CN101530752A - Method for preparing polyether sulfone microporous film by heating induced phase separation - Google Patents
Method for preparing polyether sulfone microporous film by heating induced phase separation Download PDFInfo
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- CN101530752A CN101530752A CN200910096835A CN200910096835A CN101530752A CN 101530752 A CN101530752 A CN 101530752A CN 200910096835 A CN200910096835 A CN 200910096835A CN 200910096835 A CN200910096835 A CN 200910096835A CN 101530752 A CN101530752 A CN 101530752A
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Abstract
The invention relates to a method for preparing a polyether sulfone microporous film by heating induced phase separation. Firstly, high molecular polyether sulfone resin is dissolved in a strong polar solvent, then poor solvent and gelata are added into the strong polar solvent, the mixed solution is sensitive to heating, phase separation occurs when the mixed solution is heated to a definite temperature, and then an even transparent solution is formed and statically de-foamed; under the temperature condition lower than a temperature at which the solution generates phase separation, the solution is coated on a glass sheet or a bright steel strip surface, the glass sheet/steel strip is heated, the phase separation occurs for the solution when the temperature of the glass sheet/steel strip is higher than a solution phase separation temperature to form a microporous structure and then generate a primary film; and the primary film is soaked into water and further solidified, the solvent is cleaned, and the solidified primary film is dried to form a finished product. The method has the advantage that the method is different from the prior thermally induced phase separation film-making principle, and is a heating induced phase separation process; the referred film manufacturing process is simple, does not need extra solvent/non-solvent gelling process, and does not need special solvent and additive; and the heating process is mild, the pollution is little, and the cost is low.
Description
Technical field
The invention belongs to the technology of preparing of microporous membrane of polyethersulfone, mainly is a kind of method of preparing polyether sulfone microporous film by heating induced phase separation.
Background technology
The high molecular polymer microporous barrier is a new high-tech industry that abroad grows up in the 1970's, belongs to film and separates category.Various diffusion barriers are pressed the magnitude classification in space in the film, are divided into usually in the film industry from small to large: reverse osmosis membrane (reverseosmosis membrane), NF membrane (nano-filtration membrane), milipore filter (ultrafiltrationmembrane) microporous barrier (micro-filtration membrane).Reverse osmosis membrane is generally used for desalinization, ultra-pure water and produces etc. on using, NF membrane is generally used in the water removal of big metal ions such as low molecule and calcium, magnesium, milipore filter then is generally used for the separation of Polymer Solution, the application of microporous barrier is then more complicated extensively, clarification filtration as food and drink, the aseptic filtration of pharmaceutical preparation is as wastewater membrane bioreactor construction assembly etc.
The reparation technology of microporous barrier is divided into non-solvent usually and causes phase separation method, thermally induced phase separation and pulling method.Wherein non-solvent causes the basic principle of phase separation method and is exactly: earlier polymer and certain amount of solvent and poor solvent or gel are mixed, be mixed with stable or metastable polymer under certain condition, solvent, poor solvent or gel mixed liquor, then mixed liquor is supported in glass plate or the annular polishing steel band that rotates continuously or polishing rotary drum or nonwoven with certain thickness curtain coating, change the existence condition of casting solution then, evaporate as solvent, non-solvent immersion etc., original stable or metastable casting solution can be separated because of the variation of internal component content, be usually expressed as casting solution and become muddy, bleach then, produce microcellular structure.The basic principle of the thermally induced phase separation on the ordinary meaning is: earlier polymer is mixed with poor solvent, heat temperature raising, make polymer dissolution become the mixed liquor of homogeneous phase, under heat-retaining condition, mixed liquor is supported in glass plate or the annular polishing steel band that rotates continuously or polishing rotary drum or nonwoven with certain thickness curtain coating, cooling makes it to be separated then, produces microporous barrier.
Summary of the invention
The present invention is the reverse process of traditional thermally induced phase separation system film, is a kind of new film-forming method, i.e. a kind of method of preparing polyether sulfone microporous film by heating induced phase separation.
The present invention realizes the technical scheme that above-mentioned purpose adopts.Main points of the present invention are to prepare a kind of polyethersulfone resin, solvent, poor solvent, gel mixed solution, and under lower temperature conditions, this solution is stable transparent, after this solution is heated to certain temperature, the instability of solution becomes can become muddy, and generation is separated.With scraper this solution casting is become liquid film under lower temperature conditions, heat liquid film then, liquid film can raise and the generation phase-splitting by Yin Wendu, forms microcellular structure, and the nascent film of phase-splitting is inserted clean in the water, after the oven dry film forming.
This method that the thermic phase separation method is produced microporous membrane of polyethersulfone that adds of the present invention comprises the following steps:
(1) at first the high molecular polyether sulphone resin is dissolved in the intensive polar solvent, add poor solvent and gel again, this mixed solution is at 0 ℃--and under 40 ℃ of cryogenic conditions is stable transparent, mixed solution is thermo-responsive to adding, after being heated to certain temperature (35 ℃-100 ℃), can be separated, make homogeneous transparent solution, leave standstill froth breaking, wherein high molecular polyether sulphone resin mass fraction is 8-19 part, the mass fraction of intensive polar solvent is 20-40 part, the mass fraction of poor solvent is 33-65 part, and the mass fraction of gel is 5-20 part;
(2) produce under the temperature conditions be separated being lower than solution, with scraper with above-mentioned solution casting on glass or bright steel band face, heating glass plate/steel band, when temperature was higher than the solution phase separation temperature, solution produced and is separated, and formed microcellular structure, produced nascent film;
(3) film of will coming into being immerses in the water, further solidifies cleaning solvent, drying, finished product.
Intensive polar solvent in the step of the present invention (1) is dimethyl formamide, N-methyl pyrrolidone or their mixture; Poor solvent is a PEG400, and gel is a glycerine.
Heating-up temperature in the step of the present invention (2) is 35 ℃-100 ℃, and be 15 seconds to 10 minutes heat time heating time.
Described high molecular polyether sulphone resin mean molecule quantity is 58000.
The effect that the present invention is useful: the polyether sulfone film-forming method set forth in the present invention just in time thermally induced phase separation with traditional is opposite, the Polymer Solution of tradition thermic phase method configuration is stable under the condition of high temperature, be separated at low temperatures then, and in the method provided by the present invention, macromolecule, the solvent liquid of configuration are stable transparents under the lower condition of temperature, mixed liquor will be separated under the higher condition of temperature, is a kind of filming technology that is different from conventional method.The patent of producing of usually external microporous membrane of polyethersulfone all adopts traditional non-solvent to cause phase separation method, as US patent5869174, US patent5178765, US patent 6056903 etc.The related film manufacture process of wood invention is simple, need not extra solvent/non-solvent gel process, need not special solvent and additive, and the heating process gentleness is polluted fewly, and cost is low, is fit to suitability for industrialized production.
Description of drawings:
Fig. 1 is with the micro-structure diagram of ESEM to the air contact-making surface surface of the PES microporous barrier produced among the embodiment 1;
Fig. 2 is with the micro-structure diagram of ESEM to the section of the PES microporous barrier produced among the embodiment 1;
Fig. 3 is with the micro-structure diagram of ESEM to the air contact-making surface surface of the PES microporous barrier produced among the embodiment 5;
Fig. 4 is with the micro-structure diagram of ESEM to the section of the PES microporous barrier produced among the embodiment 5.
The specific embodiment:
Below in conjunction with embodiment and accompanying drawing the present invention is further described, embodiment will help to understand the present invention better, but the present invention is not limited only to following embodiment.
Embodiment 1
Admixtured polyether sulphone resin (mean molecule quantity 58000) and dimethyl formamide, both mass ratioes are 50: 80, are heated to 110 ℃, make polyether sulfone be dissolved as the transparent clear viscous solution fully, solution is cooled to 20 ℃, add 180 parts of PEG400, acutely rock and shake up, make it to become homogeneous phase transparent solution, add 33.2 parts of glycerine again, acutely rock once more to shake up and be transparent homogeneous solution, get the heating of part solution and observe, producing the temperature that is separated is 42 ℃.The mixed solution of cooling is poured on the glass plate, wipe off with metallic spatula, the gap between scraper and the glass plate is 294 microns.Glass plate was put into 50 baking ovens of spending 5 minutes, take out.This moment, liquid film was separated, and liquid film bleaches, glass plate is immersed in the 20 degree pure water soaked 2 hours, took out white diaphragm, 80 degree oven dry.Measuring 100% ethanol bubble point pressure is the about 0.1 μ m in 0.22-0.26mpa k aperture, and flux is: 143.9L/m
2.min.bar.
Embodiment 2
Embodiment 1 configuration solution is poured on the glass plate, wipe off with metallic spatula, the gap between scraper and the glass plate is 294 microns.Glass plate was put into 100 baking ovens of spending 5 minutes, take out.This moment, liquid film was separated, and liquid film bleaches, glass plate is immersed in the 20 degree pure water soaked 2 hours, took out white diaphragm, 80 degree oven dry.Measuring 100% ethanol bubble point pressure is that the about 0.05 μ m flux in 0.32-0.36mpa aperture is: 113.3L/m
2.min.bar
Embodiment 3
Admixtured polyether sulphone resin (mean molecule quantity 58000) and dimethyl formamide, both mass ratioes are 40: 80, i.e. 40 parts of polyethersulfone resins, 80 parts of dimethyl formamides are heated to 110 ℃, make polyether sulfone be dissolved as the transparent clear viscous solution fully, solution is cooled to the following temperature of 20 degree, add 160 parts of PEG400, acutely rock and shake up, make it to become homogeneous phase transparent solution, add 29.6 parts of glycerine again, acutely rock once more to shake up and be transparent homogeneous solution, get the heating of part solution and observe, producing the temperature that is separated is 39 degree.The mixed solution of cooling is poured on the glass plate, wipe off with metallic spatula, the gap between scraper and the glass plate is 294 microns.Glass plate was put into 75 baking ovens of spending 5 minutes, take out, this moment, liquid film was separated, and liquid film bleaches, with immersion in the glass plate immersion 20 degree pure water 2 hours, took out white diaphragm, 80 ℃ of oven dry.Measuring 100% ethanol bubble point pressure is 0.28-0.3mpa, the about 0.07 μ m in aperture, and flux is: 51 seconds 141.0L/m
2.min.bar.
Embodiment 4
Get embodiment three mixed solutions and pour on the glass plate, wipe off with metallic spatula, the gap between scraper and the glass plate is 294 microns.Glass plate was put into 45 baking ovens of spending 5 minutes, take out.This moment, liquid film was separated, and liquid film bleaches, glass plate is immersed in the 20 degree pure water soaked 2 hours, took out white diaphragm, 80 degree oven dry.Measuring 100% ethanol bubble point pressure is that the about 0.09 μ m flux in 0.25--0.27mpa aperture is: 156.4L/m
2.min.bar.
Embodiment 5
Admixtured polyether sulphone resin (mean molecule quantity 58000) and N methyl pyrrolidone, both mass ratioes are 50: 111, i.e. 50 parts of polyethersulfone resins, 111 parts of dimethyl formamides are heated to 110 degree, make polyether sulfone be dissolved as the transparent clear viscous solution fully, solution is cooled to 20 ℃, add 150 parts of PEG400, acutely rock and shake up, make it to become homogeneous phase transparent solution, add 42..2 part glycerine again, acutely rock once more to shake up and be transparent homogeneous solution, get the heating of part solution and observe, producing the temperature that is separated is 35 ℃.The mixed solution of cooling is poured on the glass plate, wipe off with metallic spatula, the gap between scraper and the glass plate is 294 microns.Glass plate was put into 55 baking ovens of spending 5 minutes, take out, this moment, liquid film was separated, and liquid film bleaches.Took out 80 ℃ of oven dry of white diaphragm in 2 hours with soaking in the glass plate immersion 20 degree pure water, measuring 100% ethanol bubble point pressure is that about 0.05 flux in 0.28-0.36mpa aperture is: 89.9L/m
2.min.bar.
The PES film of the present invention preparation has carried out bubble point method pore size determination, and the film sample is washed into the disk film of diameter 47mm, has carried out flux mensuration under the vacuum draw of 0.03mpa.
Fig. 1 observes the microstructure on the air contact-making surface surface of the PES microporous barrier produced among the embodiment 1 with ESEM, and micropore is evenly distributed.
Fig. 2 observes the microstructure of the section of the PES microporous barrier produced among the embodiment 1 with ESEM, and the space is evenly distributed, the voidage height.
Fig. 3 observes the microstructure on the air contact-making surface surface of the PES microporous barrier produced among the embodiment 5 with ESEM, and micropore is evenly distributed.
Fig. 4 observes the microstructure of the section of the PES microporous barrier produced among the embodiment 5 with ESEM, and the space is evenly distributed, the voidage height.
Claims (6)
1, a kind ofly adds the method that the thermic phase separation method is produced microporous membrane of polyethersulfone, it is characterized in that: comprise the following steps:
(1) at first the high molecular polyether sulphone resin is dissolved in the intensive polar solvent, add poor solvent and gel again, this mixed solution is at 0 ℃--and under 40 ℃ of cryogenic conditions is stable transparent, mixed solution is thermo-responsive to adding, being heated to 35 ℃--can be separated after 100 ℃ of temperature, make homogeneous transparent solution, leave standstill froth breaking, wherein high molecular polyether sulphone resin mass fraction is 8-19 part, the mass fraction of intensive polar solvent is 20-40 part, the mass fraction of poor solvent is 33-65 part, and the mass fraction of gel is 5-20 part;
(2) produce under the temperature conditions be separated being lower than solution, with scraper with above-mentioned solution casting on glass or bright steel band face, heating glass plate/steel band, when temperature was higher than the solution phase separation temperature, solution produced and is separated, and formed microcellular structure, produced nascent film;
(3) film of will coming into being immerses in the water, further solidifies cleaning solvent, drying, finished product.
2, according to claim 1ly add the method that the thermic phase separation method is produced microporous membrane of polyethersulfone, it is characterized in that: the intensive polar solvent in the step (1) is dimethyl formamide, N-methyl pyrrolidone or their mixture.
3, according to claim 1ly add the method that the thermic phase separation method is produced microporous membrane of polyethersulfone, it is characterized in that: poor solvent is a PEG400 in the step (1).
4, according to claim 1ly add the method that the thermic phase separation method is produced microporous membrane of polyethersulfone, it is characterized in that: gel is a glycerine in the step (1).
5, according to claim 1ly add the method that the thermic phase separation method is produced microporous membrane of polyethersulfone, it is characterized in that: the heating-up temperature in the step (2) is 35 ℃-100 ℃, and be 15 seconds to 10 minutes heat time heating time.
6, according to claim 1ly add the method that the thermic phase separation method is produced microporous membrane of polyethersulfone, it is characterized in that: described high molecular polyether sulphone resin mean molecule quantity is 58000.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103055724A (en) * | 2011-10-19 | 2013-04-24 | 华东理工大学 | Method for preparing polysulfones polymer microporous membrane by counter-current thermally induced phase separation method |
| CN103846012A (en) * | 2012-12-04 | 2014-06-11 | 中国科学院大连化学物理研究所 | Method for preparing porous separation membrane |
| CN105771703A (en) * | 2016-03-15 | 2016-07-20 | 北京工业大学 | Preparation method of polyethersulfone-based composite positive permeable membrane |
-
2009
- 2009-03-13 CN CN200910096835A patent/CN101530752A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103055724A (en) * | 2011-10-19 | 2013-04-24 | 华东理工大学 | Method for preparing polysulfones polymer microporous membrane by counter-current thermally induced phase separation method |
| CN103055724B (en) * | 2011-10-19 | 2015-05-13 | 华东理工大学 | Method for preparing polysulfones polymer microporous membrane by counter-current thermally induced phase separation method |
| CN103846012A (en) * | 2012-12-04 | 2014-06-11 | 中国科学院大连化学物理研究所 | Method for preparing porous separation membrane |
| CN103846012B (en) * | 2012-12-04 | 2016-06-15 | 中国科学院大连化学物理研究所 | A kind of preparation method of porous diffusion barrier |
| CN105771703A (en) * | 2016-03-15 | 2016-07-20 | 北京工业大学 | Preparation method of polyethersulfone-based composite positive permeable membrane |
| CN105771703B (en) * | 2016-03-15 | 2018-03-30 | 北京工业大学 | A kind of preparation method of the compound forward osmosis membrane of polyethers sulfuryl |
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Open date: 20090916 |