CN103111190A - Method for preparing hollow fiber membranes by melt extrusion process - Google Patents
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Abstract
The invention discloses a method for preparing hollow fiber membranes by a melt extrusion process. The method adopts a membrane formation system consisting of the following components in percentage by weight: 20%-40% of cellulose acetate, 10%-25% of polymeric additives, 0-10% of organic additives, and 40%-60% of a composite porogenic agent, wherein the acetyl content of the cellulose acetate is 38%-41.5%, and the molecular weight is 30000-50000. The method adopts a preparation process comprising the following steps of: uniformly mixing the cellulose acetate and the polymeric additives in proportion, then adding the composite porogenic agent for uniformly mixing, carrying out melt extrusion on the mixture with a double-screw extruder at 150-200 DEG C, processing the extrudate with a hollow spinning pack, and solidifying and shaping the extrudate in water bath to obtain a primary hollow fiber membrane; then performing constant-length heat treatment on the primary hollow fiber membrane, wherein the draft multiple is 1.5-3 times, and the heat treatment temperature is 70-90 DEG C; and finally, extracting and washing the primary hollow fiber membrane to obtain the hollow fiber membrane.
Description
Technical field
The present invention relates to membrane preparation technology, be specially a kind of method that extrusion by melting prepares hollow-fibre membrane, described hollow-fibre membrane is the cellulose acetate hollow-fibre membrane.
Background technology
Cellulose acetate (CA) is as the existing quite long history of membrane material, and because of its good hydrophilic property, filming performance is good, has certain biocompatibility and is widely used in the aspects such as ultrafiltration, nanofiltration (NF), counter-infiltration (RO) and blood filtration.At present, a lot of research reports about CAM are arranged both at home and abroad.For example:
A kind of preparation method of cellulose acetate microporous barrier is disclosed in the meeting that Chinese desalinization in 1984 and water recycling are learned.The method is take absolute ethyl alcohol and dichloroethanes as solvent and add additive to form preparation liquid, sprawls in the plane solvent evaporation film forming.
American documentation literature US3883626A discloses a kind of preparation method of the cellulose diacetate microporous barrier for artificial kidney.The method uses acetone and methyl alcohol to be solvent take cellulose diacetate (CDA) as raw material, and calcium chloride is that additive forms preparation liquid, and preparation liquid is sprawled in the plane, and heating makes the solvent evaporation, then immerses film forming in methyl alcohol.
American documentation literature US5403485A discloses a kind of preparation method of the cellulose acetate doughnut for dialysis.The method uses acetic acid to be solvent, passes into nitrogen to form continuous hollow structure, is extruded by spinning head, enters in the coagulating bath that acetum forms to be shaped.
In above-mentioned document, the preparation method is phase inversion, needs a large amount of volatile solvents in film-forming process, and solvent evaporates in film forming procedure reclaims the solvent difficulty, and environment is caused secondary pollution.In addition, due to the lower problem of ubiquity solid content in the phase inversion film-forming process, the hollow membrane mechanical strength that makes is relatively poor.
People (Sung Soo Kim in " research of cellulose acetate doughnut leptonomorphology " literary composition such as external Sung-Soo Kim, etal.Morphological studies of cellulose acetate hollow fiber membranes[J] .Journal of Membrane Science, 1988.37 (2): 113-129) take cellulose acetate as matrix, polyethylene glycol is additive, adopts melt-spinning technology to prepare the cellulose acetate hollow-fibre membrane.But the doughnut membrane permeability that the method makes is relatively poor, and flux is less, is only 2.15ml/ (hrm
2MmHg), industrial implementation has little significance.
Summary of the invention
Not enough for prior art, the technical problem that quasi-solution of the present invention is determined is: provide a kind of extrusion by melting to prepare the method for hollow-fibre membrane, it is simple that the method has production technology, preparation efficiency is high, be adapted to the characteristics such as suitability for industrialized production, the characteristics such as prepared cellulose acetate hollow-fibre membrane has good hydrophilic property, and water flux is large, and mechanical strength is good.
The scheme that the present invention solve the technical problem is: design a kind of method that extrusion by melting prepares hollow-fibre membrane, film forming system and preparation technology that the method adopts following mass percent to form: described phragmoplast is:
Cellulose acetate 20-40wt%;
Polymeric additive 10-25wt%;
Organic additive 0-10wt%;
Composite pore-forming 40-60wt%, each component sum is 100%,
Described cellulose acetate acetyl content is 38%-41.5%, molecular weight 30000-50000;
Described polymeric additive is polyethylene glycol, molecular weight 400-6000; PEO, molecular weight 50000, or the mixture of described polyethylene glycol and PEO arbitrary proportion;
Described organic additive is the higher boiling diluent, comprises the mixture of dioctyl phthalate, benzophenone or dioctyl phthalate and benzophenone arbitrary proportion;
Described composite pore-forming is solubility pore-foaming agent and non-dissolubility pore-foaming agent, and described solubility pore-foaming agent refers to water-soluble substances, is specially the mixture of water-soluble inorganic particle, water-soluble polymer or water-soluble inorganic particle and water-soluble polymer arbitrary proportion; Described water-soluble polymer refers to that decomposition temperature is higher than the water-soluble polymer of its processing temperature; Described non-dissolubility pore-foaming agent refers to water-insoluble inorganic particulate.
The preparation technology of the method is: first cellulose acetate, the polymeric additive with described ratio mixes, add again composite pore-forming to mix, under 150-200 ℃ of condition, utilize double screw extruder to melt extrude, after the hollow spinning pack, enter the water-bath solidified forming, obtain nascent hollow-fibre membrane; Then nascent hollow-fibre membrane is carried out fixed length heat treatment, drafting multiple is 1.5-3 times, and heat treatment temperature is 70-90 ℃, namely gets the cellulose acetate hollow-fibre membrane after extraction is washed.
Compared with prior art, the inventive method adopts the design of melt-spinning technology because select to add suitable plasticizer, thereby it is simple to have preparation technology, the characteristics such as need not add volatile solvent, additive, it is good that the hollow-fibre membrane that makes has mechanical strength, and permeability is good.Compare the inventive method with the people's such as Sung-Soo Kim research:
1. film-forming method is different.The present invention adopts melt spinning-drawing process, and polymer melt melt extrudes under heavily stressed, lower than carrying out after-drawing under melt temperature.After-drawing and fixed length Technology for Heating Processing help film dynamic performance to improve;
2. pore mechanism is different.In the people's such as Sung-Soo Kim research, pore mechanism and thermally induced phase separation are similar, by extraction diluent pore-forming.The present invention is in conjunction with blend boundary pore mechanism and melt spinning-pulling method, and in film-forming process, the water-soluble portion in additive PEG and composite pore-forming is separated out, and forms the stripping hole; Non-solubization part in composite pore-forming owing to forming the interface with matrix compatibility difference, through fixed length heat treatment, forms hole, stretching interface; By adding composite pore-forming, when nascent hollow-fibre membrane is shaped, form the interface micropore, can get flux at last larger, the cellulose acetate hollow-fibre membrane of better performances;
3. the masking system is different.Be different from above-mentioned research, the present invention also adds water-insoluble organic matter except adding PEG as additive, and as dioctyl phthalate, benzophenone etc., after avoiding PEG to separate out, film dynamic performance descends obviously.Compare with thermally induced phase separation, the organic solvent use amount is little, effectively Cost reduction and be conducive to environmental protection.Separately add composite pore-forming, make hollow-fibre membrane of the present invention have multiple pore structure, adjust the ratio that composition and engineering can regulate and control various holes, thereby guarantee that hollow-fibre membrane when having better mechanical property, has higher porosity and separating property.
Description of drawings
Fig. 1 is the cross section overall picture electromicroscopic photograph figure of the prepared cellulose acetate hollow-fibre membrane of a kind of embodiment of preparation method of the present invention.
Fig. 2 is the local electromicroscopic photograph figure that amplifies of the cross section of the prepared cellulose acetate hollow-fibre membrane of a kind of embodiment of preparation method of the present invention.
The specific embodiment
Below in conjunction with example and accompanying drawing thereof, the present invention is further narrated.
A kind of extrusion by melting of the present invention's design prepares the method (abbreviation method) of hollow-fibre membrane, and the film forming system and the preparation technology that adopt following mass percent to form: described phragmoplast is:
Cellulose acetate 20-40wt%;
Polymeric additive 10-25wt%;
Organic additive 0-10wt%;
Composite pore-forming 40-60wt%, each component sum is 100%.
During hollow membrane film forming system mass percent of the present invention formed, described cellulose acetate was basal lamina material.Cellulose acetate acetyl content used is 38-41.5%, and molecular weight is 30000-50000.
Polymeric additive of the present invention is the polyethylene glycol of molecular weight 400-6000, the PEO of molecular weight 50000 or the mixture of described polyethylene glycol and PEO arbitrary proportion.
Organic additive boiling point of the present invention should higher than spinning temperature, on the one hand as polymeric diluents in the masking system, improve the hollow-fibre membrane pliability on the other hand.Described organic additive is the mixture of dioctyl phthalate, benzophenone or described dioctyl phthalate and benzophenone arbitrary proportion.
Composite pore-forming of the present invention requires decomposition temperature higher than spinning temperature, mainly solubility pore-foaming agent and non-dissolubility pore-foaming agent, described solubility pore-foaming agent refers to water-soluble substances, is specially the mixture of water-soluble inorganic particle, water-soluble polymer or water-soluble inorganic particle and water-soluble polymer arbitrary proportion; LiCl, the CaCl of the preferred average grain diameter 0.01-5 μ of described water-soluble inorganic particle m
2, any one in NaCl or KCl; Described water-soluble polymer refers to decomposition temperature higher than the water-soluble polymer of its spinning processing temperature, preferred polyoxyethylene; Described non-dissolubility pore-foaming agent refers to water-insoluble inorganic particulate, the SiO of preferred average grain diameter 0.01-5 μ m
2, CaCO
3Or SiO
2With CaCO
3The mixture of arbitrary proportion.For the present invention, other parts of described composite pore-forming are aggregated thing parcel, in drawing process because compatibility difference forms the stretching micropore.Simultaneously, when the hollow-fibre membrane extraction was washed, described composite pore-forming water-soluble portion was separated out, and can form the stripping micropore.Studies show that, along with composite pore-forming content rises, porosity and the water flux of gained hollow-fibre membrane increase gradually, but the mechanical properties decrease of hollow-fibre membrane.In the film forming system, composite pore-forming content is controlled at comparatively ideal of 40-60wt%.
The inventive method is designed to: first cellulose acetate, the polymeric additive with described proportion of composing mixes, add again described compound perforating agent to mix, under 150-200 ℃ of condition, utilize double screw extruder to melt extrude, after the hollow spinning pack, enter the water-bath solidified forming, obtain nascent hollow-fibre membrane; Then nascent hollow-fibre membrane is carried out fixed length heat treatment, drafting multiple is 1.5-3 times, and heat treatment temperature is 70-90 ℃, after conventional extraction is washed, namely obtains cellulose acetate hollow-fibre membrane of the present invention.
The further feature of the inventive method is that described preparation technology is that the film forming system is first through the twin-screw granulation, and then carries out melt spinning.Granulation process can effectively improve the uniformity coefficient that polymeric additive, organic additive, composite pore-forming in the spinning system are mixed with cellulose acetate, thereby can improve the uniformity of gained doughnut membrane pore structure.
The inventive method preparation technology is simple, and cost is lower, does not need to add volatile solvent in film-forming process, can not cause secondary pollution to environment, and prepared cellulose acetate hollow membrane has good mechanical strength.Experiment shows, after measured, the cellulose acetate hollow-fibre membrane (referring to Fig. 1,2) that the inventive method is prepared, under 0.1Mpa and 25 ℃ of conditions, pure water flux is 45-254L/m
2H, fracture strength is 6.7-11.7MPa.
The present invention does not address part and is applicable to prior art.
The below provides specific embodiments of the invention, but specific embodiment does not limit the present patent application claim protection domain.
Embodiment 1
Take acetyl content as 39.8%, the cellulose acetate of molecular weight 30000 is basal lamina material; Take the PEG of molecular weight 6000 as polymeric additive; Composite pore-forming is the SiO of 0.01 μ m
2The LiCl of powder and 0.05 μ m, the former is water-insoluble pore-foaming agent, accounts for the 30wt% of composite pore-forming total amount, the latter is water-soluble pore-foaming agent, accounts for the 70wt% of composite pore-forming total amount.Each constituent mass proportioning of film forming system is: cellulose acetate 40wt%, polymeric additive 15wt%, organic additive 0%, composite pore-forming 45wt%.
After described cellulose acetate, polymeric additive, organic additive and composite pore-forming are mixed, add in double screw extruder, through doughnut spinning pack extruding spinning, spinning temperature is 180 ℃, obtains nascent hollow membrane.Then nascent hollow membrane is carried out fixed length heat treatment, drafting multiple is 2.5 times, and heat treatment temperature is 90 ℃, after conventional extraction is washed, namely obtains described cellulose acetate hollow-fibre membrane.
After measured, under 0.1Mpa and 25 ℃ of conditions, the pure water flux of gained hollow membrane is 45L/m
2H, fracture strength is 11.7MPa.
Embodiment 2
Take acetyl content as 39.8%, the cellulose acetate of molecular weight 40000 is basal lamina material; Take the PEG of molecular weight 2000 as polymeric additive; Composite pore-forming is the SiO of 0.1 μ m
2The NaCl of powder and 0.05 μ m, the former is water-insoluble pore-foaming agent, accounts for the 30wt% of composite pore-forming total amount, the latter is water-soluble pore-foaming agent, accounts for the 70wt% of composite pore-forming total amount.Each constituent mass proportioning of film forming system is: cellulose acetate 35wt%, polymeric additive 15wt%, organic additive 0%, composite pore-forming 50wt%.
After described cellulose acetate, polymeric additive, organic additive and composite pore-forming are mixed, add in double screw extruder, through doughnut spinning pack extruding spinning, spinning temperature is 175 ℃, obtains nascent hollow membrane.Then nascent hollow membrane is carried out fixed length heat treatment, drafting multiple is 2 times, and heat treatment temperature is 85 ℃, after conventional extraction is washed, namely obtains described hollow membrane.
After measured, under 0.1Mpa and 25 ℃ of conditions, gained hollow-fibre membrane pure water flux is 76L/m
2H, fracture strength is 11.3MPa.
Embodiment 3
With acetyl content 41.5%, the cellulose acetate of molecular weight 50000 is basal lamina material; Take the PEG of molecular weight 600 as polymeric additive; Composite pore-forming is the SiO of 0.1 μ m
2The CaCl of powder and 0.1 μ m
2, the former is water-insoluble pore-foaming agent, accounts for the 30wt% of composite pore-forming total amount, the latter is water-soluble pore-foaming agent, accounts for the 70wt% of composite pore-forming total amount.Each constituent mass proportioning of film forming system is: cellulose acetate 30wt%, polymeric additive 15wt%, organic additive 0%, composite pore-forming 55wt%.
After described cellulose acetate, polymeric additive, organic additive and composite pore-forming are mixed, add in double screw extruder, through doughnut spinning pack extruding spinning, spinning temperature is 170 ℃, obtains nascent hollow membrane.Then nascent hollow membrane is carried out fixed length heat treatment, drafting multiple is 1.5 times, and heat treatment temperature is 85 ℃, after conventional extraction is washed, namely obtains described hollow membrane.
After measured, under 0.1Mpa and 25 ℃ of conditions, the pure water flux of gained hollow membrane is 55L/m
2H, fracture strength is 10.9MPa.
Embodiment 4
Take acetyl content as 39.8%, the cellulose acetate of molecular weight 30000 is basal lamina material; Take the PEO of the PEG of molecular weight 400 and molecular weight 20000 as polymeric additive; Composite pore-forming is the SiO of 5 μ m
2The LiCl of powder and 0.01 μ m, the former is water-insoluble pore-foaming agent, accounts for the 30wt% of composite pore-forming total amount, the latter is water-soluble pore-foaming agent, accounts for the 70wt% of composite pore-forming total amount.Each constituent mass proportioning of film forming system is: cellulose acetate 32wt%, polymeric additive PEG12wt%, PEO 6wt%, organic additive 0%, composite pore-forming 50wt%.
After described cellulose acetate, polymeric additive, organic additive and composite pore-forming are mixed, add in double screw extruder, through doughnut spinning pack extruding spinning, spinning temperature is 170 ℃, obtains nascent hollow membrane.Then
Nascent hollow-fibre membrane is carried out fixed length heat treatment, and drafting multiple is respectively 1.5,1.75,2,2.25,2.5 times, and heat treatment temperature is 85 ℃, gets described hollow membrane after extraction is washed, and is labeled as respectively hollow membrane 1#, 2#, 3#, 4# and 5#.
After measured, under 0.1Mpa and 25 ℃ of conditions, the pure water flux that hollow membrane 1#, 2#, 3#, 4# and 5# are corresponding is respectively 34.8L/m
2H, 52.1L/m
2H, 58.7L/m
2H, 81.4L/m
2H and 92L/m
2H, fracture strength is respectively 6MPa, 6.3MPa, 6.8MPa, 7.1MPa and 7.4MPa.
Embodiment 5
Take acetyl content as 39.8%, the cellulose acetate of molecular weight 30000 is basal lamina material; Take the PEO of the PEG of molecular weight 400 and molecular weight 20000 as polymeric additive; Organic additive is dioctyl phthalate; Composite pore-forming is the CaCO of 0.01 μ m
3The NaCl of powder and 0.05 μ m, the former is water-insoluble pore-foaming agent, accounts for the 30wt% of composite pore-forming total amount, the latter is water-soluble pore-foaming agent, accounts for the 70wt% of composite pore-forming total amount.Each constituent mass proportioning of film forming system is: cellulose acetate 29wt%, polymeric additive PEG10wt%, PEO 5%, organic additive 6%, composite pore-forming 50wt%.
After described cellulose acetate, polymeric additive, organic additive and composite pore-forming are mixed, add in double screw extruder, through doughnut spinning pack extruding spinning, spinning temperature is 170 ℃, obtains nascent hollow membrane.Then nascent hollow membrane is carried out fixed length heat treatment, drafting multiple is 2.5 times, and heat treatment temperature is 80 ℃, namely gets described hollow membrane after extraction is washed.
After measured, under 0.1Mpa and 25 ℃ of conditions, gained hollow-fibre membrane pure water flux is 91L/m
2H, fracture strength is 7.8MPa.
Embodiment 6
Take acetyl content as 39.8%, the cellulose acetate of molecular weight 35000 is basal lamina material; Take the PEO of the PEG of molecular weight 600 and molecular weight 20000 as polymeric additive; Organic additive is dioctyl phthalate; Composite pore-forming is the CaCO of 0.01 μ m
3The CaCl of powder and 0.05 μ m
2, the former is water-insoluble pore-foaming agent, accounts for the 30wt% of composite pore-forming total amount, the latter is water-soluble pore-foaming agent, accounts for the 70wt% of composite pore-forming total amount.Each constituent mass proportioning of film forming system is: cellulose acetate 25.2wt%, polymeric additive PEG9.3wt%, PEO 4.5%, organic additive 5.5%, composite pore-forming 55.5wt%.
After described cellulose acetate, polymeric additive, organic additive and composite pore-forming are mixed, add in double screw extruder, through doughnut spinning pack extruding spinning, spinning temperature is 170 ℃, obtains nascent hollow membrane.Then nascent hollow membrane is carried out fixed length heat treatment, drafting multiple is 2.5 times, and heat treatment temperature is 80 ℃, namely gets the cellulose acetate hollow-fibre membrane after extraction is washed.
After measured, under 0.1Mpa and 25 ℃ of conditions, gained hollow membrane pure water flux is 177L/m
2H, fracture strength is 7.5MPa.
Embodiment 7
Take acetyl content as 38%, the cellulose acetate of molecular weight 40000 is basal lamina material; Take the PEO of the PEG of molecular weight 1000 and molecular weight 20000 as polymeric additive; Organic additive is dioctyl phthalate; Composite pore-forming is the SiO of 0.1 μ m
2The KCl of powder and 5 μ m, the former is water-insoluble pore-foaming agent, accounts for the 30wt% of composite pore-forming total amount, the latter is water-soluble pore-foaming agent, accounts for the 70wt% of composite pore-forming total amount.Each constituent mass proportioning of film forming system is: cellulose acetate 20wt%, polymeric additive PEG10wt%, PEO 5%, organic additive 5%, composite pore-forming 60wt%.
After described cellulose acetate, polymeric additive, organic additive and composite pore-forming are mixed, add in double screw extruder, through doughnut spinning pack extruding spinning, spinning temperature is 175 ℃, obtains nascent hollow membrane.Then nascent hollow membrane is carried out fixed length heat treatment, drafting multiple is 2.5 times, and heat treatment temperature is 80 ℃, namely gets described hollow membrane after extraction is washed.
After measured, under 0.1Mpa and 25 ℃ of conditions, gained hollow membrane pure water flux is 254L/m
2H, fracture strength is 6.7MPa.
Embodiment 8
Take acetyl content as 38%, the cellulose acetate of molecular weight 40000 is basal lamina material; Take the PEO of the PEG of molecular weight 400 and molecular weight 20000 as polymeric additive; Organic additive is benzophenone; Composite pore-forming is the CaCO of 0.5 μ m
3The LiCl of powder and 0.01 μ m, the former is water-insoluble pore-foaming agent, accounts for the 30wt% of composite pore-forming total amount, the latter is water-soluble pore-foaming agent, accounts for the 70wt% of composite pore-forming total amount.Each constituent mass proportioning of film forming system is: cellulose acetate 29wt%, polymeric additive PEG10wt%, PEO 5%, organic additive 6%, composite pore-forming 50wt%.
After described cellulose acetate, polymeric additive, organic additive and composite pore-forming are mixed, add in double screw extruder, through doughnut spinning pack extruding spinning, spinning temperature is 170 ℃, obtains nascent hollow membrane.Then nascent hollow membrane is carried out fixed length heat treatment, drafting multiple is 2 times, and heat treatment temperature is 70 ℃, namely gets hollow membrane after extraction is washed.
After measured, under 0.1Mpa and 25 ℃ of conditions, gained hollow membrane pure water flux is 75L/m
2H, fracture strength is 8.2MPa.
Embodiment 9
Take acetyl content as 39.8%, the cellulose acetate of molecular weight 35000 is basal lamina material; Take the PEO of the PEG of molecular weight 600 and molecular weight 20000 as polymeric additive; Organic additive is benzophenone; Composite pore-forming is the CaCO of 0.01 μ m
3The LiCl of powder and 0.05 μ m, the former is water-insoluble pore-foaming agent, accounts for the 30wt% of composite pore-forming total amount, the latter is water-soluble pore-foaming agent, accounts for the 70wt% of composite pore-forming total amount.Each constituent mass proportioning of film forming system is: cellulose acetate 25.2wt%, polymeric additive PEG9.3wt%, PEO 4.5%, organic additive 5.5%, composite pore-forming 55.5wt%.
After described cellulose acetate, polymeric additive, organic additive and composite pore-forming are mixed, add in double screw extruder, through doughnut spinning pack extruding spinning, spinning temperature is 170 ℃, obtains nascent hollow membrane.Then nascent hollow membrane is carried out fixed length heat treatment, drafting multiple is 2 times, and heat treatment temperature is 70 ℃, namely gets hollow membrane after extraction is washed.
After measured, under 0.1Mpa and 25 ℃ of conditions, gained hollow-fibre membrane pure water flux is 159L/m
2H, fracture strength is 7.7MPa.
Embodiment 10
Take acetyl content as 39.8%, the cellulose acetate of molecular weight 30000 is basal lamina material; Take the PEO of the PEG of molecular weight 1000 and molecular weight 20000 as polymeric additive; Organic additive is benzophenone; Composite pore-forming is the CaCO of 0.5 μ m
3The LiCl of powder and 0.05 μ m, the former is water-insoluble pore-foaming agent, accounts for the 30wt% of composite pore-forming total amount, the latter is water-soluble pore-foaming agent, accounts for the 70wt% of composite pore-forming total amount.Each constituent mass proportioning of film forming system is: cellulose acetate 20wt%, polymeric additive PEG10wt%, PEO 5%, organic additive 5%, composite pore-forming 60wt%.
After described cellulose acetate, polymeric additive, organic additive and composite pore-forming are mixed, add in double screw extruder, through doughnut spinning pack extruding spinning, spinning temperature is 175 ℃, obtains nascent hollow membrane.Then nascent hollow-fibre membrane is carried out fixed length heat treatment, drafting multiple is 3 times, and heat treatment temperature is 75 ℃, namely gets described hollow membrane after extraction is washed.
After measured, under 0.1Mpa and 25 ℃ of conditions, gained hollow-fibre membrane pure water flux is 231L/m
2H, fracture strength is 7MPa.
Claims (3)
1. an extrusion by melting prepares the method for hollow-fibre membrane, and film forming system and preparation technology that the method adopts following mass percent to form: described phragmoplast is:
Cellulose acetate 20-40wt%;
Polymeric additive 10-25wt%;
Organic additive 0-10wt%;
Composite pore-forming 40-60wt%, each component sum is 100%,
Described cellulose acetate acetyl content is 38%-41.5%, molecular weight 30000-50000;
Described polymeric additive is polyethylene glycol, molecular weight 400-6000; PEO, molecular weight 50000, or the mixture of described polyethylene glycol and PEO arbitrary proportion;
Described organic additive is the higher boiling diluent, comprises the mixture of dioctyl phthalate, benzophenone or dioctyl phthalate and benzophenone arbitrary proportion;
Described composite pore-forming is solubility pore-foaming agent and non-dissolubility pore-foaming agent, and described solubility pore-foaming agent refers to water-soluble substances, is specially the mixture of water-soluble inorganic particle, water-soluble polymer or water-soluble inorganic particle and water-soluble polymer arbitrary proportion; Described water-soluble polymer refers to that decomposition temperature is higher than the water-soluble polymer of its processing temperature; Described non-dissolubility pore-foaming agent refers to water-insoluble inorganic particulate;
The preparation technology of the method is: first cellulose acetate, the polymeric additive with described ratio mixes, add again composite pore-forming to mix, under 150-200 ℃ of condition, utilize double screw extruder to melt extrude, after the hollow spinning pack, enter the water-bath solidified forming, obtain nascent hollow-fibre membrane; Then nascent hollow-fibre membrane is carried out fixed length heat treatment, drafting multiple is 1.5-3 times, and heat treatment temperature is 70-90 ℃, namely gets described hollow-fibre membrane after extraction is washed.
2. extrusion by melting prepares the method for hollow-fibre membrane according to claim 1, it is characterized in that described preparation technology is, the film forming system is first through the twin-screw granulation, and then carries out melt spinning.
According to claim 1 or described extrusion by melting prepare the cellulose acetate hollow-fibre membrane that the method for hollow-fibre membrane prepares; Under 0.1Mpa and 25 ℃ of conditions, the pure water flux of gained cellulose acetate hollow-fibre membrane is 45-254L/m
2H, fracture strength is 6.7-11.7MPa.
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| CN111558334A (en) * | 2020-05-26 | 2020-08-21 | 南通醋酸纤维有限公司 | Method and device for preparing cellulose acetate particles |
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| CN110860217B (en) * | 2019-11-22 | 2022-01-18 | 天津工业大学 | Green preparation method of pressure response type polyvinylidene fluoride hollow fiber membrane |
| CN111558334A (en) * | 2020-05-26 | 2020-08-21 | 南通醋酸纤维有限公司 | Method and device for preparing cellulose acetate particles |
| CN114471201A (en) * | 2022-03-23 | 2022-05-13 | 烟台大学 | Polyether-ether-ketone hollow fiber membrane, preparation method thereof and membrane absorption application |
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