CN101036862A - Polyarylethersuifone with cardo and hollow fiber ultra-filtration membrane of poly(arylether Ketone)s - Google Patents
Polyarylethersuifone with cardo and hollow fiber ultra-filtration membrane of poly(arylether Ketone)s Download PDFInfo
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- CN101036862A CN101036862A CN 200710063414 CN200710063414A CN101036862A CN 101036862 A CN101036862 A CN 101036862A CN 200710063414 CN200710063414 CN 200710063414 CN 200710063414 A CN200710063414 A CN 200710063414A CN 101036862 A CN101036862 A CN 101036862A
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Abstract
Phenolphthalein-based PES-C and PEK-C blend hollow fiber ultra-filtration membrane and its preparing method belong to the membrane separation technic field. In the invention, PES-C and PEK-C blends containing phenolphthalein side groups are used as high polymer, their glass temperatures are 63 DEG C to 115 DEG C higher than that of commercial polysulfone, simultaneously, their chemical stability is better; accordingly, the forming method and process condition for PES-C and PEK-C blend hollow fiber ultra-filtration membrane are provided. Experiments show that the hollow fiber membrane is provided with high-temperature resistant, solvent resistance, acidproof and alkaliproof, and antioxidant performances.
Description
Technical field
Phenolphthalein base polyether sulphone and PAEK blend hollow fiber ultrafiltration membrane and preparation method thereof belong to the membrane separation technique field, relate in particular to the hollow fiber ultrafiltration membrane separation technology field.
Background technology
It is emerging isolation technics at the beginning of the sixties that film separates, very rapid with its characteristics development such as energy-conservation, simple to operate, has made some traditional industries that the essence change has taken place.Such as, the concentrating of medical product, purification and separate and pyrogen (claims bacterial endotoxin again, polarity and non-polar solution all there is compatibility, have hear resistance, decomposition rate is more than 200 ℃, and it can cause fever, headache, feels sick, vomiting, stupor etc., cause death when serious) removal in, the conventional method such as the way of distillation etc. can cause the discharging of a large amount of spent acid alkali, cause certain environmental pollution, and cost are bigger.In recent years, utilize membrane separation technique in medicine production, to obtain very big effect, both can break away from environmental pollution, reduce production costs again, improve the quality of products, demonstrate obvious superiority.Film market, the world has effectively promoted society, expanding economy with 20～30% speed increments every year.Milipore filter is one of present most popular diffusion barrier, more and more widely is used for industrial circles such as food, medicine, biological products, sewage disposal, realizes that macromolecular substances, colloidal substance separate with little molecular solvent.
The development of membrane separation technique is developed as basis and core with film.The our times various countries offer user's milipore filter commodity, mainly contain CAM (CA), PS membrane (PSF), poly (ether sulfone) film (PES), polypropylene nitrile (PAN), polyvinylidene fluoride film (PVDF) etc.The serviceability temperature of these milipore filters all can not surpass 70 ℃, and for example the maximum operation (service) temperature of CA film is 30 ℃, and the maximum operation (service) temperature of PAN film is 60 ℃, and the maximum operation (service) temperature of pvdf membrane, PSF film, PES film is 70 ℃.Application of membrane separation technology concentrates at medical product, in the removal of separation, purification and pyrogen, film high-temp. need be sterilized, general steam sterilizing more than 120 ℃, and this has just limited the application of film.In order to satisfy the demands, to press for research and development and have the milipore filter high temperature resistant, that molecular cut off is little simultaneously concurrently.
Containing phenolphthalein lateral group polyarylether sulfone (PES-C) is the independently developed in recent years a kind of new membrane material of China, be the highest a kind of (the DTA measured value is 263 ℃) of vitrification point in the present polysulfones series, physical and mechanical properties and chemical stability with PES, and because high glass transition temperature has improved serviceability temperature, particularly solved after the processing fluidity of PES-C, widened its range of application in engineering plastics.
PES-C has several ten thousand hours service life under 200 ℃, have good dimensional performance, low thermal coefficient of expansion, and good flame retardant property, outstanding chemically-resistant, decay resistance, its every technical indicator all is better than polysulfones.Except that extremely strong polar solvent is arranged on a small quantity, acid, alkali and conventional solvent all there are good chemical stability, and can bear the steam high-temperature sterilization and handle or chemical treatment, sulfuryl and ehter bond are introduced macromolecular chain segment, have increased the hydrophily and the pliability of material itself.In addition, the ultrafiltration apparatus inner membrance easily causes mushroom to pollute under long-term the use, but the polyether sulphone milipore filter can bear processing of high-temperature steam heat sterilization or chemically treated acid and alkali-resistance etc., and these performances make polyether sulphone become a kind of comparatively ideal separation membrane.Therefore, PES-C can bear the steam high-temperature sterilization and handle or chemical treatment as membrane material.
The PAEK (PEK-C) that contains the phenolphthalein side group is that China at first synthesizes successfully and dropped into the model engineering plastic of batch process, its combination property can be compared U.S. with polyether-ether-ketone, and have the not available good solubilized processing characteristics of polyether-ether-ketone, therefore can be directly used in the preparation of milipore filter.In addition, the hear resistance of PEK-C is higher than polysulfones, can high temperature-resistant disinfectedly handle at aspects such as medical industry, food industry, bioengineering, and reasonable application prospect can be arranged.
According to existing bibliographical information, people such as Lu Xueren have prepared flat plate ultrafiltration membrane with polyether sulphone and PAEK respectively in the laboratory, adopting N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), dimethylacetylamide is solvent, butanone, EGME, acetone, polyethylene glycol and triethyl phosphate etc. are as additive system film.The mass percent concentration of polyether sulphone is (14～18) % in the preparation liquid, and the mass percent concentration of additive is (4～12) %.The hear resistance result of film shows, in 100 ℃ of boiling water, film digestion 5min is found out to the result of the test of 60min, along with the digestion time increases, the water flux of film with do not have digestion before compare, all do not have significant change.After 150 ℃ of processed, the water flux of polyether sulphone film and PAEK film descends 84% and 87% respectively approximately.
Be the experiment of the chemical stability of film in the table 1, the result shows that film soaks after three months in HCI and NaOH solution, and water flux slightly increases, but changes not obvious.At H
2O
2Soak after 24 days in the aqueous solution, the polyether sulphone membrane flux does not have significant change.PAEK is along with the increase of soak time, and water flux slowly increases, and has increased by 18% approximately after 24 days.
The experimental result that table 1 soaks in 3 kinds of solution
| The soak type | NaOH(PH＝12) | H 2O 21％(wt) | HCL(PH＝2.0) |
| Soak time | 3 months | 24 days | 3 months |
They have also investigated the structure of film, and polyether sulphone film surface is the thin finger-like pore of marshalling down, and following again is finger-like pore, and thin finger-like pore and finger-like pore major part are straight-through.The aperture layer of similar sponge structure under the PAEK film surface, following again is the finger-like pore layer.
People such as Wu Kaifen utilize PAEK to be raw material in the laboratory, make the flat plate ultrafiltration membrane that molecular cut off is 2000-10000.When solvent was N-methyl pyrrolidone (NMP), additive PEG-600, EGME, solvent were N, and during N-dimethylacetylamide (DMAC), additive is oxolane, PVP-10000, gamma-butyrolacton.The concentration of polymer is 24%-32%, and the concentration of additive is 4%-12%.Obtain molecular cut off and be 2000,6000,10000 film, permeable speed is respectively 2-6,4-10,8-15ml/cm
2H (0.3MPa) all can reach more than 99% the rejection of alpha-interferon.
Summary of the invention
The purpose of this invention is to provide polyether sulphone and PAEK blend hollow fiber ultrafiltration membrane and preparation method thereof.The present invention selects for use two kinds of high polymer blend as membrane material, prepares the milipore filter of high temperature resistant, anti-solvent, resistance to oxidation, acid-alkali-corrosive-resisting, superior performance.
Contain in polyether sulphone of the present invention and the PAEK blend hollow fiber ultrafiltration membrane preparation liquid:
Polyether sulphone and PAEK blended polymer P: it is polyether sulphone (PES-C) and PAEK (PEK-C) blend that contains the phenolphthalein side group;
Solvent S: be selected from N-methyl pyrrolidone (NMP), morpholine, chloroform (CHCl
3), carrene (CH
2Cl
2) or N, the blend of N-dimethylacetylamide (DMAc) and N-methyl pyrrolidone (NMP);
Additive A: be selected from formamide, polyvinylpyrrolidone (PVP), formic acid, propionic acid, ethylene glycol, n-butanol or lithium nitrate;
Wherein: P/ (P+S)=14%～25%wt;
The mass ratio of A/P=0～1: 1.
Compare with flat sheet membrane, it is simple that hollow-fibre membrane has the membrane module manufacturing process, and the filling area is big, and advantages such as low cost of manufacture are beneficial to large-scale promotion application.Therefore one of feature of the present invention is to prepare high temperature resistant, anti-solvent, resistance to oxidation, acid and alkali-resistance hollow fiber ultrafiltration membrane with polyether sulphone and PAEK blend.The present invention tests the chemical stability of these two kinds of materials, and the result is as shown in table 2.Experiment condition is: the film with these two kinds of material preparation thickness are 50 μ m～60 μ m, film is soaked in 11 kinds of aqueous solution shown in the table 2, and the temperature of solution is 40 ℃, soak time is 30 days.Through experiment test, quality, thickness and the intensity of film all do not change before and after soaking, and prove that these two kinds of materials have good acid and alkali-resistance, resistance to oxidation, chlorine resistance.
The chemical stability experimental result of table 2 film under 40 ℃ of temperature
| The soak type | O 3 10ppm | HCI (2％) | H 2SO 4 (2％) | HNO 3 (2％) | NaOH (2％) | NaOH (5％) | NaCIO (1％) | NaCIO (5％) | H 2O 2 (1％) | H 2O 2 (5％) |
| Polyether sulphone and PAEK blend hollow fiber membrane | The outward appearance of film, quality, thickness, the equal no change of intensity | |||||||||
Polyether sulphone of the present invention and PAEK blend hollow fiber ultrafiltration membrane have well high temperature resistant, anti-oxidant, acid and alkali-resistance and oxidative resistance.
Concrete embodiment
Polyether sulphone of the present invention can be represented with following general formula, its intrinsic viscosity 0.6-1.0:
PAEK of the present invention can represent that intrinsic viscosity is 0.5-0.9 with following general formula:
Solvent of the present invention comprises N-methyl pyrrolidone (NMP), morpholine, chloroform (CHCl
3), carrene (CH
2Cl
2) or N, the blend of N-dimethylacetylamide (DMAc) and N-methyl pyrrolidone (NMP);
The used additive of the present invention comprises formamide, polyvinylpyrrolidone (PVP), formic acid, propionic acid, ethylene glycol, n-butanol or lithium nitrate;
The present invention adopts dry-wet spinning, and dipping gel phase conversionization legal system is equipped with hollow fiber ultrafiltration membrane.Its preparation method comprises the following steps:
1. the composition of raw material in the preparation liquid
High polymer (P) shared mass percent concentration in the mixture of high polymer (P) and solvent (S) is 14%～25%wt, i.e. P/ (P+S)=14%～25%wt; Additive (A) is 0～1/1 with the mass ratio of high polymer (P), A/P=0～1/1.
2. the preparation of preparation liquid
With high polymer (P), solvent (S), additive (A), by after proportioning weighing in " 1 ", be placed on earlier in the molten material still.
3. dissolving
The film liquid of preparation in " 2 " was stirred 12～36 hours under 60 ℃～100 ℃ temperature, high polymer and additive fully are dissolved in the solvent, become uniform preparation liquid.
4. filter
Filter the uniform preparation liquid of dissolving down to remove insoluble impurity at 50 ℃～80 ℃.
5. deaeration
Under ℃ condition of room temperature～80, carry out vacuum defoamation.
6. hollow fiber ultrafiltration membrane forming method and process conditions
Spinning process:
Open molten material still baiting valve, preparation liquid is sprayed from the spinneret annular space; Open the inner gel of doughnut spinning-drawing machine and bathe (core liquid), and control valve is transferred to suitable aperture, core liquid is flowed out from hydrojet plate centre bore, form the nascent state hollow-fibre membrane; The nascent state tunica fibrosa is introduced the first gel groove and the second gel groove in proper order through the air gap of certain altitude, guide winding-roller again into.Regulate suitable coiling (drawing-off) speed, spinning still pressure and core flow quantity, make hollow-fibre membrane with suitable wall thickness.
Process conditions:
Spinning still pressure: 0.1MPa～0.4MPa,
The temperature of spinning solution: room temperature～60 ℃,
Hauling speed: 10m/min～40m/min,
Core liquid: ultrafiltration water, or contain the aqueous solution of 0～50%wt organic solvent, 5 ℃～60 ℃ of temperature, stream
Amount 0.5～3.0L/h,
The air gap: 0～1000mm, evaporation atmosphere air themperature: room temperature,
First coagulation bath: ultrafiltration water, 0～60 ℃ of temperature,
Second coagulation bath: ultrafiltration water, 30 ℃～60 ℃ of temperature.
The present invention is φ 0.5mm～φ 2mm by the external diameter of the hollow fiber ultrafiltration membrane of above-mentioned preparation method " 1～6 " preparation, and wall thickness is 0.1mm～0.4mm.
The present invention measures the pure water flux and the rejection of the hollow-fibre membrane made.Condition determination is the deionized water under 25 ℃, and operating pressure is 0.1MPa, and the molecular weight of bovine serum albumin is 67000, and the molecular weight of gamma Globulin is 150000.Heat treatment 30min in 100 ℃ of water, the water flux situation of change of mensuration film.
High temperature resistant, the anti-solvent corrosion of hollow fiber ultrafiltration membrane energy of the present invention's preparation has well anti-oxidant, resistance to acids and bases and chlorine resistance.In order to investigate the stability of membrane structure, behind the processing 30min, surveying its water flux result does not all have significant change in 100 ℃ water.
Embodiment:
Embodiment one, get membrane material polyether sulphone 50g PAEK 20g, solvent DMAc (S1) 100g and NMP (S2) 230g form mixed solvent, additive propionic acid (A) 25g, preparation 425g film liquid.Under 90 ℃ of temperature, stirred 15 hours, make uniform preparation liquid.After filtration, after the deaeration, by preparation method of the present invention " 6 " preparation hollow-fibre membrane.Spinning still pressure 0.1MPa, 30 ℃ of spinning solution temperature (still temperature), draft speed 25m/min, core liquid are 60 ℃ of water, and the air gap is that 0, the first coagulation bath is a water, and temperature is 60 ℃, and second coagulation bath is 60 ℃ a water.
In 25 ℃ water, soak after 24 hours the performance of test membrane.At operating pressure is 0.1MPa, and temperature is that the pure water flux of film is 650L/m under 25 ℃ the condition
2.h, film is 96% to the rejection of bovine serum albumin, is 98% to the rejection of gamma Globulin.
Film is compared when surveying its water flux with heat treatment not behind 100 ℃ water treatment 30min, does not have significant change.
Following examples see Table 3-table 10.
The preparation condition of table 3. example 2～8 and film properties tabulation
| Embodiment number | 2 | 3 | 4 | 5 | 6 | 7 | 8 | ||
| Film liquid is formed | Membrane material P (g) | Polyether sulphone [54] PAEK [6] | Polyether sulphone [6] PAEK [54] | Polyether sulphone [14] PAEK [70] | Polyether sulphone [70] PAEK [14] | Polyether sulphone [52.5] PAEK [52.5] | Polyether sulphone [12] PAEK [48] | Polyether sulphone [48] PAEK [12] | |
| Solvent S (g) | DMAC[360] | DMAC[360] | DMAC[360] | DMAC[360] | DMAC[360] | NMP[360] | NMP[360] | ||
| Additive A (g) | 0 | 0 | 0 | 0 | 0 | 0 | 0 | ||
| Intrinsic viscosity | 0.58 | 0.52 | 0.65 | 0.57 | 0.70 | 0.64 | 0.55 | ||
| Dissolution conditions | Temperature (℃) | 80 | 80 | 80 | 80 | 80 | 80 | 80 | |
| Time (h) | 15 | 15 | 15 | 15 | 15 | 15 | 15 | ||
| Hollow-fibre membrane preparation technology | Still is pressed (MPa) | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | |
| The still temperature (℃) | 30 | 30 | 30 | 30 | 30 | 30 | 30 | ||
| Draft speed (m/min) | 30 | 30 | 30 | 30 | 30 | 30 | 30 | ||
| The air gap (mm) | 20 | 20 | 20 | 20 | 20 | 20 | 20 | ||
| Evaporating temperature (℃) | There is not evaporation | There is not evaporation | There is not evaporation | There is not evaporation | There is not evaporation | There is not evaporation | There is not evaporation | ||
| Core liquid | Temperature (℃) | 30 | 30 | 30 | 30 | 30 | 30 | 30 | |
| Form | Water | Water | Water | Water | Water | Water | Water | ||
| First coagulation bath | Temperature (℃) | 0 | 0 | 0 | 0 | 0 | 0 | 0 | |
| Form | Water | Water | Water | Water | Water | Water | Water | ||
| Second coagulation bath | Temperature (℃) | 30 | 30 | 30 | 30 | 30 | 30 | 30 | |
| Form | Water | Water | Water | Water | Water | Water | Water | ||
| Film properties | Pure water flux (L/m 2.h) | 920 | 1020 | 490 | 670 | 120 | 850 | 896 | |
| The bovine serum albumin rejection | 83.6％ | 76.0％ | 88.2％ | 81.0％ | 94.0％ | 86.1％ | 88.6％ | ||
| The gamma Globulin rejection | 88.1％ | 83.0％ | 93.6％ | 95.0％ | 96.0％ | 93.5％ | 97.0％ | ||
Annotate: 1.[] interior quantity is for making the quality (g) of pleurodiaphragmatic in terspace material;
The preparation condition of table 4 example 9～16 and film properties tabulation
| Embodiment number | 9 | 10 | 11 | 12 | 13 | 14 | 15 | 16 | ||
| Film liquid is formed | Membrane material P (g) | Polyether sulphone [99.5] PAEK [5.5] | Polyether sulphone [5.5] PAEK [99.5] | Polyether sulphone [3] PAEK [57] | Polyether sulphone [57] PAEK [3] | Polyether sulphone [80] PAEK [4] | Polyether sulphone [4] PAEK [80] | Polyether sulphone [52.5] PAEK [52.5] | Polyether sulphone [52.5] PAEK [52.5] | |
| Solvent S (g) | NMP[360] | NMP[360] | DMAC [165] NMP[165] | DMAC [165] NMP[165] | DMAC [165] NMP[165] | DMAC [165] NMP[165] | DMAC [165] NMP[165] | DMAC[165] NMP[165] | ||
| Additive A (g) | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | ||
| Intrinsic viscosity | 0.83 | 0.76 | 0.57 | 0.56 | 0.69 | 0.6 | 0.75 | 0.73 | ||
| Dissolution conditions | Temperature (℃) | 80 | 80 | 80 | 80 | 80 | 80 | 80 | 80 | |
| Time (h) | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | ||
| Hollow-fibre membrane preparation technology | Still is pressed (MPa) | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | |
| The still temperature (℃) | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | ||
| Draft speed (m/min) | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | ||
| The air gap (mm) | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | ||
| Evaporating temperature (℃) | There is not evaporation | There is not evaporation | There is not evaporation | There is not evaporation | There is not evaporation | There is not evaporation | There is not evaporation | There is not evaporation | ||
| Core liquid | Temperature (℃) | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | |
| Form | Water | Water | Water | Water | Water | Water | Water | Water | ||
| First coagulation bath | Temperature (℃) | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | |
| Form | Water | Water | Water | Water | Water | Water | Water | Water | ||
| Second coagulation bath | Temperature (℃) | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | |
| Form | Water | Water | Water | Water | Water | Water | Water | Water | ||
| Film properties | Pure water flux (L/m 2.h) | 120 | 168 | 980 | 860 | 403 | 500 | 126 | 180 | |
| The bovine serum albumin rejection | 96.5％ | 94.6％ | 82.3％ | 85.2％ | 89.0％ | 85.8％ | 96.0％ | 95.2 | ||
| The gamma Globulin rejection | —— | —— | 83.1％ | 92.6％ | 96.9％ | 94.3％ | —— | —— | ||
Annotate: 1.[] interior quantity is for making the quality (g) of pleurodiaphragmatic in terspace material;
The preparation condition of table 5. example 17～24 and film properties tabulation
| Embodiment number | 17 | 18 | 19 | 20 | 21 | 22 | 23 | 24 | ||
| Film liquid is formed | Membrane material P (g) | Polyether sulphone [30] PAEK [30] | Polyether sulphone [30] PAEK [30] | Polyether sulphone [72] PAEK [8] | Polyether sulphone [8] PAEK [72] | Polyether sulphone [100] PAEK [5] | Polyether sulphone [5] PAEK [100] | Polyether sulphone [50] PAEK [10] | Polyether sulphone [10] PAEK [50] | |
| Solvent S (g) | DMAC [360] | DMAC [360] | DMAC [360] | DMAC [360] | DMAC [360] | DMAC [360] | NMP [360] | NMP[360] | ||
| Additive A (g) | Propionic acid [20] | Propionic acid [20] | Propionic acid [20] | Propionic acid [20] | Propionic acid [20] | Propionic acid [20] | Propionic acid [20] | Propionic acid [20] | ||
| Intrinsic viscosity | 0.67 | 0.53 | 0.75 | 0.7 | 0.86 | 0.8 | 0.71 | 0.62 | ||
| Dissolution conditions | Temperature (℃) | 80 | 80 | 80 | 80 | 80 | 80 | 80 | 80 | |
| Time (h) | 24 | 24 | 24 | 24 | 24 | 24 | 24 | 24 | ||
| Hollow-fibre membrane preparation technology | Still is pressed (MPa) | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | |
| The still temperature (℃) | 30 | 30 | 30 | 30 | 30 | 60 | 60 | 60 | ||
| Draft speed (m/min) | 30 | 30 | 30 | 30 | 30 | 30 | 30 | 30 | ||
| The air gap (mm) | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | ||
| Evaporating temperature (℃) | There is not evaporation | There is not evaporation | There is not evaporation | There is not evaporation | There is not evaporation | There is not evaporation | There is not evaporation | There is not evaporation | ||
| Core liquid | Temperature (℃) | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | |
| Form | Water | Water | Water | Water | Water | Water | Water | Water | ||
| First coagulation bath | Temperature (℃) | 60 | 60 | 60 | 60 | 60 | 60 | 60 | 60 | |
| Form | Water | Water | Water | Water | Water | Water | Water | Water | ||
| Second coagulation bath | Temperature (℃) | 60 | 60 | 60 | 60 | 60 | 60 | 60 | 60 | |
| Form | Water | Water | Water | Water | Water | Water | Water | Water | ||
| Film properties | Pure water flux (L/m 2.h) | 1022 | 1100 | 620 | 740 | 130 | 229 | 980 | 1020 | |
| The bovine serum albumin rejection | 82.54％ | 79.1％ | 91.6％ | 87.7％ | 96.0％ | 93.1％ | 89.0％ | 87.2％ | ||
| The gamma Globulin rejection | 85.6％ | 83.5％ | 94.3％ | 92.6％ | 98.7％ | 97.2％ | 97.9％ | 95.2％ | ||
Annotate: 1.[] interior quantity is for making the quality (g) of pleurodiaphragmatic in terspace material;
The preparation condition of table 6. example 25～31 and film properties tabulation
| Embodiment number | 25 | 26 | 27 | 28 | 29 | 30 | 31 | ||
| Film liquid is formed | Membrane material P (g) | Polyether sulphone [84] PAEK [21] | Polyether sulphone [21] PAEK [84] | Polyether sulphone [55] PAEK [5] | Polyether sulphone [5] PAEK [55] | Polyether sulphone [63] PAEK [21] | Polyether sulphone [21] PAEK [63] | Polyether sulphone [52.5] PAEK [52.5] | |
| Solvent S (g) | NMP[360] | NMP[360] | DMAC [165] NMP[165] | DMAC [165] NMP[165] | DMAC [165] NMP[165] | DMAC [165] NMP[165] | DMAC [165] NMP[165] | ||
| Additive A (g) | Propionic acid [20] | Propionic acid [20] | Propionic acid [20] | Propionic acid [20] | Propionic acid [20] | Propionic acid [20] | Propionic acid [20] | ||
| Intrinsic viscosity | 0.94 | 0.86 | 0.70 | 0.58 | 0.76 | 0.72 | 0.88 | ||
| Dissolution conditions | Temperature (℃) | 100 | 100 | 100 | 100 | 100 | 100 | 100 | |
| Time (h) | 24 | 24 | 24 | 24 | 24 | 24 | 24 | ||
| Hollow-fibre membrane preparation technology | Still is pressed (MPa) | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | |
| The still temperature (℃) | 30 | 30 | 30 | 30 | 30 | 30 | 30 | ||
| Draft speed (m/min) | 30 | 30 | 30 | 30 | 30 | 30 | 30 | ||
| The air gap (mm) | 0 | 0 | 0 | 0 | 0 | 0 | 0 | ||
| Evaporating temperature (℃) | There is not evaporation | There is not evaporation | There is not evaporation | There is not evaporation | There is not evaporation | There is not evaporation | There is not evaporation | ||
| Core liquid | Temperature (℃) | 5 | 5 | 5 | 5 | 5 | 5 | 5 | |
| Form | Water | Water | Water | Water | Water | Water | Water | ||
| First coagulation bath | Temperature (℃) | 60 | 60 | 60 | 60 | 60 | 60 | 60 | |
| Form | Water | Water | Water | Water | Water | Water | Water | ||
| Second coagulation bath | Temperature (℃) | 60 | 60 | 60 | 60 | 60 | 60 | 60 | |
| Form | Water | Water | Water | Water | Water | Water | Water | ||
| Film properties | Pure water flux (L/m 2.h) | 95 | 177 | 1020 | 1103 | 498 | 600 | 116 | |
| The bovine serum albumin rejection | 97.8％ | 97.2％ | 85.8％ | 88.0％ | 93.7％ | 92.6％ | 98.6％ | ||
| The gamma Globulin rejection | —— | —— | 94.1％ | 96.9％ | 96.8％ | 95.3％ | —— | ||
Annotate: 1.[] interior quantity is for making the quality (g) of pleurodiaphragmatic in terspace material;
The preparation condition of table 7. example 32～38 and film properties tabulation
| Embodiment number | 32 | 33 | 34 | 35 | 36 | 37 | 38 | ||
| Film liquid is formed | Membrane material P (g) | Polyether sulphone [50] PAEK [10] | Polyether sulphone [10] PAEK [50] | Polyether sulphone [63] PAEK [21] | Polyether sulphone [21] PAEK [63] | Polyether sulphone [100] PAEK [5] | Polyether sulphone [30] PAEK [30] | Polyether sulphone [43] PAEK [43] | |
| Solvent S (g) | DMAC [360] | DMAC [360] | DMAC [360] | DMAC [360] | DMAC [360] | NMP[360] | NMP[360] | ||
| Additive A (g) | Propionic acid [38] | Propionic acid [38] | Propionic acid [38] | Propionic acid [38] | Propionic acid [40] | Propionic acid [38] | Propionic acid [38] | ||
| Intrinsic viscosity | 0.75 | 0.71 | 0.89 | 0.75 | 0.83 | 0.81 | 0.94 | ||
| Dissolution conditions | Temperature (℃) | 100 | 100 | 100 | 100 | 100 | 100 | 100 | |
| Time (h) | 34 | 34 | 34 | 34 | 34 | 34 | 34 | ||
| Hollow-fibre membrane preparation technology | Still is pressed (MPa) | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | |
| The still temperature (℃) | 30 | 30 | 30 | 30 | 30 | 30 | 30 | ||
| Draft speed (m/min) | 30 | 30 | 30 | 30 | 30 | 30 | 30 | ||
| The air gap (mm) | 0 | 0 | 0 | 0 | 0 | 0 | 0 | ||
| Evaporating temperature (℃) | There is not evaporation | There is not evaporation | There is not evaporation | There is not evaporation | There is not evaporation | There is not evaporation | There is not evaporation | ||
| Core liquid | Temperature (℃) | 5 | 5 | 5 | 5 | 5 | 5 | 5 | |
| Form | Water | Water | Water | Water | Water | Water | Water | ||
| First coagulation bath | Temperature (℃) | 60 | 60 | 60 | 60 | 60 | 60 | 60 | |
| Form | Water | Water | Water | Water | Water | Water | Water | ||
| Second coagulation bath | Temperature (℃) | 60 | 60 | 60 | 60 | 60 | 60 | 60 | |
| Form | Water | Water | Water | Water | Water | Water | Water | ||
| Film properties | Pure water flux (L/m 2.h) | 790 | 890 | 400 | 497 | 380 | 696 | 320 | |
| The bovine serum albumin rejection | 88.8％ | 89.7％ | 96.3％ | 92.2％ | 93.2％ | 92.2％ | 95.9％ | ||
| The gamma Globulin rejection | 94.7％ | 92.1％ | 98.0％ | 96.1％ | 96.0％ | 95.3％ | 98.7％ | ||
Annotate: 1.[] interior quantity is for making the quality (g) of pleurodiaphragmatic in terspace material;
The preparation condition of table 8. example 39～45 and film properties tabulation
| Embodiment number | 39 | 40 | 41 | 42 | 43 | 44 | 45 | ||
| Film liquid is formed | Membrane material P (g) | Polyether sulphone [52] PAEK [52] | Polyether sulphone [30] PAEK [30] | Polyether sulphone [4] PAEK [56] | Polyether sulphone [80] PAEK [4] | Polyether sulphone [4] PAEK [80] | Polyether sulphone [63] PAEK [42] | Polyether sulphone [42] PAEK [63] | |
| Solvent S (g) | NMP[360] | DMAC [165] NMP[165] | DMAC[165] NMP[165] | DMAC [165] NMP[165] | DMAC [165] NMP[165] | DMAC [165] NMP[165] | DMAC[165] NMP[165] | ||
| Additive A (g) | Propionic acid [40] | Propionic acid [38] | Propionic acid [38] | Propionic acid [38] | Propionic acid [38] | Propionic acid [38] | Propionic acid [38] | ||
| Intrinsic viscosity | 0.88 | 0.79 | 0.73 | 0.90 | 0.71 | 0.92 | 0.88 | ||
| Dissolution conditions | Temperature (℃) | 100 | 100 | 100 | 100 | 100 | 100 | 100 | |
| Time (h) | 34 | 34 | 34 | 34 | 34 | 34 | 34 | ||
| Hollow-fibre membrane preparation technology | Still is pressed (MPa) | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | |
| The still temperature (℃) | 30 | 30 | 30 | 30 | 30 | 30 | 30 | ||
| Draft speed (m/min) | 30 | 30 | 30 | 30 | 30 | 30 | 30 | ||
| The air gap (mm) | 0 | 0 | 0 | 0 | 0 | 0 | 0 | ||
| Evaporating temperature (℃) | There is not evaporation | There is not evaporation | There is not evaporation | There is not evaporation | There is not evaporation | There is not evaporation | There is not evaporation | ||
| Core liquid | Temperature (℃) | 5 | 5 | 5 | 30 | 30 | 30 | 30 | |
| Form | Water | Water | Water | Water | Water | Water | Water | ||
| First coagulation bath | Temperature (℃) | 60 | 60 | 60 | 60 | 60 | 60 | 60 | |
| Form | Water | Water | Water | Water | Water | Water | Water | ||
| Second coagulation bath | Temperature (℃) | 60 | 60 | 60 | 60 | 60 | 60 | 60 | |
| Form | Water | Water | Water | Water | Water | Water | Water | ||
| Film properties | Pure water flux (L/m 2.h) | 260 | 700 | 790 | 320 | 398 | 272 | 291 | |
| The bovine serum albumin rejection | 96.9％ | 86.9％ | 88.2％ | 92.2％ | 95.5％ | 96.1％ | 95.9％ | ||
| The gamma Globulin rejection | —— | 924.9％ | 92.7％ | 95.7％ | 97.7％ | —— | —— | ||
Annotate: 1.[] interior quantity is for making the quality (g) of pleurodiaphragmatic in terspace material;
The preparation condition of table 9. example 46～52 and film properties tabulation
| Embodiment number | 46 | 47 | 48 | 49 | 650 | 51 | 52 | ||
| Film liquid is formed | Membrane material P (g) | Polyether sulphone [80] PAEK [4] | Polyether sulphone [80] PAEK [4] | Polyether sulphone [80] PAEK [4] | Polyether sulphone [80] PAEK [4] | Polyether sulphone [80] PAEK [4] | Polyether sulphone [80] PAEK [4] | Polyether sulphone [80] PAEK [4] | |
| Solvent S (g) | DMAC [360] | DMAC[360] | Chloroform [360] | NMP[360] | DMF[165] | DMAC[165] NMP[165] | Carrene [360] | ||
| Additive A (g) | Formamide 20 [60] | Formamide 80[40] | Formamide 20[40] | Formamide 80 [40] | PEG600[45] | PEG2000 [45] | PVPK30 [45] | ||
| Intrinsic viscosity | 0.67 | 0.76 | 0.70 | 0.80 | 0.66 | 0.76 | 0.80 | ||
| Dissolution conditions | Temperature (℃) | 90 | 90 | 90 | 90 | 90 | 90 | 90 | |
| Time (h) | 15 | 15 | 15 | 15 | 24 | 24 | 24 | ||
| Hollow-fibre membrane preparation technology | Still is pressed (MPa) | 0.1 | 0.1 | 0.1 | 0.1 | 0.2 | 0.2 | 0.2 | |
| The still temperature (℃) | 30 | 30 | 30 | 30 | 30 | 30 | 30 | ||
| Draft speed (m/min) | 25 | 25 | 30 | 30 | 20 | 20 | 30 | ||
| The air gap (mm) | 0 | 0 | 0 | 0 | 0 | 0 | 0 | ||
| Evaporating temperature (℃) | There is not evaporation | There is not evaporation | There is not evaporation | There is not evaporation | There is not evaporation | There is not evaporation | There is not evaporation | ||
| Core liquid | Temperature (℃) | 20 | 20 | 20 | 20 | 5 | 5 | 5 | |
| Form | The aqueous solution that contains 30%NMP | The aqueous solution that contains 50%NMP | The aqueous solution that contains 30%NMP | The aqueous solution that contains 50%NMP | Water | Water | Water | ||
| First coagulation bath | Temperature (℃) | 60 | 60 | 60 | 60 | 60 | 60 | 60 | |
| Form | Water | Water | Water | Water | Water | Water | Water | ||
| Second coagulation bath | Temperature (℃) | 60 | 60 | 60 | 60 | 60 | 60 | 60 | |
| Form | Water | Water | Water | Water | Water | Water | Water | ||
| Film properties | Pure water flux (L/m 2.h) | 700 | 780 | 650 | 600 | 800 | 700 | 780 | |
| The bovine serum albumin rejection | 56.0％ | 52.2％ | 65.9％ | 77.5％ | 92.0％ | 92.0％ | 90.3％ | ||
| The gamma Globulin rejection | 63.5％ | 60.1％ | 82.2％ | 90.2％ | 96.3％ | 95.9％ | 95.0％ | ||
Annotate: 1.[] interior quantity is for making the quality (g) of pleurodiaphragmatic in terspace material;
The preparation condition of table 10. example 53～58 and film properties tabulation
| Embodiment number | 53 | 46 | 55 | 56 | 57 | 58 | ||
| Film liquid is formed | Membrane material P (g) | Polyether sulphone [30] PAEK [30] | Polyether sulphone [40] PAEK [40] | Polyether sulphone [52.5] PAEK [52.5] | Polyether sulphone [40] PAEK [40] | Polyether sulphone [40] PAEK [40] | Polyether sulphone [52.5] PAEK [52.5] | |
| Solvent S (g) | NMP[360] | DMAC[360] | DMAC[165] NMP[165] | NMP[360] | DMAC[165] NMP[165] | DMAC[360] | ||
| Additive A (g) | N-butanol [60] | Lithium nitrate [20] | Formic acid [50] | Acetone [60] | Ethanol [60] | OA[15] PVPK30[15] | ||
| Intrinsic viscosity | 0.66 | 0.75 | 0.80 | 0.78 | 0.73 | 0.82 | ||
| Dissolution conditions | Temperature (℃) | 80 | 80 | 80 | 80 | 80 | 80 | |
| Time (h) | 15 | 15 | 15 | 15 | 15 | 24 | ||
| Hollow-fibre membrane preparation technology | Still is pressed (MPa) | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | |
| The still temperature (℃) | 60 | 60 | 60 | 60 | 60 | 60 | ||
| Draft speed (m/min) | 20 | 20 | 30 | 20 | 20 | 30 | ||
| The air gap (mm) | 20 | 20 | 20 | 20 | 20 | 0 | ||
| Evaporating temperature (℃) | Room temperature | Room temperature | Room temperature | Room temperature | Room temperature | There is not evaporation | ||
| Core liquid | Temperature (℃) | 30 | 30 | 30 | 30 | 30 | 5 | |
| Form | Water | Water | Water | Water | Water | Water | ||
| First coagulation bath | Temperature (℃) | 30 | 30 | 0 | 30 | 30 | 60 | |
| Form | Water | Water | Water | Water | Water | Water | ||
| Second coagulation bath | Temperature (℃) | 30 | 30 | 30 | 30 | 30 | 60 | |
| Form | Water | Water | Water | Water | Water | Water | ||
| Film properties | Pure water flux (L/m 2.h) | 720 | 660 | 200 | 789 | 760 | 598 | |
| The bovine serum albumin rejection | 92.3％ | 93.6％ | 97.0％ | 90.1％ | 92.9％ | 70.0％ | ||
| The gamma Globulin rejection | 97.0％ | 97.0％ | —— | 93.2％ | 93.8％ | 81.2％ | ||
Annotate: 1.[] interior quantity is for making the quality (g) of pleurodiaphragmatic in terspace material;
Claims (1)
1. a phenolphthalein base polyether sulphone and PAEK blend hollow fiber ultrafiltration membrane and preparation method thereof is characterized in that:
Contain:
P: it is two kinds of high polymers, and expression is to contain the polyether sulphone of phenolphthalein side group and PAEK blend by a certain percentage;
Solvent S: be selected from N-methyl pyrrolidone, morpholine, chloroform, carrene or N, the blend of N-dimethylacetylamide and N-methyl pyrrolidone;
Additive A: be selected from formamide, polyvinylpyrrolidone, formic acid, propionic acid, ethylene glycol, n-butanol or lithium nitrate;
Wherein: P/ (P+S)=14%～25%wt
The mass ratio of A/P=0～1: 1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710063414 CN101036862A (en) | 2007-01-31 | 2007-01-31 | Polyarylethersuifone with cardo and hollow fiber ultra-filtration membrane of poly(arylether Ketone)s |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710063414 CN101036862A (en) | 2007-01-31 | 2007-01-31 | Polyarylethersuifone with cardo and hollow fiber ultra-filtration membrane of poly(arylether Ketone)s |
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| CN101036862A true CN101036862A (en) | 2007-09-19 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102512997A (en) * | 2011-12-21 | 2012-06-27 | 天邦膜技术国家工程研究中心有限责任公司 | Hydrophilic polyethersulfone with cardo alloy ultrafiltration membrane and preparation method thereof |
| CN102762285A (en) * | 2009-08-03 | 2012-10-31 | 索尔维特殊聚合物意大利有限公司 | Process for the preparation of ethylene/chlorotrifluoroethylene polymer membranes |
| CN103638828A (en) * | 2013-12-20 | 2014-03-19 | 苏州膜华材料科技有限公司 | Preparation method of ultralow-pressure polyvinylidene fluoride alloy membrane for drinking water treatment |
| CN112619432A (en) * | 2019-09-24 | 2021-04-09 | 中国石油化工股份有限公司 | Ultrafiltration membrane and preparation method thereof |
-
2007
- 2007-01-31 CN CN 200710063414 patent/CN101036862A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102762285A (en) * | 2009-08-03 | 2012-10-31 | 索尔维特殊聚合物意大利有限公司 | Process for the preparation of ethylene/chlorotrifluoroethylene polymer membranes |
| CN102512997A (en) * | 2011-12-21 | 2012-06-27 | 天邦膜技术国家工程研究中心有限责任公司 | Hydrophilic polyethersulfone with cardo alloy ultrafiltration membrane and preparation method thereof |
| CN102512997B (en) * | 2011-12-21 | 2014-02-26 | 天邦膜技术国家工程研究中心有限责任公司 | Hydrophilic polyethersulfone with cardo alloy ultrafiltration membrane and preparation method thereof |
| CN103638828A (en) * | 2013-12-20 | 2014-03-19 | 苏州膜华材料科技有限公司 | Preparation method of ultralow-pressure polyvinylidene fluoride alloy membrane for drinking water treatment |
| CN112619432A (en) * | 2019-09-24 | 2021-04-09 | 中国石油化工股份有限公司 | Ultrafiltration membrane and preparation method thereof |
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