CN103566773A - Preparation method of hollow fibrous membrane, hollow fibrous membrane, and latent solvent composition - Google Patents
Preparation method of hollow fibrous membrane, hollow fibrous membrane, and latent solvent composition Download PDFInfo
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- CN103566773A CN103566773A CN201310297902.1A CN201310297902A CN103566773A CN 103566773 A CN103566773 A CN 103566773A CN 201310297902 A CN201310297902 A CN 201310297902A CN 103566773 A CN103566773 A CN 103566773A
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Abstract
The invention relates to a preparation method of a polysulfone or polyether sulfone hollow fibrous membrane, a latent solvent composition and the polysulfone or polyether sulfone hollow fibrous membrane. The preparation method comprises the following steps: preparing the polysulfone or polyether sulfone, the latent solvent composition and a non-solvent into a homogenous film-forming solution; introducing the film-forming solution together with a core solution into a cooling bath through an intubation-tube sprayer, separating composite phase to obtain a polysulfone or polyether sulfone hollow fibrous membrane; removing the latent solvent composition or non-solvent from the hollow fibrous membrane, thus obtaining the hollow fibrous membrane. The latent solvent composition is one or mixture of more selected from gamma-butyrolactone, epsilon-caprolactone, epsilon-hexanolactam, triethyl phosphate and tetramethylurea. The hollow fibrous membrane has high density, high separation precision, high flux and excellent chemical resistance.
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 polyether sulphone hollow fibre film and preparation method, this hollow-fibre membrane has high strength, high separation accuracy and high flux and excellent chemical-resistance.
Background technology
Membrane separation technique is widely used in chemical industry, food, medicine, the city fields such as electronics of having stable political situation.
The polymeric material of main masking has that cellulose acetate, polypropylene are fine, polyvinyl chloride, polysulfones, Kynoar and polyether sulfone etc.
Film-forming method has fusion drawn method, sintering process, phase separation method and thermally induced phase separation, and wherein topmost film-forming method is that non-solvent causes phase separation method and thermally induced phase separation.
The film relating in water treatment diffusion barrier application process cleans may be needed larger current scour and use acid, alkali, oxidant or surfactant, needs film itself to have good mechanical performance, chemical resistance and oxidative resistance.The polymeric film material of at present generally acknowledged mechanical performance, chemical resistance and oxidative resistance excellence has Kynoar, polysulfones and polyether sulfone etc.Kynoar is due to its hydrophobicity, film easily occurs and pollute, and contains fluorine element in membrane material simultaneously, waits that to scrap intractability very large by burning.
Polysulfones, polyether sulfone combination property are good, and mechanical performance is excellent, under high temperature, use continuously and temperature environment jumpy in use and still keep stability, chemical-resistance is good, especially alkaline resistance properties excellence under high temperature.Its doughnut film-strength is high, and film silk is easy fracture not.And its molecular structure determines that membrane rigidity is good, withstand voltage properties excellence.
Polysulfones, polyether sulphone hollow fibre film generally adopt phase separation legal system standby, in preparation liquid, add larger proportion solvent, there is large finger-like pore structure in made hollow-fibre membrane inside, dense layer surface is partially thick, cannot obtain narrow distribution hole structure, cause film-strength, water flux and crushing resistance all on the low side.And spherical particle structure causes film mechanical performance and chemical-resistance to reduce.
Compound phase partition method combines phase separation method and the two advantage of thermally induced phase separation.A certain proportion of polymer, mixed solvent (may comprise solvent, cosolvent, non-solvent) and/or additive are configured to preparation liquid, after deaeration, with certain form, enter and solidify cooling bath moment, non-solvent generation mass transfer exchange in nascent state hymeniderm layer solvent and coagulating bath, therefore cortex generation phase separation method film forming; Afterwards because the formation of surface compact cortex has hindered further mass transfer and heat transfer rate is faster than mass transfer velocity, when so phase separation is not also able to do in time to top layer with inner future development, inner because heat transmission generation thermic is separated, initiation solution liquid phase separation forms inierpeneirating network structure.
Summary of the invention
In view of the deficiency that the problem of above-mentioned prior art exists, the object of the invention is to provide a kind of polymeric material of chemical-resistance, satisfactory mechanical property that adopts by compound phase separation method, to prepare the preparation method of high strength, high separation accuracy and high-throughout hollow-fibre membrane.
To achieve these goals, a kind of polysulfones proposing according to the present invention or the preparation method of polyether sulphone hollow fibre film, it comprises the following steps:
Step 1: the polysulfones of 15-30wt% or polyether sulfone, the cosolvent composition of 50-75wt% and the non-solvent of 10-20wt% are added in stirred tank, stirring and dissolving at the temperature of 120-150 ℃, mixing time is 18-36 hour, then vacuum defoamation 6-12 hour at this temperature, is prepared into homogeneous preparation liquid;
Step 2: by the preparation liquid in step 1,,, enter in cooling bath through being highly the air section of 10-25cm together by cannula type shower nozzle with core liquid, compound phase separation occurs and obtain polysulfones or polyether sulphone hollow fibre film;
Step 3: remove cosolvent composition and non-solvent in the hollow-fibre membrane that above-mentioned steps 2 obtains.
Aforesaid preparation method, wherein cosolvent composition is gamma-butyrolacton, with one or more mixture in 6-caprolactone, epsilon-caprolactams, triethyl phosphate and tetramethylurea.Preferred gamma-butyrolacton, with the mixture of 6-caprolactone and/or epsilon-caprolactams.
Aforesaid preparation method, gamma-butyrolacton in cosolvent composition wherein, with one or more ratio in 6-caprolactone, epsilon-caprolactams, triethyl phosphate and tetramethylurea be 1/3～3/1.
Aforesaid preparation method, wherein non-solvent is glycerine, ethylene glycol, diethylene glycol (DEG), tetraethylene glycol or polyethylene glycol; Preferred glycerine or diethylene glycol (DEG).
Aforesaid preparation method, its SMIS liquid is comprised of 60-100% deionized water, 0-20% cosolvent and 0-20% non-solvent; Preferably by 60-80% deionized water, 10-20% cosolvent and 10-20% non-solvent, formed.
Aforesaid preparation method, wherein cooling bath is comprised of 40-100% deionized water, 0-30% cosolvent and 0-30% non-solvent; Preferably by 40-60% deionized water, 20-30% cosolvent and 20-30% non-solvent, formed.Chilling temperature 0-60 ℃, preferably 10-30 ℃.
Aforesaid preparation method, wherein step 3 is by immersing described hollow-fibre membrane in extractant and realize, and wherein said extractant is comprised of 40-100% deionized water and 0-60% cosolvent, and temperature is 20-80 ℃, and extraction time is 12-36 hour.Be preferably, extractant is comprised of 60-80% deionized water and 20-40% cosolvent, and temperature is 40-60 ℃, and extraction time is 24 hours.
Aforesaid preparation method, the wherein said mode that removes is multistep or step extraction.Multistep extraction refers to that in extract, solvent reduces to 0% by 40% gradually.
If no special instructions, in the present invention, all proportions of its related substances is all weight percentage.
Another object of the present invention is to provide a kind of hollow-fibre membrane, make it have high-chemical-resistance.
To achieve these goals, a kind of polysulfones or the polyether sulphone hollow fibre film that according to the present invention, propose, it is 50 ℃, the clorox of 5000ppm effective chlorine and 2wt% sodium hydrate aqueous solution seven days that this hollow-fibre membrane is put into temperature, and the tensile strength conservation rate of this hollow-fibre membrane is 85-95%.
Aforesaid hollow-fibre membrane, wherein said hollow-fibre membrane section presents co-continuous cavernous structure, porosity 65-80%, pure water flux is 300-1500L/m
2hbar25 ℃, average pore size is 0.01-0.15 μ m, tensile strength 4.0-6.5N/mm
2, percentage elongation is 50%-200%,, internal diameter is 0.60-1.50 ㎜, compression strength 0.6-1.0MPa.
A further object of the present invention is to provide a kind of cosolvent composition that is applicable to the preparation method of aforesaid hollow-fibre membrane.
To achieve these goals, a kind of cosolvent composition proposing according to the present invention, said composition is gamma-butyrolacton, with one or more mixture in 6-caprolactone, epsilon-caprolactams, triethyl phosphate and tetramethylurea.Gamma-butyrolacton, with one or more ratio in 6-caprolactone, epsilon-caprolactams, triethyl phosphate and tetramethylurea be 1:3～3:1.Be preferably, gamma-butyrolacton, with the mixture of 6-caprolactone and/or epsilon-caprolactams.
A further object of the present invention is to provide a kind of core liquid that comprises above-mentioned cosolvent composition.
The present invention compared with prior art has obvious advantage and beneficial effect.By technique scheme, the hollow-fibre membrane that the method according to this invention adopts above-mentioned composite thermotropic phase separation method preparation technology to obtain has high strength, high separation accuracy and high flux and excellent chemical-resistance.This hollow-fibre membrane is put into 5000ppm(effective chlorine) clorox+2wt% sodium hydrate aqueous solution, in 50 ℃ of processing 7 days, its tensile strength conservation rate was up to 85-95%.
Accompanying drawing explanation
Fig. 1 is comparative example 1 section electromicroscopic photograph, and section can obviously be seen finger-like pore structure.
Fig. 2 is comparative example 1 section electromicroscopic photograph, and section can obviously be seen spherical particle structure.
Fig. 3 is comparative example 2 section electromicroscopic photographs, and section can obviously be seen 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 section photo.
Fig. 6 is that embodiment 1 is near inner surface section photo.
Fig. 7 is embodiment 1 section enlarged photograph, can see that film section cavernous body presents bicontinuous structure.
The specific embodiment
For further setting forth the present invention, reach technological means and the effect that predetermined goal of the invention is taked, below in conjunction with accompanying drawing and preferred embodiment, the hollow-fibre membrane proposing according to the present invention and preparation method's the specific embodiment, step are elaborated.
Embodiment 1
The gamma-butyrolacton of the polyether sulfone of the 20wt% of oven dry, 65wt% and epsilon-caprolactams mixing cosolvent, 15wt% glycerine non-solvent are joined in stirred tank, wherein cosolvent gamma-butyrolacton: epsilon-caprolactams=3/1.
Above mixture is at the temperature of 120 ℃, and to stir 18 hours under 100 revs/min of conditions of rotating speed, at the temperature of 120 ℃, vacuum defoamation is 12 hours, obtains homogeneous preparation liquid.
Keep 120 ℃ of preparation liquids by entering cannula type spinning head after 250 order screen packs, spray with together with core liquid in shower nozzle central tube.Core liquid is comprised of 60wt% deionized water, 25wt% gamma-butyrolacton and 15wt% glycerine.The preparation liquid of ejection is through 10cm air section, enter in 10 ℃ of cooling baths, cooling bath is comprised of 40wt% deionized water, 30wt% gamma-butyrolacton and 30wt% glycerine, spinning speed 15m/min, make polyether sulphone hollow fibre film and immerse extraction in the solution that 60 ℃ of 60% pure water and 40% gamma-butyrolacton form and 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/m
2hbar25 ℃, inner surface average pore size is 0.03 μ m, tensile strength is 5.0N/mm
2, percentage elongation is 89%, compression strength 0.70Mpa.
This hollow-fibre membrane is put into 5000ppm(effective chlorine) clorox+2wt% sodium hydrate aqueous solution, in 50 ℃ ± 2 ℃ processing 7 days, its tensile strength was 4.7N/mm
2, tensile strength conservation rate is 94.0%, illustrates that the chemical-resistance of this hollow-fibre membrane is fine.
As shown in Figures 4 to 7, be respectively the section electromicroscopic photograph of the hollow-fibre membrane that makes of embodiment 1, the close outer surface section electromicroscopic photograph of hollow-fibre membrane that embodiment 1 makes, the close inner surface section electromicroscopic photograph of hollow-fibre membrane and the local electromicroscopic photograph that amplifies of the section of the hollow-fibre membrane that embodiment 1 makes that embodiment 1 makes.The whole film section of the hollow-fibre membrane that embodiment 1 makes presents cavernous body 30 structures, and this cavernous structure presents co-continuous 40 structures.
Embodiment 2
The gamma-butyrolacton of the polyether sulfone of the 21wt% of oven dry, 65wt% and epsilon-caprolactams mixing cosolvent, 14wt% ethylene glycol non-solvent are joined in stirred tank, wherein cosolvent gamma-butyrolacton: epsilon-caprolactams=1/3.
Above mixture is at the temperature of 150 ℃, and to stir 36 hours under 100 revs/min of conditions of rotating speed, at the temperature of 150 ℃, vacuum defoamation is 6 hours, obtains homogeneous preparation liquid.
Keep 150 ℃ of preparation liquids by entering cannula type spinning head after 250 order screen packs, spray with together with core liquid in shower nozzle central tube.Core liquid is comprised of 80wt% deionized water, 10wt% gamma-butyrolacton and 10wt% ethylene glycol.The preparation liquid of ejection is through 15cm air section, enter in 25 ℃ of cooling baths, cooling bath is comprised of 60wt% deionized water, 20wt% gamma-butyrolacton and 20wt% ethylene glycol, spinning speed 15m/min, make polyether sulphone hollow fibre film and immerse extraction in the solution that 40 ℃ of 80% pure water and 20% gamma-butyrolacton form and 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/m
2hbar25 ℃, inner surface average pore size is 0.04 μ m, tensile strength is 5.2N/mm
2, percentage elongation is 120%, compression strength 0.82Mpa.
This hollow-fibre membrane is put into 5000ppm(effective chlorine) clorox+2wt% sodium hydrate aqueous solution, in 50 ℃ ± 2 ℃ processing 7 days, its tensile strength was 4.9N/mm
2, tensile strength conservation rate is 94.2%.
Embodiment 3
By the polysulfones of 30wt% of drying,, the gamma-butyrolacton of 57wt% and epsilon-caprolactams mixing cosolvent, 13wt% tetraethylene glycol non-solvent joins in stirred tank, wherein cosolvent gamma-butyrolacton: epsilon-caprolactams=1/1.
Above mixture is at the temperature of 130 ℃, and to stir 24 hours under 100 revs/min of conditions of rotating speed, at the temperature of 130 ℃, vacuum defoamation is 8 hours, obtains homogeneous preparation liquid.
Keep 130 ℃ of preparation liquids by entering cannula type spinning head after 250 order screen packs, spray with together with core liquid in shower nozzle central tube.Core liquid is comprised of 60wt% deionized water, 20wt% gamma-butyrolacton and 20wt% tetraethylene glycol.The preparation liquid of ejection is through 20cm air section, enter in 15 ℃ of cooling baths, cooling bath is comprised of 50wt% deionized water, 25wt% gamma-butyrolacton and 25wt% tetraethylene glycol, spinning speed 15m/min, make extraction in 20 ℃ of pure water of polyether sulphone hollow fibre film immersion and process 12 hours, obtain composite thermotropic phase separation 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/m
2hbar25 ℃, inner surface average pore size is 0.015 μ m, tensile strength is 6.5N/mm
2, percentage elongation is 200%, compression strength 1.0Mpa.
This hollow-fibre membrane is put into 5000ppm(effective chlorine) clorox+2wt% sodium hydrate aqueous solution, in 50 ℃ ± 2 ℃ processing 7 days, its tensile strength was 6.2N/mm
2, tensile strength conservation rate is 95.4%.
Embodiment 4
The gamma-butyrolacton of the polyether sulfone of the 15wt% of oven dry, 71wt% and epsilon-caprolactams mixing cosolvent, 14wt% glycerine non-solvent are joined in stirred tank, wherein cosolvent gamma-butyrolacton: epsilon-caprolactams=1/2.
Above mixture is at the temperature of 140 ℃, and to stir 28 hours under 100 revs/min of conditions of rotating speed, at the temperature of 140 ℃, vacuum defoamation is 8 hours, obtains homogeneous preparation liquid.
Keep 140 ℃ of preparation liquids by entering cannula type spinning head after 250 order screen packs, spray with together with core liquid in shower nozzle central tube.Core liquid is comprised of 70wt% deionized water, 20wt% gamma-butyrolacton and 10wt% glycerine.The preparation liquid of ejection is through 25cm air section, enter in 30 ℃ of cooling baths, cooling bath is comprised of 60wt% deionized water, 25wt% gamma-butyrolacton and 15wt% glycerine, spinning speed 15m/min, making polyether sulphone hollow fibre film immerses extraction in the solution that 80 ℃ of 40% pure water and 60% gamma-butyrolacton form and processes 12 hours, immerse again extraction in the solution that 40 ℃ of 60% pure water and 40% gamma-butyrolacton form and process 18 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 1.5 millimeters/2.1 millimeters, and porosity is 80%, and pure water flux is 1490L/m
2hbar25 ℃, inner surface average pore size is 0.15 μ m, tensile strength is 4.3N/mm
2, percentage elongation is 52%, compression strength 0.6Mpa.
This hollow-fibre membrane is put into 5000ppm(effective chlorine) clorox+2wt% sodium hydrate aqueous solution, in 50 ℃ ± 2 ℃ processing 7 days, its tensile strength was 4.0N/mm
2, tensile strength conservation rate is 93.0%.
Embodiment 5
Except core liquid and cooling bath all adopt pure water, other is identical with embodiment 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/m
2hbar25 ℃, inner surface average pore size is 0.01 μ m, tensile strength is 5.8N/mm
2, percentage elongation is 140%, compression strength is greater than 0.85Mpa.
This hollow-fibre membrane is put into 5000(effective chlorine) ppm clorox+2wt% sodium hydrate aqueous solution, in 50 ℃ ± 2 ℃ processing 7 days, its tensile strength was 5.3N/mm
2, tensile strength conservation rate is 91.4%.
Embodiment 6
The gamma-butyrolacton of the polyether sulfone of the 20wt% of oven dry, 65wt% and 6-caprolactone mixing cosolvent, 15wt% glycerine non-solvent are joined in stirred tank, wherein cosolvent gamma-butyrolacton: 6-caprolactone=2/1.
Above mixture is at the temperature of 130 ℃, and to stir 24 hours under 100 revs/min of conditions of rotating speed, at the temperature of 130 ℃, vacuum defoamation is 8 hours, obtains homogeneous preparation liquid.
Keep 130 ℃ of preparation liquids by entering cannula type spinning head after 250 order screen packs, spray with together with core liquid in shower nozzle central tube.Core liquid is comprised of 60wt% deionized water, 20wt% gamma-butyrolacton and 20wt% glycerine.The preparation liquid of ejection is through 15cm air section, enter in 20 ℃ of cooling baths, cooling bath is comprised of 40wt% deionized water, 30wt% gamma-butyrolacton and 30wt% glycerine, spinning speed 15m/min, make polyether sulphone hollow fibre film and immerse extraction in the solution that 60 ℃ of 80% pure water and 20% gamma-butyrolacton form and 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/m
2hbar25 ℃, inner surface average pore size is 0.03 μ m, tensile strength is 5.2N/mm
2, percentage elongation is 97%, compression strength 0.74Mpa.
This hollow-fibre membrane is put into 5000ppm(effective chlorine) clorox+2wt% sodium hydrate aqueous solution, in 50 ℃ ± 2 ℃ processing 7 days, its tensile strength was 4.8N/mm
2, tensile strength conservation rate is 92.3%, illustrates that the chemical-resistance of this hollow-fibre membrane is fine.
Embodiment 7
The gamma-butyrolacton of the polyether sulfone of the 21wt% of oven dry, 66wt% and tetramethylurea mixing cosolvent, 13wt% glycerine non-solvent are joined in stirred tank, wherein cosolvent gamma-butyrolacton: tetramethylurea=1:1.
Above mixture is at the temperature of 120 ℃, and to stir 18 hours under 100 revs/min of conditions of rotating speed, at the temperature of 120 ℃, vacuum defoamation is 12 hours, obtains homogeneous preparation liquid.
Keep 120 ℃ of preparation liquids by entering cannula type spinning head after 250 order screen packs, spray with together with core liquid in shower nozzle central tube.Core liquid is comprised of 60wt% deionized water, 30wt% gamma-butyrolacton and 10wt% glycerine.The preparation liquid of ejection is through 15cm air section, enter in 25 ℃ of cooling baths, cooling bath is comprised of 60wt% deionized water, 20wt% gamma-butyrolacton and 20wt% glycerine, spinning speed 15m/min, make polyether sulphone hollow fibre film and immerse extraction in the solution that 50 ℃ of 80% pure water and 20% gamma-butyrolacton form and 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/m
2hbar25 ℃, inner surface average pore size is 0.025 μ m, tensile strength is 5.6N/mm
2, percentage elongation is 112%, compression strength 0.76Mpa.
This hollow-fibre membrane is put into 5000ppm(effective chlorine) clorox+2wt% sodium hydrate aqueous solution, in 50 ℃ ± 2 ℃ processing 7 days, its tensile strength was 5.2N/mm
2, tensile strength conservation rate is 92.8%, illustrates that the chemical-resistance of this hollow-fibre membrane is fine.
Comparative example 1
Except cosolvent adopts gamma-butyrolacton, all the other are 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/m
2hbar25 ℃, inner surface average pore size is 0.05 μ m, tensile strength is 3.6N/mm
2, percentage elongation is 62%, compression strength 0.56Mpa.
This hollow-fibre membrane is put into 5000ppm(effective chlorine) clorox+2wt% sodium hydrate aqueous solution, in 50 ℃ ± 2 ℃ processing 7 days, its tensile strength was 1.3N/mm
2, tensile strength conservation rate is only 36.1%.
As shown in Figure 1 and Figure 2, be the section electromicroscopic photograph of the polyether sulphone hollow fibre film that makes of comparative example 1.The polyether sulphone hollow fibre film section that comparative example 1 makes can obviously be seen finger-like pore structure 10 and spherical particle structure 20.
Comparative example 2
Adopt traditional phase separation preparation method (being the existing conventional polyether sulphone hollow fibre film technology of preparing), the DMA solvent of the polyether sulfone of the 19wt% of oven dry, 68wt%, 13wt%PEG-600 non-solvent are joined in stirred tank.
Above mixture is at the temperature of 50 ℃, and to stir 24 hours under 100 revs/min of conditions of rotating speed, at the temperature of 50 ℃, vacuum defoamation is 8 hours, obtains homogeneous preparation liquid.
Keep 50 ℃ of preparation liquids by entering cannula type spinning head after 250 order screen packs, spray with together with core liquid in shower nozzle central tube.Core liquid is by 70wt% deionized water and 30wt%N, and N-dimethylacetylamide forms.The preparation liquid of ejection, through 15cm air section, enters cooling bath, and cooling bath is by 50wt% deionized water and 50wt%N, and N-dimethylacetylamide forms, and spinning speed 15m/min, obtains phase separation 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/m
2hbar25 ℃, inner surface average pore size is 0.025 μ m, tensile strength 3.0N/mm
2, percentage elongation is 35%, compression strength 0.52Mpa.
This hollow-fibre membrane is put into 5000ppm(effective chlorine) clorox+2wt% sodium hydrate aqueous solution, in 50 ℃ ± 2 ℃ processing 7 days, its tensile strength was greater than 2.2N/mm
2, tensile strength conservation rate is 73.3%.
As shown in Figure 3, be the section electromicroscopic photograph of the polyether sulphone hollow fibre film that makes of comparative example 2.The section of the polyether sulphone hollow fibre film that comparative example 2 makes can obviously be seen finger-like macroporous structure 10.
Although the present invention discloses as above with preferred embodiment, so not in order to limit scope of the invention process, the simple equivalence of doing according to claims of the present invention and description changes and modifies, and still belongs in the scope of technical solution of the present invention.
Claims (16)
1. a preparation method for polysulfones or polyether sulphone hollow fibre film, is characterized in that comprising the steps:
Step 1: by the polysulfones of 15-30wt% or polyether sulfone, the cosolvent composition of 50-75wt% and the non-solvent of 10-20wt% stirring and dissolving at the temperature of 120-150 ℃, then vacuum defoamation 6-12 hour at this temperature, is prepared into homogeneous preparation liquid;
Step 2: the preparation liquid in step 1 and core liquid are together passed through to cannula type shower nozzle, through being highly the air section of 10-25cm, enter in cooling bath, compound phase separation occurs and obtain polysulfones or polyether sulphone hollow fibre film; With
Step 3: remove cosolvent composition and non-solvent in the hollow-fibre membrane that step 2 obtains;
Wherein, described cosolvent composition is gamma-butyrolacton, with one or more mixture in 6-caprolactone, epsilon-caprolactams, triethyl phosphate and tetramethylurea.
2. preparation method as claimed in claim 1, is characterized in that wherein said cosolvent composition is gamma-butyrolacton, with at least one mixture in 6-caprolactone and epsilon-caprolactams.
3. preparation method as claimed in claim 1, is characterized in that wherein said cosolvent composition, gamma-butyrolacton, with one or more weight ratio in 6-caprolactone, epsilon-caprolactams, triethyl phosphate and tetramethylurea be 1:3-3:1.
4. preparation method as claimed in claim 1, is characterized in that wherein said non-solvent is glycerine, ethylene glycol, diethylene glycol (DEG), tetraethylene glycol or polyethylene glycol.
5. preparation method as claimed in claim 4, is characterized in that wherein said non-solvent is glycerine or diethylene glycol (DEG).
6. preparation method as claimed in claim 1, is characterized in that wherein said core liquid is comprised of 60-100% deionized water, 0-20% cosolvent and 0-20% non-solvent.
7. preparation method as claimed in claim 1, is characterized in that wherein said cooling bath is comprised of 40-100% deionized water, 0-30% cosolvent and 0-30% non-solvent, and chilling temperature is 0-60 ℃.
8. preparation method as claimed in claim 7, is characterized in that wherein said cooling bath is comprised of 40-60% deionized water, 20-30% cosolvent and 20-30% non-solvent, and chilling temperature is 10-30 ℃.
9. preparation method as claimed in claim 1, it is characterized in that step 3 is by immersing described hollow-fibre membrane in extractant and realize, wherein said extractant is comprised of 40-100% deionized water and 0-60% cosolvent, and temperature is 20-80 ℃, and extraction time is 12-36 hour.
10. preparation method as claimed in claim 9, is characterized in that wherein said extractant is comprised of 60-80% deionized water and 20-40% cosolvent, and temperature is 40-60 ℃, and extraction time is 24 hours.
11. preparation methods as described in claim 1,9 or 10, is characterized in that the wherein said mode that removes is multistep or step extraction.
12. 1 kinds of cosolvent compositions, is characterized in that this cosolvent composition is, gamma-butyrolacton, with one or more mixture in 6-caprolactone, epsilon-caprolactams, triethyl phosphate and tetramethylurea.
13. cosolvent compositions as claimed in claim 12, is characterized in that wherein, gamma-butyrolacton, with one or more weight ratio in 6-caprolactone, epsilon-caprolactams, triethyl phosphate and tetramethylurea be 1:3-3:1.
The purposes of 14. cosolvent compositions as described in claim 12 or 13 in preparing polysulfones or polyether sulphone hollow fibre film.
15. 1 kinds of polysulfones or polyether sulphone hollow fibre film, is characterized in that, it is 50 ℃, the clorox of 5000ppm effective chlorine and 2wt% sodium hydrate aqueous solution seven days that this hollow-fibre membrane is put into temperature, and the tensile strength conservation rate of this hollow-fibre membrane is 85-95%.
16. hollow-fibre membranes as claimed in claim 15, is characterized in that described hollow-fibre membrane section presents co-continuous cavernous structure, porosity 65-80%, and pure water flux is 300-1500L/m
2hbar25 ℃, average pore size is 0.01-0.15 μ m, tensile strength 4.0-6.5N/mm
2, percentage elongation is 50%-200%, compression strength 0.6-1.0MPa.
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| 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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| CN103566773B (en) | 2016-09-14 |
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