CN103566773B - Doughnut membrane preparation method, hollow-fibre membrane and cosolvent compositions - Google Patents
Doughnut membrane preparation method, hollow-fibre membrane and cosolvent compositions Download PDFInfo
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Abstract
The present invention is about a kind of polysulfones or the preparation method of polyether sulphone hollow fibre film, cosolvent compositions and polysulfones or polyether sulphone hollow fibre film.This preparation method, by polysulfones or polyether sulfone, cosolvent compositions and non-solvent, is prepared as homogenizing preparation liquid；This preparation liquid and core liquid, together by cannula type shower nozzle, enter in cooling bath, compound phase isolated polysulfones or polyether sulphone hollow fibre film occur；Cosolvent compositions in removing hollow-fibre membrane and non-solvent, prepare hollow-fibre membrane.Described cosolvent compositions is gamma butyrolactone, with one or more mixture in ε caprolactone, ε caprolactam, triethyl phosphate and tetramethylurea.This hollow-fibre membrane has high intensity, high separation accuracy and high flux and the chemical-resistance of excellence.
Description
Technical field
The present invention relates to a kind of hollow-fibre membrane and preparation method, particularly relate to a kind of polysulfones or polyethers
Sulfone hollow-fibre membrane and preparation method, this hollow-fibre membrane has high intensity, high separation accuracy and high pass
Amount and the chemical-resistance of excellence.
Background technology
Membrane separation technique is widely used in chemical industry, food, medicine, city have stable political situation the fields such as electronics.
The polymeric material of main masking has that cellulose acetate, polypropylene be fine, polrvinyl chloride, polysulfones,
Kynoar and polyether sulfone etc..
Film-forming method has fusion drawn method, sintering process, phase separation method and thermally induced phase separation,
The most topmost film-forming method is that non-solvent causes phase separation method and thermally induced phase separation.
Water process separate in film application process the Membrane cleaning that relates to may the bigger current scour of needs and
Use acid, alkali, oxidant or surfactant, need film itself have preferable mechanical performance,
Chemical resistance and oxidative resistance.Mechanical performance, chemical resistance and the oxidative resistance generally acknowledged at present are excellent
Different polymeric film material has Kynoar, polysulfones and polyether sulfone etc..Kynoar is dredged due to it
Aqueous, is susceptible to fouling membrane, simultaneously containing fluorine element in membrane material, scraps process by burning etc.
Difficulty is the biggest.
Polysulfones, polyether sulfone combination property are good, and mechanical performance is excellent, use continuously and temperature under high temperature
Using in environment jumpy and remain in that stability, chemical-resistance is good, especially under high temperature
Alkaline resistance properties is excellent.Its doughnut film-strength is high, film silk not easy fracture.And its molecular structure is certainly
Determine membrane rigidity good, pressure excellent performance.
Polysulfones, polyether sulphone hollow fibre film commonly used phase separation method is prepared, in preparation liquid
Add larger proportion solvent, inside made hollow-fibre membrane, there is big finger-like pore structure, dense layer surface
Partially thick, it is impossible to obtain narrow ditribution pore structure, cause film-strength, water flux and crushing resistance the most on the low side.And
Spherical particle structure causes film mechanical performance and chemical-resistance to reduce.
Compound phase partition method combines both phase separation method and thermally induced phase separation advantage.Will
A certain proportion of polymer, mixed solvent (potentially including solvent, cosolvent, non-solvent) and/or add
Add agent and be configured to preparation liquid, after deaeration, enter solidification cooling bath moment, nascent state hymeniderm with certain form
Layer solvent and non-solvent generation mass transfer exchange in coagulating bath, therefore cortex generation phase separation method becomes
Film；Further mass transfer and heat transfer rate is hindered than biography afterwards due to the formation of surface compact cortex
Matter speed is fast, during so phase separation is not able to do in time to develop with inner direction to top layer, internal
Due to heat transfer generation Thermal inactive, liquid liquid phase separation is caused to form inierpeneirating network structure.
Summary of the invention
The deficiency existed in view of above-mentioned problem of the prior art, present invention aim at providing a kind of employing
Chemical-resistance, satisfactory mechanical property polymeric material by compound phase separation method prepare high intensity,
High separation accuracy and the preparation method of high-throughout hollow-fibre membrane.
To achieve these goals, a kind of polysulfones proposed according to the present invention or polyether sulphone hollow fibre film
Preparation method, it comprises the following steps:
Step 1: by the polysulfones of 15-30wt% or polyether sulfone, the cosolvent compositions of 50-75wt% and
The non-solvent of 10-20wt% adds in stirred tank, and stirring and dissolving at a temperature of 120-150 DEG C, during stirring
Between be 18-36 hour, vacuum defoamation 6-12 hour the most at such a temperature, be prepared as homogenizing preparation liquid；
Step 2: by the preparation liquid in step 1, with core liquid together by cannula type shower nozzle, through height
For the air section of 10-25cm, enter in cooling bath, compound phase isolated polysulfones or polyether sulfone occur
Hollow-fibre membrane；
Step 3: the cosolvent compositions in the hollow-fibre membrane that removing above-mentioned steps 2 obtains and non-solvent.
Aforesaid preparation method, wherein cosolvent compositions is gamma-butyrolacton, with 6-caprolactone, ε-own interior
The mixture of one or more in amide, triethyl phosphate and tetramethylurea.Preferably gamma-butyrolacton, with ε-
Caprolactone and/or the mixture of epsilon-caprolactams.
Aforesaid preparation method, wherein gamma-butyrolacton in cosolvent compositions, with 6-caprolactone, ε-own interior
In amide, triethyl phosphate and tetramethylurea, the ratio of one or more is 1/3～3/1.
Aforesaid preparation method, wherein non-solvent be glycerol, ethylene glycol, diethylene glycol, tetraethylene glycol (TEG) or
Polyethylene Glycol；Preferably glycerol or diethylene glycol.
Aforesaid preparation method, its SMIS liquid is by 60-100% deionized water, 0-20% cosolvent and 0-20%
Non-solvent forms；Preferably by 60-80% deionized water, 10-20% cosolvent and 10-20% non-solvent group
Become.
Aforesaid preparation method, wherein cooling bath by 40-100% deionized water, 0-30% cosolvent and
0-30% non-solvent forms；Preferably non-molten by 40-60% deionized water, 20-30% cosolvent and 20-30%
Agent forms.Chilling temperature 0-60 DEG C, preferably 10-30 DEG C.
Aforesaid preparation method, wherein step 3 is real by being immersed in extractant by described hollow-fibre membrane
Existing, wherein said extractant is made up of 40-100% deionized water and 0-60% cosolvent, and temperature is
20-80 DEG C, extraction time is 12-36 hour.Be preferably, extractant by 60-80% deionized water and
20-40% cosolvent forms, and temperature is 40-60 DEG C, and extraction time is 24 hours.
Aforesaid preparation method, wherein said removing mode is multistep or step extraction.Multistep extracts
Refer to that in extract, solvent is gradually reduced to 0% by 40%.
If no special instructions, in the present invention, all proportions about content of material is all weight percentage.
Another object of the present invention is to provide a kind of hollow-fibre membrane so that it is there is high-chemical-resistance.
To achieve these goals, a kind of polysulfones proposed according to the present invention or polyether sulphone hollow fibre film,
It is 50 DEG C, the sodium hypochlorite of 5000ppm effective chlorine and 2wt% hydrogen-oxygen that this hollow-fibre membrane is put into temperature
Changing in sodium water solution seven days, the tensile strength retention of this hollow-fibre membrane is 85-95%.
Aforesaid hollow-fibre membrane, wherein said hollow-fibre membrane section presents co-continuous spongy body knot
Structure, porosity 65-80%, pure water flux is 300-1500L/m2H bar 25 DEG C, average pore size is
0.01-0.15 μm, tensile strength 4.0-6.5N/mm2, elongation percentage is 50%-200%, internal diameter is
0.60-1.50, comprcssive strength 0.6-1.0MPa.
It is still another object of the present invention to provide a kind of preparation method being applicable to aforesaid hollow-fibre membrane
Cosolvent compositions.
To achieve these goals, a kind of cosolvent compositions proposed according to the present invention, said composition
For a kind of or many in gamma-butyrolacton, with 6-caprolactone, epsilon-caprolactams, triethyl phosphate and tetramethylurea
The mixture planted.Gamma-butyrolacton, with 6-caprolactone, epsilon-caprolactams, triethyl phosphate and tetramethylurea
In one or more ratio be 1:3～3:1.Be preferably, gamma-butyrolacton, with 6-caprolactone and/or ε-
The mixture of caprolactam.
It is still another object of the present invention to provide a kind of core liquid comprising above-mentioned cosolvent compositions.
The present invention compared with prior art has clear advantage and beneficial effect.By above-mentioned technical side
Case, the hollow that the method according to the invention uses above-mentioned composite thermotropic phase separation method preparation technology to obtain is fine
Dimension film has high intensity, high separation accuracy and high flux and the chemical-resistance of excellence.By this hollow
Fibrous membrane puts into 5000ppm(effective chlorine) in sodium hypochlorite+2wt% sodium hydrate aqueous solution, in 50 DEG C
Processing 7 days, its tensile strength retention is up to 85-95%.
Accompanying drawing explanation
Fig. 1 is comparative example 1 section electromicroscopic photograph, and section is it can clearly be seen that finger-like pore structure.
Fig. 2 is comparative example 1 section electromicroscopic photograph, and section is it can clearly be seen that spherical particle structure.
Fig. 3 is comparative example 2 section electromicroscopic photograph, and section is it can clearly be seen that finger-like macroporous structure.
Fig. 4 is embodiment 1 section electromicroscopic photograph, and whole film section presents cavernous structure.
Fig. 5 is that embodiment 1 is near outer surface cross-section photographs.
Fig. 6 is that embodiment 1 is near inner surface cross-section photographs.
Fig. 7 is embodiment 1 section enlarged photograph, it can be seen that film section spongy body presents co-continuous knot
Structure.
Detailed description of the invention
By technological means and effect that the present invention by reach predetermined goal of the invention taked is expanded on further,
Below in conjunction with accompanying drawing and preferred embodiment, to the hollow-fibre membrane proposed according to the present invention and preparation method
Detailed description of the invention, step is described in detail.
Embodiment 1
By dry the polyether sulfone of 20wt%, the gamma-butyrolacton of 65wt% and epsilon-caprolactams mixing cosolvent,
15wt% glycerol non-solvent joins in stirred tank, wherein cosolvent gamma-butyrolacton: epsilon-caprolactams
=3/1。
Thing mixed above is at a temperature of 120 DEG C, to stir 18 hours under the conditions of rotating speed 100 revs/min,
Vacuum defoamation 12 hours at a temperature of 120 DEG C, obtain homogenizing preparation liquid.
Preparation liquid 120 DEG C is kept to enter cannula type spinning head, with shower nozzle center after passing through 250 mesh drainage screens
Core liquid in pipe sprays together.Core liquid is by 60wt% deionized water, 25wt% gamma-butyrolacton and 15wt% third
Triol forms.Ejection preparation liquid through 10cm air section, enter in 10 DEG C of cooling baths, cooling bath by
40wt% deionized water, 30wt% gamma-butyrolacton and 30wt% glycerol composition, spinning speed 15m/min,
Prepare in the solution of polyether sulphone hollow fibre film 60 DEG C of 60% pure water of immersion and 40% gamma-butyrolacton composition and extract
Process 36 hours, obtain composite thermotropic phase separation method polyether sulphone hollow fibre film.
Gained composite thermotropic phase polyether sulphone hollow fibre film performance is as follows:
Internal-and external diameter is 0.8 millimeter/1.4 millimeters, and porosity is 70%, and pure water flux is
720L/m2H bar 25 DEG C, inner surface average pore size is 0.03 μm, and tensile strength is 5.0N/mm2, prolong
The rate of stretching is 89%, comprcssive strength 0.70Mpa.
This hollow-fibre membrane is put into 5000ppm(effective chlorine) sodium hypochlorite+2wt% sodium hydroxide is water-soluble
In liquid, processing 7 days in 50 DEG C ± 2 DEG C, its tensile strength is 4.7N/mm2, tensile strength retention is
94.0%, illustrate that the chemical-resistance of this hollow-fibre membrane is fine.
As shown in Figures 4 to 7, be respectively the hollow-fibre membrane that embodiment 1 prepares section electromicroscopic photograph,
During the prepared close outer surface section electromicroscopic photograph of hollow-fibre membrane of embodiment 1, embodiment 1 prepare
The section of the hollow-fibre membrane that the close inner surface section electromicroscopic photograph of hollow fiber film and embodiment 1 prepare
Partial enlargement electromicroscopic photograph.The whole film section of the hollow-fibre membrane that embodiment 1 prepares presents spongy body 30
Structure, this cavernous structure presents co-continuous 40 structure.
Embodiment 2
By dry the polyether sulfone of 21wt%, the gamma-butyrolacton of 65wt% and epsilon-caprolactams mixing cosolvent,
14wt% ethylene glycol non-solvent joins in stirred tank, wherein cosolvent gamma-butyrolacton: epsilon-caprolactams
=1/3。
Thing mixed above is at a temperature of 150 DEG C, to stir 36 hours under the conditions of rotating speed 100 revs/min,
Vacuum defoamation 6 hours at a temperature of 150 DEG C, obtain homogenizing preparation liquid.
Preparation liquid 150 DEG C is kept to enter cannula type spinning head, with shower nozzle center after passing through 250 mesh drainage screens
Core liquid in pipe sprays together.Core liquid is by 80wt% deionized water, 10wt% gamma-butyrolacton and 10wt% second
Glycol forms.Ejection preparation liquid through 15cm air section, enter in 25 DEG C of cooling baths, cooling bath by
60wt% deionized water, 20wt% gamma-butyrolacton and 20wt% ethylene glycol composition, spinning speed 15m/min,
Prepare in the solution of polyether sulphone hollow fibre film 40 DEG C of 80% pure water of immersion and 20% gamma-butyrolacton composition and extract
Process 24 hours, obtain composite thermotropic phase separation method polyether sulphone hollow fibre film.
Gained composite thermotropic phase polyether sulphone hollow fibre film performance is as follows:
Internal-and external diameter is 0.6 millimeter/1.2 millimeters, and porosity is 74%, and pure water flux is
680L/m2H bar 25 DEG C, inner surface average pore size is 0.04 μm, and tensile strength is 5.2N/mm2, prolong
The rate of stretching is 120%, comprcssive strength 0.82Mpa.
This hollow-fibre membrane is put into 5000ppm(effective chlorine) sodium hypochlorite+2wt% sodium hydroxide is water-soluble
In liquid, processing 7 days in 50 DEG C ± 2 DEG C, its tensile strength is 4.9N/mm2, tensile strength retention is
94.2%。
Embodiment 3
The polysulfones of 30wt%, the gamma-butyrolacton of 57wt% and the epsilon-caprolactams mixing cosolvent that will dry,
13wt% tetraethylene glycol (TEG) non-solvent joins in stirred tank, wherein cosolvent gamma-butyrolacton: epsilon-caprolactams
=1/1。
Thing mixed above is at a temperature of 130 DEG C, to stir 24 hours under the conditions of rotating speed 100 revs/min,
Vacuum defoamation 8 hours at a temperature of 130 DEG C, obtain homogenizing preparation liquid.
Preparation liquid 130 DEG C is kept to enter cannula type spinning head, with shower nozzle center after passing through 250 mesh drainage screens
Core liquid in pipe sprays together.Core liquid is by 60wt% deionized water, 20wt% gamma-butyrolacton and 20wt% tetra-
Glycol forms.Ejection preparation liquid through 20cm air section, enter in 15 DEG C of cooling baths, cooling bath by
50wt% deionized water, 25wt% gamma-butyrolacton and 25wt% tetraethylene glycol (TEG) composition, spinning speed 15m/min,
Prepare polyether sulphone hollow fibre film and immerse extraction process 12 hours in 20 DEG C of pure water, obtain composite thermotropic phase
Partition method ps hollow fiber uf membrane.
Gained composite thermotropic phase ps hollow fiber uf membrane performance is as follows:
Internal-and external diameter is 1.0 millimeters/1.6 millimeters, and porosity is 65%, and pure water flux is
420L/m2H bar 25 DEG C, inner surface average pore size is 0.015 μm, and tensile strength is 6.5N/mm2,
Elongation percentage is 200%, comprcssive strength 1.0Mpa.
This hollow-fibre membrane is put into 5000ppm(effective chlorine) sodium hypochlorite+2wt% sodium hydroxide is water-soluble
In liquid, processing 7 days in 50 DEG C ± 2 DEG C, its tensile strength is 6.2N/mm2, tensile strength retention is
95.4%。
Embodiment 4
By dry the polyether sulfone of 15wt%, the gamma-butyrolacton of 71wt% and epsilon-caprolactams mixing cosolvent,
14wt% glycerol non-solvent joins in stirred tank, wherein cosolvent gamma-butyrolacton: epsilon-caprolactams
=1/2。
Thing mixed above is at a temperature of 140 DEG C, to stir 28 hours under the conditions of rotating speed 100 revs/min,
Vacuum defoamation 8 hours at a temperature of 140 DEG C, obtain homogenizing preparation liquid.
Preparation liquid 140 DEG C is kept to enter cannula type spinning head, with shower nozzle center after passing through 250 mesh drainage screens
Core liquid in pipe sprays together.Core liquid is by 70wt% deionized water, 20wt% gamma-butyrolacton and 10wt% third
Triol forms.Ejection preparation liquid through 25cm air section, enter in 30 DEG C of cooling baths, cooling bath by
60wt% deionized water, 25wt% gamma-butyrolacton and 15wt% glycerol composition, spinning speed 15m/min,
Prepare in the solution of polyether sulphone hollow fibre film 80 DEG C of 40% pure water of immersion and 60% gamma-butyrolacton composition and extract
Process 12 hours, then immerse extraction process 18 in the solution of 40 DEG C of 60% pure water and 40% gamma-butyrolacton composition
Hour, obtain composite thermotropic phase separation method polyether sulphone hollow fibre film.
Gained composite thermotropic phase polyether sulphone hollow fibre film performance is as follows:
Internal-and external diameter is 1.5 millimeters/2.1 millimeters, and porosity is 80%, and pure water flux is
1490L/m2H bar 25 DEG C, inner surface average pore size is 0.15 μm, and tensile strength is 4.3N/mm2,
Elongation percentage is 52%, comprcssive strength 0.6Mpa.
This hollow-fibre membrane is put into 5000ppm(effective chlorine) sodium hypochlorite+2wt% sodium hydroxide is water-soluble
In liquid, processing 7 days in 50 DEG C ± 2 DEG C, its tensile strength is 4.0N/mm2, tensile strength retention is
93.0%。
Embodiment 5
In addition to core liquid and cooling bath all use pure water, other is same as in Example 1.
Gained composite thermotropic phase polyether sulphone hollow fibre film performance is as follows:
Internal-and external diameter is 1.2 millimeters/1.8 millimeters, and porosity is 68%, and pure water flux is
320L/m2H bar 25 DEG C, inner surface average pore size is 0.01 μm, and tensile strength is 5.8N/mm2, prolong
The rate of stretching is 140%, and comprcssive strength is more than 0.85Mpa.
This hollow-fibre membrane is put into 5000(effective chlorine) ppm sodium hypochlorite+2wt% sodium hydroxide is water-soluble
In liquid, processing 7 days in 50 DEG C ± 2 DEG C, its tensile strength is 5.3N/mm2, tensile strength retention is
91.4%。
Embodiment 6
By dry the polyether sulfone of 20wt%, the gamma-butyrolacton of 65wt% and 6-caprolactone mixing cosolvent,
15wt% glycerol non-solvent joins in stirred tank, wherein cosolvent gamma-butyrolacton: 6-caprolactone=2/1.
Thing mixed above is at a temperature of 130 DEG C, to stir 24 hours under the conditions of rotating speed 100 revs/min,
Vacuum defoamation 8 hours at a temperature of 130 DEG C, obtain homogenizing preparation liquid.
Preparation liquid 130 DEG C is kept to enter cannula type spinning head, with shower nozzle center after passing through 250 mesh drainage screens
Core liquid in pipe sprays together.Core liquid is by 60wt% deionized water, 20wt% gamma-butyrolacton and 20wt% third
Triol forms.Ejection preparation liquid through 15cm air section, enter in 20 DEG C of cooling baths, cooling bath by
40wt% deionized water, 30wt% gamma-butyrolacton and 30wt% glycerol composition, spinning speed 15m/min,
Prepare in the solution of polyether sulphone hollow fibre film 60 DEG C of 80% pure water of immersion and 20% gamma-butyrolacton composition and extract
Process 20 hours, obtain composite thermotropic phase separation method polyether sulphone hollow fibre film.
Gained composite thermotropic phase polyether sulphone hollow fibre film performance is as follows:
Internal-and external diameter is 0.9 millimeter/1.5 millimeters, and porosity is 71%, and pure water flux is
740L/m2H bar 25 DEG C, inner surface average pore size is 0.03 μm, and tensile strength is 5.2N/mm2, prolong
The rate of stretching is 97%, comprcssive strength 0.74Mpa.
This hollow-fibre membrane is put into 5000ppm(effective chlorine) sodium hypochlorite+2wt% sodium hydroxide is water-soluble
In liquid, processing 7 days in 50 DEG C ± 2 DEG C, its tensile strength is 4.8N/mm2, tensile strength retention is
92.3%, illustrate that the chemical-resistance of this hollow-fibre membrane is fine.
Embodiment 7
By dry the polyether sulfone of 21wt%, the gamma-butyrolacton of 66wt% and tetramethylurea mixing cosolvent,
13wt% glycerol non-solvent joins in stirred tank, wherein cosolvent gamma-butyrolacton: tetramethylurea=1:
1。
Thing mixed above is at a temperature of 120 DEG C, to stir 18 hours under the conditions of rotating speed 100 revs/min,
Vacuum defoamation 12 hours at a temperature of 120 DEG C, obtain homogenizing preparation liquid.
Preparation liquid 120 DEG C is kept to enter cannula type spinning head, with shower nozzle center after passing through 250 mesh drainage screens
Core liquid in pipe sprays together.Core liquid is by 60wt% deionized water, 30wt% gamma-butyrolacton and 10wt% third
Triol forms.Ejection preparation liquid through 15cm air section, enter in 25 DEG C of cooling baths, cooling bath by
60wt% deionized water, 20wt% gamma-butyrolacton and 20wt% glycerol composition, spinning speed 15m/min,
Prepare in the solution of polyether sulphone hollow fibre film 50 DEG C of 80% pure water of immersion and 20% gamma-butyrolacton composition and extract
Process 24 hours, obtain composite thermotropic phase separation method polyether sulphone hollow fibre film.
Gained composite thermotropic phase polyether sulphone hollow fibre film performance is as follows:
Internal-and external diameter is 0.8 millimeter/1.4 millimeters, and porosity is 70%, and pure water flux is 620L/m2·h·bar·25
DEG C, inner surface average pore size is 0.025 μm, and tensile strength is 5.6N/mm2, elongation percentage is 112%,
Comprcssive strength 0.76Mpa.
This hollow-fibre membrane is put into 5000ppm(effective chlorine) sodium hypochlorite+2wt% sodium hydroxide is water-soluble
In liquid, processing 7 days in 50 DEG C ± 2 DEG C, its tensile strength is 5.2N/mm2, tensile strength retention is
92.8%, illustrate that the chemical-resistance of this hollow-fibre membrane is fine.
Comparative example 1
In addition to cosolvent uses gamma-butyrolacton, remaining is identical with enforcement 1.
The polyether sulphone hollow fibre film performance of gained is as follows:
Internal-and external diameter is 0.8 millimeter/1.4 millimeters, and porosity is 62%, and pure water flux is
230L/m2H bar 25 DEG C, inner surface average pore size is 0.05 μm, and tensile strength is 3.6N/mm2, prolong
The rate of stretching is 62%, comprcssive strength 0.56Mpa.
This hollow-fibre membrane is put into 5000ppm(effective chlorine) sodium hypochlorite+2wt% sodium hydroxide is water-soluble
In liquid, processing 7 days in 50 DEG C ± 2 DEG C, its tensile strength is 1.3N/mm2, tensile strength retention is only
It is 36.1%.
As shown in Figure 1 and Figure 2, it is that the section Electronic Speculum of the polyether sulphone hollow fibre film that comparative example 1 prepares is shone
Sheet.Polyether sulphone hollow fibre film section that comparative example 1 prepares is it can clearly be seen that finger-like pore structure 10 He
Spherical particle structure 20.
Comparative example 2
(the most existing commonly using prepares polyether sulphone hollow fibre film to use tradition phase separation preparation method
Technology), by dry the polyether sulfone of 19wt%, the N,N-dimethylacetamide solvent of 68wt%,
13wt%PEG-600 non-solvent joins in stirred tank.
Thing mixed above is at a temperature of 50 DEG C, to stir 24 hours under the conditions of rotating speed 100 revs/min,
Vacuum defoamation 8 hours at a temperature of 50 DEG C, obtain homogenizing preparation liquid.
Preparation liquid 50 DEG C is kept to enter cannula type spinning head, with shower nozzle central canal after passing through 250 mesh drainage screens
Interior core liquid sprays together.Core liquid is by 70wt% deionized water and 30wt%N, N-dimethyl acetylamide group
Become.The preparation liquid of ejection, through 15cm air section, enters cooling bath, and cooling bath is by 50wt% deionization
Water and 50wt%N, N-dimethyl acetylamide forms, spinning speed 15m/min, obtains non-solvent and causes to divide mutually
From method polyether sulphone hollow fibre film.
Gained phase separation method polyether sulphone hollow fibre film performance is as follows:
Internal-and external diameter is 0.8 millimeter/1.4 millimeters, and porosity is 51%, and pure water flux is
210L/m2H bar 25 DEG C, inner surface average pore size is 0.025 μm, tensile strength 3.0N/mm2, prolong
The rate of stretching is 35%, comprcssive strength 0.52Mpa.
This hollow-fibre membrane is put into 5000ppm(effective chlorine) sodium hypochlorite+2wt% sodium hydroxide is water-soluble
In liquid, processing 7 days in 50 DEG C ± 2 DEG C, its tensile strength is more than 2.2N/mm2, tensile strength retention is
73.3%。
As it is shown on figure 3, be the section electromicroscopic photograph of the polyether sulphone hollow fibre film that comparative example 2 prepares.
The section of the polyether sulphone hollow fibre film that comparative example 2 prepares is it can clearly be seen that finger-like macroporous structure 10.
Although the present invention is disclosed above with preferred embodiment, so it is not limited to what the present invention implemented
Scope, the simple equivalence made according to claims of the present invention and description changes and modifies,
Still fall within the range of technical solution of the present invention.
Claims (11)
1. a polysulfones or the preparation method of polyether sulphone hollow fibre film, it is characterised in that include walking as follows
Rapid:
Step 1: by the polysulfones of 15-30wt% or polyether sulfone, the cosolvent compositions of 50-75wt% and
The non-solvent of 10-20wt% stirring and dissolving at a temperature of 120-150 DEG C, vacuum takes off the most at such a temperature
Steep 6-12 hour, be prepared as homogenizing preparation liquid；
Step 2: by the preparation liquid in step 1 with core liquid together by cannula type shower nozzle, through height be
The air section of 10-25cm, enters in cooling bath, compound phase isolated polysulfones or polyether sulfone hollow occurs
Fibrous membrane；With
Step 3: the cosolvent compositions in the hollow-fibre membrane that removing step 2 obtains and non-solvent；
Wherein, described cosolvent compositions is gamma-butyrolacton, with 6-caprolactone, ε-own interior acyl
The mixture of one or more in amine, triethyl phosphate and tetramethylurea.
2. preparation method as claimed in claim 1, it is characterised in that wherein said cosolvent combination
Thing is the mixture of at least one in gamma-butyrolacton, with 6-caprolactone and epsilon-caprolactams.
3. preparation method as claimed in claim 1, it is characterised in that wherein said cosolvent combination
Thing, in gamma-butyrolacton, with 6-caprolactone, epsilon-caprolactams, triethyl phosphate and tetramethylurea one
Plant or multiple weight ratio is 1:3-3:1.
4. preparation method as claimed in claim 1, it is characterised in that wherein said non-solvent is third
Triol, ethylene glycol, diethylene glycol, tetraethylene glycol (TEG) or Polyethylene Glycol.
5. preparation method as claimed in claim 4, it is characterised in that wherein said non-solvent is third
Triol or diethylene glycol.
6. preparation method as claimed in claim 1, it is characterised in that wherein said core liquid by
60-100% deionized water, 0-20% cosolvent and 0-20% non-solvent composition.
7. preparation method as claimed in claim 1, it is characterised in that wherein said cooling bath by
40-100% deionized water, 0-30% cosolvent and 0-30% non-solvent composition, chilling temperature is 0-60 DEG C.
8. preparation method as claimed in claim 7, it is characterised in that wherein said cooling bath by
40-60% deionized water, 20-30% cosolvent and 20-30% non-solvent composition, chilling temperature is 10-30 DEG C.
9. preparation method as claimed in claim 1, it is characterised in that step 3 is by by described hollow
Fibrous membrane immerses in extractant and realizes, and wherein said extractant is by 40-100% deionized water and 0-60%
Cosolvent forms, and temperature is 20-80 DEG C, and extraction time is 12-36 hour.
10. preparation method as claimed in claim 9, it is characterised in that wherein said extractant by
60-80% deionized water and 20-40% cosolvent composition, temperature is 40-60 DEG C, and extraction time is 24 little
Time.
11. preparation methoies as described in claim 1,9 or 10, it is characterised in that wherein said
Removing mode is multistep or step extraction.
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| EP4389264A1 (en) * | 2022-12-23 | 2024-06-26 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Polymer casting solution for ultrafiltration membranes |
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| CN105854650A (en) * | 2016-06-17 | 2016-08-17 | 安庆市天虹新型材料科技有限公司 | Anti-fouling high-throughput polysulfone composite membrane |
| CN115475536A (en) * | 2022-09-30 | 2022-12-16 | 浙江工业大学 | Preparation method of permanent hydrophilic polyether sulfone hollow fiber membrane with gradient structure |
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| JP2009095812A (en) * | 2007-10-19 | 2009-05-07 | Kawasaki Heavy Ind Ltd | Separation membrane consisting of polyethersulfone, method for manufacturing the same, and undiluted solution of deposition |
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| US6218441B1 (en) * | 1997-09-18 | 2001-04-17 | Timothy B. Meluch | Melt-spun polysulfone semipermeable membranes and methods for making the same |
| US8827086B2 (en) * | 2006-05-06 | 2014-09-09 | Membrana Gmbh | Ultrafiltration membrane |
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| JP2009095812A (en) * | 2007-10-19 | 2009-05-07 | Kawasaki Heavy Ind Ltd | Separation membrane consisting of polyethersulfone, method for manufacturing the same, and undiluted solution of deposition |
| CN101396641A (en) * | 2008-10-31 | 2009-04-01 | 孟广祯 | Composite thermotropic phase separation film-making method |
| CN102202772A (en) * | 2008-11-03 | 2011-09-28 | 泽农科技合股公司 | Filtration membrane with tubular support |
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| EP4389264A1 (en) * | 2022-12-23 | 2024-06-26 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Polymer casting solution for ultrafiltration membranes |
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