent accounts for 5～10wt% in the mixing solutions, and additive accounts for 1～3wt%, is configured to film-casting liquid;
(2). the asymmetric membrane preparation
With the film-casting liquid of step (1) after filtration, deaeration and leave standstill after, curtain coating is on polyester non-woven fabric, curtain coating thickness is 150 μ m～180 μ m, through at air evaporation after 10～120 seconds, gel in 8～20 ℃ water, through repeatedly washing, make asymmetrical polyimide copolymer infiltration vaporization film, dry standby under the room temperature;
(3). aftertreatment
The asymmetrical polyimide copolymer infiltration vaporization film that step (2) is obtained dries back with acetone or Virahol rinse, use the acid solution (mass percent concentration is about 10～30%) of linking agent to apply then, after solidifying taking-up under the room temperature, in vacuum drying oven, after under 80～120 ℃ dry 5～12 hours, get finished film.
Solvent in the described step (1) is N, dinethylformamide, N,N-dimethylacetamide or N-methyl 2-Pyrrolidone etc.
Non-solvent in the described step (1) is acetone, butanone or Virahol etc.
Additive in the described step (1) is an organic acid, can be toxilic acid, methylene-succinic acid, oxalic acid or Lalgine etc.
Described asymmetrical polyimide copolymer infiltration vaporization film contains and can be used to crosslinked carboxyl.
Linking agent in the described step (3) is 1,10-certain herbaceous plants with big flowers glycol, glycol ether or octafluorohexane diol etc.
Acid in the described step (3) is sulfuric acid, Phenylsulfonic acid or hydrochloric acid etc.
Air evaporation in the described step (2) can be under suitable Heating temperature, and temperature range can be between 30～60 ℃.
The preparation method of the polyimide copolymer of described fluorine-containing dianhydride and two kinds of diamines termonomer: adopt cryogenic fluid polycondensation-chemical imidization method two-step approach synthetic.Synthesis step is in nitrogen protection and churned mechanically container are housed, under the condition of ice bath, to contain the carboxyl diamines earlier is dissolved in the solvent (N, dinethylformamide, N,N-dimethylacetamide or N-methyl 2-Pyrrolidone etc.), then fluorine-containing dianhydride is added in the reaction system, stir after 1～3 hour, add fluorinated diamine in reaction system, wherein, fluorinated diamine and the mol ratio that contains the carboxyl diamines are between 1: 1～5: 1, and the total mol ratio of dianhydride and diamines is 1: 1; Continue stirring reaction and form the heavy-gravity polyamic acid solution after 6～8 hours.Add excessive triethylamine and diacetyl oxide then in reaction system, carry out chemical imidization, form corresponding polyimide solution.With excessive industrial spirit precipitation, washing, drying.
The infiltration vaporization separation film that is used for the phenolic wastewater processing of the present invention's preparation, simple in structure, production cost is low.In removing phenol in waste water test, be used for infiltration vaporization separation film highly selective that phenolic wastewater handles with feedstream be split up into contain the low retentate of phenol amount and contain the phenol amount high see through thing.When being used to contain phenol 2～8wt% wastewater treatment, the permeation flux of film is 500～1160g/ (m
2H
-1), phenol concentration can reach 18～45wt% in the penetrating fluid.Novelty of the present invention is to have made full use of high molecular modification by copolymerization theory, given full play to the specific function of specific groups in the multipolymer, the advantage of polyimide is all given full play of, make it better physics and chemical property be arranged, enlarged the use range of polyimide effectively than homopolymer.
Description of drawings
Fig. 1. the infiltration evaporation membrane separating property determinator synoptic diagram that the present invention is used.
Reference numeral
1. tensimeter 2. film devices 3. feed side 4. see through side
5. cold-trap 6. vacuum pumps 7. material liquid tanks 8. feed pumps
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is further described.
In nitrogen protection and churned mechanically container are housed, under the condition of ice bath, earlier DABA is dissolved in solvent N, in the N-N,N-DIMETHYLACETAMIDE, then 6FDA is added in the reaction system, stir after 1～3 hour, add BAPOFP in reaction system, wherein, the mol ratio of BAPOFP and DABA is between 2: 1, and the total mol ratio of dianhydride and diamines is 1: 1; Continue stirring reaction and form the heavy-gravity polyamic acid solution after 6～8 hours.Add excessive triethylamine and diacetyl oxide then in reaction system, carry out chemical imidization, form corresponding polyimide solution.With excessive industrial spirit precipitation, washing, drying, obtain the polyimide copolymer of fluorine-containing dianhydride and two kinds of diamines termonomer.
(mol ratio of two kinds of diamines is 2: 1 with 6FDA/BAPOFP/DABA, the total mol ratio of dianhydride and diamines is 1: 1) polyimide copolymer is dissolved in N, in the N-dimethylacetamide solvent, be mixed with mass percent concentration and be 12% film liquid, add acetone and toxilic acid, the mass percent concentration of acetone is 8% in the mixing solutions, and the mass percent concentration of toxilic acid is 1%; Filter, curtain coating is on polyester non-woven fabric after the deaeration, curtain coating thickness is 180 μ m, through at air evaporation after 15 seconds, gel in 15 ℃ water, repeatedly wash with big water gaging, in water, soak 5～10 hours again after, make asymmetrical polyimide copolymer infiltration vaporization film.Take out and at room temperature dry.In the beaker of 50ml, add 1 of 30ml, 10-certain herbaceous plants with big flowers glycol, the 1ml Phenylsulfonic acid, it is standby to obtain aftertreatment fluid after fully stirring.With polyimide film earlier once with the acetone rinse, then the aftertreatment fluid for preparing is coated on the polyimide film after the acetone rinse, earlier drying at room temperature 2 hours, continued dry 8 hours down in 120 ℃ in vacuum drying oven the back, film gets product, the epidermal area of this film is ultrafine fine and close separating layer, and passive short texture is the porous supporting layer below the epidermal area, and thickness is about 30 μ m.Measure the Pervaporation Separation of film to phenolic wastewater.
See also Fig. 1.The waste water solution that will contain phenol is as in the material liquid tank 7, phenol concentration is 8wt% in feed liquid, under the working pressure of 2MPa (tensimeter 1), with feed pump 8 raw material is extracted out, heat by absorbing the product material is with raw material preheating to 20～60 ℃, by multiple type of heating such as steam, electricity or hot water, raw material is heated to 60 ℃, keeping film rear side vacuum tightness is 380Pa (seeing through side).In film device 2, asymmetrical polyimide copolymer infiltration vaporization film is divided into two chambers of upstream side, downstream side (feed side 3, see through side 4) with film device 2, feed side is a liquid-phase chamber, seeing through side is the vapour phase chamber, the vapour phase chamber is connected with vacuum system by cold-trap 5, keeps the absolute pressure of 30mmHg by the suction of vacuum pump 6.In the film device, liquid phase material flows through at the upstream side of film, and film has the selection trafficability characteristic to the phenol in the feed liquid, and the phenol molecular melting is adsorbed in the film surface, and phenol preferentially diffuses through under the effect of both sides vapor partial pressure difference.Along with liquid phase material the flowing of face, phenol content reduces gradually in the stock liquid, obtains highly purified fishery products in the membrane separation apparatus exit, the permeation flux of film is 870g/ (m
2H), phenol concentration is 42.5wt% in the penetrating fluid.
In nitrogen protection and churned mechanically container are housed, under the condition of ice bath, earlier DABA is dissolved in solvent N, in the dinethylformamide, then 6FDA is added in the reaction system, stir after 1～3 hour, add BAPOFP in reaction system, wherein, the mol ratio of BAPOFP and DABA is between 1: 1, and the total mol ratio of dianhydride and diamines is 1: 1; Continue stirring reaction and form the heavy-gravity polyamic acid solution after 6～8 hours.Add excessive triethylamine and diacetyl oxide then in reaction system, carry out chemical imidization, form corresponding polyimide solution.With excessive industrial spirit precipitation, washing, drying, obtain the polyimide copolymer of fluorine-containing dianhydride and two kinds of diamines termonomer.
(mol ratio of two kinds of diamines is 1: 1 with 6FDA/BAPOFP/DABA, the total mol ratio of dianhydride and diamines is 1: 1) polyimide copolymer is dissolved in N, in the dinethylformamide solvent, be mixed with mass percent concentration and be 14% film liquid, add acetone and Lalgine, the mass percent concentration of acetone is 10% in the mixing solutions, and the mass percent concentration of Lalgine is 2%; Filter, curtain coating is on polyester non-woven fabric after the deaeration, curtain coating thickness is 180 μ m, through at air evaporation after 50 seconds, gel in 20 ℃ water, repeatedly wash with big water gaging, in water, soak 5～10 hours again after, make asymmetrical polyimide copolymer infiltration vaporization film.Take out and at room temperature dry.In the beaker of 50ml, add the octafluorohexane diol of 35ml, 1ml sulfuric acid, it is standby to obtain aftertreatment fluid after fully stirring.With polyimide film earlier once with the acetone rinse, then the aftertreatment fluid for preparing is coated on the polyimide film after the acetone rinse, earlier drying at room temperature 2 hours, continued dry 10 hours down in 120 ℃ in vacuum drying oven the back, film gets product, the epidermal area of this film is ultrafine fine and close separating layer, and passive short texture is the porous supporting layer below the epidermal area, and thickness is about 25 μ m.Measure the Pervaporation Separation of film to phenolic wastewater.
See also Fig. 1.The waste water solution that will contain phenol is as in the material liquid tank 7, phenol concentration is 5wt% in feed liquid, under the working pressure of 2MPa (tensimeter 1), with feed pump 8 raw material is extracted out, heat by absorbing the product material is with raw material preheating to 20～60 ℃, by multiple type of heating such as steam, electricity or hot water, raw material is heated to 60 ℃, keeping film rear side vacuum tightness is 380Pa (seeing through side).In film device 2, asymmetrical polyimide copolymer infiltration vaporization film is divided into two chambers of upstream side, downstream side (feed side 3, see through side 4) with film device 2, feed side is a liquid-phase chamber, seeing through side is the vapour phase chamber, the vapour phase chamber is connected with vacuum system by cold-trap 5, keeps the absolute pressure of 30mmHg by the suction of vacuum pump 6.In the film device, liquid phase material flows through at the upstream side of film, and film has the selection trafficability characteristic to the phenol in the feed liquid, and the phenol molecular melting is adsorbed in the film surface, and phenol preferentially diffuses through under the effect of both sides vapor partial pressure difference.Along with liquid phase material the flowing of face, phenol content reduces gradually in the stock liquid, obtains highly purified fishery products in the membrane separation apparatus exit, the permeation flux of film is 950g/ (m
2H), phenol concentration is 35.8wt% in the penetrating fluid.
In nitrogen protection and churned mechanically container are housed, under the condition of ice bath, earlier DABA is dissolved in the solvent N-methyl 2-Pyrrolidone solvent, then 6FDA is added in the reaction system, stir after 1～3 hour, add BAPOFP in reaction system, wherein, the mol ratio of BAPOFP and DABA is between 5: 1, and the total mol ratio of dianhydride and diamines is 1: 1; Continue stirring reaction and form the heavy-gravity polyamic acid solution after 6～8 hours.Add excessive triethylamine and diacetyl oxide then in reaction system, carry out chemical imidization, form corresponding polyimide solution.With excessive industrial spirit precipitation, washing, drying, obtain the polyimide copolymer of fluorine-containing dianhydride and two kinds of diamines termonomer.
(mol ratio of two kinds of diamines is 5: 1 with 6FDA/BAPOFP/DABA, the total mol ratio of dianhydride and diamines is 1: 1) polyimide copolymer is dissolved in the N-methyl 2-Pyrrolidone solvent, be mixed with mass percent concentration and be 12% film liquid, add acetone and methylene-succinic acid, the mass percent concentration of acetone is 7% in the mixing solutions, and the mass percent concentration of methylene-succinic acid is 1%; Filter, curtain coating is on polyester non-woven fabric after the deaeration, curtain coating thickness is 180 μ m, through at air evaporation after 100 seconds, gel in 15 ℃ water, repeatedly wash with big water gaging, in water, soak 5～10 hours again after, make asymmetrical polyimide copolymer infiltration vaporization film.Take out and at room temperature dry.In the beaker of 50ml, add the glycol ether of 30ml, 1ml hydrochloric acid, it is standby to obtain aftertreatment fluid after fully stirring.With polyimide film earlier once with the acetone rinse, then the aftertreatment fluid for preparing is coated on the polyimide film after the acetone rinse, earlier drying at room temperature 2 hours, continued dry 10 hours down in 120 ℃ in vacuum drying oven the back, film gets product, the epidermal area of this film is ultrafine fine and close separating layer, and passive short texture is the porous supporting layer below the epidermal area, and thickness is about 50 μ m.Measure the Pervaporation Separation of film to phenolic wastewater.
See also Fig. 1.The waste water solution that will contain phenol is as in the material liquid tank 7, phenol concentration is 2wt% in feed liquid, under the working pressure of 2MPa (tensimeter 1), with feed pump 8 raw material is extracted out, heat by absorbing the product material is with raw material preheating to 20～60 ℃, by multiple type of heating such as steam, electricity or hot water, raw material is heated to 60 ℃, keeping film rear side vacuum tightness is 380Pa (seeing through side).In film device 2, asymmetrical polyimide copolymer infiltration vaporization film is divided into two chambers of upstream side, downstream side (feed side 3, see through side 4) with film device 2, feed side is a liquid-phase chamber, seeing through side is the vapour phase chamber, the vapour phase chamber is connected with vacuum system by cold-trap 5, keeps the absolute pressure of 30mmHg by the suction of vacuum pump 6.In the film device, liquid phase material flows through at the upstream side of film, and film has the selection trafficability characteristic to the phenol in the feed liquid, and the phenol molecular melting is adsorbed in the film surface, and phenol preferentially diffuses through under the effect of both sides vapor partial pressure difference.Along with liquid phase material the flowing of face, phenol content reduces gradually in the stock liquid, obtains highly purified fishery products in the membrane separation apparatus exit, the permeation flux of film is 900g/ (m
2H), phenol concentration is 18.2wt% in the penetrating fluid.
Claims (10)
1. one kind is used for the polyimide copolymer infiltration vaporization separation film that phenolic wastewater is handled, it is characterized in that: this polyimide copolymer infiltration vaporization separation film is asymmetrical polyimide copolymer infiltration vaporization film, the epidermal area of this film is ultrafine fine and close separating layer, passive short texture is the porous supporting layer below the epidermal area, and the thickness of described film is between 20～60 μ m;
Described polyimide copolymer is formed by fluorine-containing dianhydride and the copolymerization of two kinds of diamines termonomer, wherein two kinds of diamines are respectively fluorinated diamines and contain the carboxyl diamines, fluorinated diamine and the mol ratio that contains the carboxyl diamines are between 1: 1～5: 1, and the total mol ratio of dianhydride and diamines is 1: 1.
2. polyimide copolymer infiltration vaporization separation film according to claim 1 is characterized in that: described fluorine-containing dianhydride is 4,4 '-hexafluoroisopropyli,ene-Tetra hydro Phthalic anhydride.
3. polyimide copolymer infiltration vaporization separation film according to claim 1 is characterized in that: described fluorinated diamine is 2, two [4, (4-amino-benzene oxygen) phenyl] HFC-236fa of 2-.
4. polyimide copolymer infiltration vaporization separation film according to claim 1 is characterized in that: the described carboxyl diamines that contains is 3, the 5-diaminobenzoic acid.
5. the preparation method according to each described polyimide copolymer infiltration vaporization separation film of claim 1～4 is characterized in that, this method may further comprise the steps:
(1). the film-casting liquid preparation
With fluorine-containing dianhydride, fluorinated diamine and the polyimide copolymer that contains the carboxyl diamines by mass percentage concentration be 8～20% to be dissolved in the solvent, wherein, fluorinated diamine and the mol ratio that contains the carboxyl diamines are between 1: 1～5: 1, and the total mol ratio of dianhydride and diamines is 1: 1; Add non-solvent and additive then, wherein, non-solvent accounts for 5～10wt% in the mixing solutions, and additive accounts for 1～3wt%, is configured to film-casting liquid;
(2). the asymmetric membrane preparation
With the film-casting liquid of step (1) after filtration, deaeration and leave standstill after, curtain coating is on polyester non-woven fabric, through at air evaporation after 10～120 seconds, gel in 8～20 ℃ water, asymmetrical polyimide copolymer infiltration vaporization film is made in washing, dries standby under the room temperature;
(3). aftertreatment
The asymmetrical polyimide copolymer infiltration vaporization film that step (2) is obtained dries the back with acetone or Virahol rinse, and the acid solution with linking agent applies then, solidify under the room temperature take out after, in vacuum drying oven after 80～120 ℃ of following dryings finished film;
Described solvent is N, dinethylformamide, N,N-dimethylacetamide or N-methyl 2-Pyrrolidone;
Described non-solvent is acetone, butanone or Virahol;
Described additive is an organic acid.
6. method according to claim 5, it is characterized in that: the polyimide copolymer of described fluorine-containing dianhydride and two kinds of diamines termonomer is prepared by following method: in nitrogen protection and churned mechanically container are housed, under the condition of ice bath, to contain the carboxyl diamines earlier is dissolved in the solvent, then fluorine-containing dianhydride is added in the reaction system, stir, add fluorinated diamine in reaction system, wherein, fluorinated diamine and the mol ratio that contains the carboxyl diamines are between 1: 1～5: 1, and the total mol ratio of dianhydride and diamines is 1: 1; Continue to form the heavy-gravity polyamic acid solution behind the stirring reaction; Add excessive triethylamine and diacetyl oxide then in reaction system, carry out chemical imidization, form corresponding polyimide solution; With excessive industrial spirit precipitation, washing, drying.
7. method according to claim 6 is characterized in that: described fluorine-containing dianhydride is 4,4 '-hexafluoroisopropyli,ene-Tetra hydro Phthalic anhydride; Described fluorinated diamine is 2, two [4, (4-amino-benzene oxygen) phenyl] HFC-236fa of 2-; The described carboxyl diamines that contains is 3, the 5-diaminobenzoic acid.
8. method according to claim 5 is characterized in that: described organic acid is toxilic acid, methylene-succinic acid, oxalic acid or Lalgine.
9. method according to claim 5 is characterized in that: the linking agent in the described step (3) is 1,10-certain herbaceous plants with big flowers glycol, glycol ether or octafluorohexane diol;
Described acid is sulfuric acid, Phenylsulfonic acid or hydrochloric acid.
10. method according to claim 6 is characterized in that: described churning time is 1～3 hour; Continuing the stirring reaction time is 6～8 hours.
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| CN103007771A (en) * | 2012-12-11 | 2013-04-03 | 天邦膜技术国家工程研究中心有限责任公司 | After-treatment process for gas separation membrane |
| CN112933987A (en) * | 2014-07-29 | 2021-06-11 | 奥加诺株式会社 | Organic solvent purification system and method |
| CN112933987B (en) * | 2014-07-29 | 2022-07-26 | 奥加诺株式会社 | Organic solvent purification system and method |
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| CN106795285B (en) * | 2014-10-10 | 2020-06-05 | 东丽株式会社 | Polyimide solution, heat-resistant nonwoven fabric, and method for producing same |
| CN107281942A (en) * | 2017-06-28 | 2017-10-24 | 常州大学 | It is a kind of to be used to separate infiltration vaporization blending film of methanol tetrahydrofuran and preparation method thereof |
| CN107281942B (en) * | 2017-06-28 | 2020-02-14 | 常州大学 | Pervaporation blending membrane for separating methanol-tetrahydrofuran and preparation method thereof |
| CN108939949A (en) * | 2018-07-17 | 2018-12-07 | 大连理工大学 | A kind of pair of bilirubin has the polyimides affinity membrane and preparation method thereof of high absorption property |
| CN109745875A (en) * | 2019-03-05 | 2019-05-14 | 中复新水源科技有限公司 | A kind of preparation method of high throughput polyimides composite hyperfiltration membrane |
| CN111116912A (en) * | 2019-12-31 | 2020-05-08 | 山东华夏神舟新材料有限公司 | Polyimide resin, preparation method thereof and method for preparing polyimide film/cross-linked polyimide film by using polyimide resin |
| CN111318184A (en) * | 2020-02-27 | 2020-06-23 | 太原理工大学 | Click chemical grafting functionalized polyimide CO2Method for producing separation membrane |
| CN111318184B (en) * | 2020-02-27 | 2021-12-03 | 太原理工大学 | Click chemical grafting functionalized polyimide CO2Method for producing separation membrane |
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