CN108905655B - Preparation method of microporous polyphenylene sulfide hollow fiber membrane - Google Patents
Preparation method of microporous polyphenylene sulfide hollow fiber membrane Download PDFInfo
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- CN108905655B CN108905655B CN201810734553.8A CN201810734553A CN108905655B CN 108905655 B CN108905655 B CN 108905655B CN 201810734553 A CN201810734553 A CN 201810734553A CN 108905655 B CN108905655 B CN 108905655B
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- 239000012528 membrane Substances 0.000 title claims abstract description 75
- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 69
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 69
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 34
- 239000003085 diluting agent Substances 0.000 claims abstract description 27
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- 238000000034 method Methods 0.000 claims abstract description 18
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
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- 229930195733 hydrocarbon Natural products 0.000 claims description 12
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- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical group CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 claims description 11
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- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 8
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 8
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- 239000000377 silicon dioxide Substances 0.000 claims description 6
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- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical group CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 4
- 229950005499 carbon tetrachloride Drugs 0.000 claims description 4
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- LERGDXJITDVDBZ-UHFFFAOYSA-N dioctyl benzene-1,3-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=CC(C(=O)OCCCCCCCC)=C1 LERGDXJITDVDBZ-UHFFFAOYSA-N 0.000 claims description 4
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 4
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
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- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910003472 fullerene Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 238000005191 phase separation Methods 0.000 abstract description 5
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 33
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a preparation method of a microporous polyphenylene sulfide hollow fiber membrane, which comprises the following steps: 1) uniformly mixing a diluent, a pore-forming agent, inorganic nano particles and polyphenylene sulfide to obtain a homogeneous polyphenylene sulfide casting solution; 2) adjusting the feeding speed of the screw machine, the rotating speed of the main machine, the rotating speed of the metering pump and the heating temperature of each part; then throwing the polyphenylene sulfide casting solution obtained in the step 1) into a screw machine; 3) setting the gas flow rate or core liquid flow rate of a nozzle of the screw machine, setting the temperature and the receiving distance of the coagulation bath, and spinning; 4) immersing the membrane wire obtained in the step 3) in a heated extracting agent, and drying to remove the organic solvent to obtain the microporous polyphenylene sulfide hollow fiber membrane. Adding inorganic nano particles and an auxiliary diluent to regulate and control the crystallization rate and the phase separation process of the casting solution; and separating out the diluent by using the extraction liquid to obtain the hollow fiber membrane with the inner surface and the outer surface forming micro-nano through holes which are communicated with each other and uniformly distributed.
Description
Technical Field
The invention relates to the field of preparation of polymer hollow fiber membranes, in particular to a preparation method of a microporous polyphenylene sulfide hollow fiber membrane.
Background
The membrane separation technology has been regarded and approved by various countries in the world as a novel high-efficiency separation technology, and plays an increasingly important role in industrial energy conservation, optimization and improvement of production process and efficiency, reutilization of raw materials and environmental pollution treatment. In recent years, membrane technology has been rapidly developed and widely applied in the fields of sewage treatment, seawater desalination, energy-saving technology, petrochemical pharmacy, environment, electronics, energy, aerospace and the like. However, the separation problem under some harsh environments is concentrated and prominent, and particularly, the treatment of corrosive waste liquid/waste gas in the fields of medicine, energy, petrifaction, food, smelting and the like becomes a bottleneck problem for the continuous development of various industries. Therefore, the application of the special membrane technology with harsh environment resistance to the treatment of the waste liquid and the waste gas is a hotspot and a focus in the development of the current membrane technology.
Polyphenylene Sulfide (PPS) is a novel thermoplastic resin, has excellent high temperature resistance, solvent resistance, acid and alkali corrosion resistance, radiation resistance, flame retardance and good mechanical property and electrical property, has wide application in the fields of electronics, automobiles, machinery and chemical industry, and is known as 'sixth engineering plastic'. PPS material can be used in acid, alkali and organic solvents for a long time at high temperature, so that the PPS material can be directly treated by the organic solvent as a membrane material. The PPS has the decomposition temperature of more than 450 ℃ in the air, the long-term use temperature of about 200 ℃, can stand the high temperature of 260 ℃ in a short term, and has better thermal stability. The development of PPS filter materials, in particular PPS membrane materials, has the following advantages: (1) PPS has excellent solvent resistance, and can realize direct treatment of corrosive organic solvents; (2) the direct separation of strong acid or strong alkaline fluid is realized; (3) high-temperature filtration is realized to improve the membrane flux, reduce membrane pollution and the like. Taken together, PPS membranes have a strong potential for use under extreme conditions.
In recent years, the PPS flat membrane is successfully prepared by utilizing a TIPS (TIPS membrane scraping) technology, has a certain excellent performance, and is successfully applied to the fields of acid-base wastewater treatment, oil-water separation, removal of organic molecules in a solvent and the like. The rapidly developed hollow fiber membranes have many advantages over flat sheet membranes: (1) the packing density per unit area is high. The water yield per unit area is increased due to the high filling density of the hollow fibers, and the water recovery rate is high; (2) the device does not need any supporting body, simplifies the structure, is convenient to manufacture a small and light device, and is applied to the aspects of filtration and the like in harsh environment.
PPS is a semi-crystalline polymer that can be dissolved without any solvent at 200 c, so that it is difficult to prepare a PPS film by a non-solvent induced phase separation (NIPS) method at normal temperature. The PPS hollow fiber microfiltration membrane is prepared by carrying out hot drawing after melt spinning by a melt spinning machine in the literature 'Wangli polyphenylene sulfide hollow fiber microfiltration membrane research [ D ]. Tianjin university of industry, 2000'; the influence of the spinning temperature, the spinning speed, the nitrogen flux and the like on the formation of the PPS hollow fiber membrane is researched; but has the disadvantages of non-uniform pores and low flux.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to solve the technical problem of providing a preparation method of a microporous polyphenylene sulfide hollow fiber membrane.
The technical scheme for solving the technical problem is to provide a preparation method of a microporous polyphenylene sulfide hollow fiber membrane, which is characterized by comprising the following steps:
1) uniformly mixing a diluent accounting for 20-60% of the total mass, a pore-forming agent accounting for 0-2% of the total mass, inorganic nano particles accounting for 0-2% of the total mass and polyphenylene sulfide accounting for 40-80% of the total mass to obtain a homogeneous polyphenylene sulfide casting solution; the sum of the four is 100%;
the diluent is a benign diluent and an auxiliary diluent; the benign diluent is at least one of caprolactam, benzophenone, diphenyl ether, benzoin or diphenyl sulfone; the auxiliary diluent is dibutyl sebacate, dibutyl phthalate, dioctyl phthalate or dioctyl isophthalate;
2) adjusting the feeding speed of the screw machine, the rotating speed of the main machine, the rotating speed of the metering pump and the heating temperature of each part; then throwing the polyphenylene sulfide casting solution obtained in the step 1) into a screw machine;
3) setting the gas flow rate or core liquid flow rate of a nozzle of the screw machine, setting the temperature and the receiving distance of the coagulation bath, and spinning; the core liquid is at least one of water, an alcohol solvent, a halogenated hydrocarbon solvent, an ether solvent, an ester solvent, a hydrocarbon solvent or an amide solvent; the coagulating bath is at least one of water, alcohol solvent, halogenated hydrocarbon solvent, ether solvent, ester solvent, hydrocarbon solvent or amide solvent;
4) immersing the membrane wires obtained in the step 3) in an extracting agent heated to 50-80 ℃ for 24-48h, and drying to remove the organic solvent to obtain the microporous polyphenylene sulfide hollow fiber membrane; the extracting agent is at least one of an alcohol solvent, a halogenated hydrocarbon solvent, an ether solvent, an ester solvent, a hydrocarbon solvent or an amide solvent.
Compared with the prior art, the invention has the beneficial effects that:
(1) the homogeneous PPS casting solution is prepared by taking solvent-resistant and acid-alkali-resistant polyphenylene sulfide as a film forming material, adopting a thermally induced phase separation method (TIPS) and a non-solvent induced phase separation method (NIPS) and compounding a benign diluent and an auxiliary diluent. Adding inorganic nano particles and an auxiliary diluent to regulate and control the crystallization rate and the phase separation process of the casting solution; the method comprises the following steps of (1) utilizing a coagulating bath to extract a solvent, and adjusting the opening rate and the pore size of a membrane cortex; and then, separating out the diluent by using the extraction liquid to obtain the hollow fiber membrane with the inner surface and the outer surface forming micro-nano through holes which are communicated with each other inside and outside and are uniformly distributed.
(2) The diffusion moving speed of a PPS molecular chain in a benign diluent is adjusted by using an auxiliary diluent, the PPS is well dissolved in a compound solvent by using the action of a double screw to form a homogeneous casting solution, meanwhile, the added auxiliary diluent can slow down the moving speed of the molecular chain, namely the purpose of slowing down the crystallization speed of the PPS is achieved, meanwhile, the phase separation temperature of the casting solution can be reduced, and a hollow fiber membrane with a large number of penetrating micro-nano holes is obtained. The addition of the pore-forming agent and the inorganic nano particles can create more through channels and enhance the properties of the membrane matrix such as strength and the like.
(3) By comparing the structures of membranes made from various solvents, it was found that a membrane made by adding 0.1% GO to the total amount of the ingredients and 50% ethylene glycol/50% water in the coagulation bath (temperature 60 ℃) in proportion (PPS: BP: BZ: DBS: 50%: 22.5%: 22.5%: 5%) had permeable pores, both the inner and outer surfaces had uniform micropores, and the mechanical properties of the fiber membrane were good.
Drawings
FIG. 1 is a sectional electron microscope image of a microporous polyphenylene sulfide hollow fiber membrane in example 3 of the method for producing a microporous polyphenylene sulfide hollow fiber membrane according to the present invention;
FIG. 2 is an enlarged electron microscope image of position 1 of FIG. 1 illustrating a method for preparing a microporous polyphenylene sulfide hollow fiber membrane according to the present invention;
FIG. 3 is an enlarged electron micrograph of position 2 of FIG. 1 of a microporous polyphenylene sulfide hollow fiber membrane according to the method of the present invention;
FIG. 4 is an enlarged electron micrograph of position 3 of FIG. 1 illustrating a method for preparing a microporous polyphenylene sulfide hollow fiber membrane according to the present invention;
FIG. 5 is an electron microscope image of the inner surface of a microporous polyphenylene sulfide hollow fiber membrane in example 3 of the method for preparing a microporous polyphenylene sulfide hollow fiber membrane of the present invention.
Detailed Description
Specific examples of the present invention are given below. The specific examples are only intended to illustrate the invention in further detail and do not limit the scope of protection of the claims of the present application.
The invention provides a preparation method (method for short) of a microporous polyphenylene sulfide hollow fiber membrane, which is characterized by comprising the following steps:
1) grinding a diluent into powder at room temperature, and uniformly mixing the diluent accounting for 20-60% of the total mass, a pore-forming agent accounting for 0-2% of the total mass, inorganic nano particles accounting for 0-2% of the total mass and polyphenylene sulfide accounting for 40-80% of the total mass in a stirrer to obtain a homogeneous phase polyphenylene sulfide casting solution; the sum of the four is 100%;
the diluent is at least one of caprolactam (CP L), Benzophenone (BP), diphenyl ether (DPE), Benzoin (BZ) or diphenyl sulfone (DPS), and the auxiliary diluent is dibutyl sebacate (DBS), dibutyl phthalate (DBP), dioctyl phthalate (DOP) or dioctyl isophthalate (DOTP);
the pore-foaming agent is polyethylene glycol or nano salt;
the inorganic nanoparticles are Graphene Oxide (GO), silicon dioxide, titanium dioxide, carbon nanotubes or fullerene;
the polyphenylene sulfide is powder with uniform particles, has uniform molecular weight distribution, no impurities and no large-size agglomeration, and is dried for 12 hours at 80 ℃ before use.
2) Adjusting the feeding speed of the screw machine, the rotating speed of the main machine, the rotating speed of the metering pump and the heating temperature of each part; then throwing the polyphenylene sulfide casting solution obtained in the step 1) into a screw machine;
the screw machine adopts a sectional heating double-screw machine, the temperature of the screw section is 220-; the feeding speed is 40-80r/min, the main machine speed is 20-60r/min, and the metering pump speed is 15-30 r/min; the double screws can effectively promote the dissolution of the polyphenylene sulfide in the diluent and the dispersion of the pore-forming agent and the inorganic nano particles in the membrane casting solution, and shorten the dissolution time;
3) setting the gas flow rate or core liquid flow rate of a nozzle of the screw machine, setting the temperature and the receiving distance of the coagulation bath, and spinning;
the gas is nitrogen; the gas flow rate is 0.1-0.5 NI/Min; the core liquid flow is 0.2-2 times of the casting film liquid flow, and the casting film liquid flow is related to the rotating speed of the metering pump; the core liquid and the coagulating bath are at least one of water, alcohol solvent, halogenated hydrocarbon solvent, ether solvent, ester solvent, hydrocarbon solvent or amide solvent; the temperature of the coagulating bath is 25-60 ℃; the receiving distance of the coagulating bath is 5cm-15 cm;
4) immersing the membrane wires obtained in the step 3) in an extracting agent heated to 50-80 ℃ for 24-48h, and drying to remove the organic solvent to obtain the microporous polyphenylene sulfide hollow fiber membrane.
The extracting agent is at least one of an alcohol solvent, a halogenated hydrocarbon solvent, an ether solvent, an ester solvent, a hydrocarbon solvent or an amide solvent.
The alcohol solvent in the step 3) is at least one of propanol, isopropanol, butanol, isobutanol or benzyl alcohol; the halogenated hydrocarbon solvent is at least one of tetrachloromethane, 1, 2-dichloroethane or tetrahydropalmiran; the ether solvent is butyl ether; the ester solvent is at least one of ethyl acetate, butyl acetate, ethyl benzoate, ethyl formate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate or dipropyl carbonate; the hydrocarbon solvent is at least one of cyclohexane, benzene or toluene; the amide solvent is N, N-dimethylformamide or N, N-diethylacetamide;
the alcohol solvent in the step 4) is at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol or benzyl alcohol; the halogenated hydrocarbon solvent is at least one of tetrachloromethane, 1, 2-dichloroethane or tetrahydropalmiran; the ether solvent is butyl ether; the ester solvent is at least one of ethyl acetate, butyl acetate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate or dipropyl carbonate; the hydrocarbon solvent is at least one of cyclohexane, benzene or toluene; the amide solvent is N, N-dimethylformamide, N-methylpyrrolidone or N, N-diethylacetamide;
example 1
(1) The materials (PPS: BP: BZ 80%: 10%: 10%) are pulverized and mixed uniformly by a pulverizer, the heating temperature of each section of a screw section (240 ℃, 282 ℃, 294 ℃, 290 ℃, 292 ℃), the temperature of a spinning nozzle and the temperature of a metering pump (264 ℃ ) are set, and the rotating speed of a main machine, the feeding rotating speed and the rotating speed of the metering pump are adjusted after the temperatures are stable.
(2) The nitrogen flow rate of the nozzle is adjusted to be 0.1NI/min by adopting a nitrogen-introducing hollow mode.
(3) In the spinning process, mixed liquid compounded according to the weight ratio of water to ethylene glycol of 1:1 is used as coagulation bath, the temperature is adjusted to be 60 ℃, and the receiving distance of the coagulation bath is 12 cm.
(4) Soaking membrane filaments in 60 deg.C ethanol for 48 hr, soaking in distilled water for 24 hr, freeze drying, and storing. The inner surface, the outer surface and the cross section of the glass are analyzed by an electron microscope to have fine granular crystals and rod-shaped crystals which are not dissolved benzophenone and benzoin, the inner diameter and the outer diameter are respectively 0.02mm and 1.5mm, no holes exist on the inner surface and the outer surface, no through holes exist, and a small amount of spherical structures exist on the cross section.
Example 2
(1) The materials (PPS: BP: BZ 50%: 50%: 0%), the pulverizer pulverizes and mixes uniformly, sets the heating temperature of each segment (225 ℃, 264 ℃, 265 ℃, 261 ℃, 260 ℃, 260 ℃), the spinneret temperature and the metering pump temperature (245 ℃ ), and adjusts the rotating speed of the main machine, the feeding rotating speed and the metering pump rotating speed after the temperatures are stable.
(2) The nitrogen flow rate of the nozzle is adjusted to be 0.1NI/min by adopting a nitrogen-introducing hollow mode.
(3) In the spinning process, mixed liquid compounded according to the weight ratio of water to ethylene glycol of 1:1 is used as coagulation bath, the temperature is adjusted to be 60 ℃, and the receiving distance of the coagulation bath is 12 cm.
(4) Soaking membrane filaments in 60 deg.C ethanol for 48 hr, soaking in distilled water for 24 hr, freeze drying, and storing. The section of the benzophenone composite material is analyzed by an electron microscope to have fine crystal particles which are undissolved benzophenone, a large number of spherical structures exist, the inner diameter and the outer diameter are respectively 0.15mm and 1.4mm, holes are not found on the outer surface, holes which are not uniformly distributed exist on the inner surface, and no through hole exists.
Example 3
(1) The materials (PPS: BP: BZ 50%: 25%: 25%) are pulverized and mixed uniformly by a pulverizer, the heating temperature of each section (220 ℃, 260 ℃, 265 ℃, 262 ℃, 251 ℃, 251 ℃) is set, the temperature of a spinning nozzle and the temperature of a metering pump (240 ℃ ) are set, and the rotating speed of a main machine, the rotating speed of the feeding and the rotating speed of the metering pump are adjusted after the temperatures are stabilized.
(2) The nitrogen flow rate of the nozzle is adjusted to be 0.1NI/min by adopting a nitrogen-introducing hollow mode.
(3) In the spinning process, mixed liquid compounded according to the weight ratio of water to ethylene glycol of 1:1 is used as coagulation bath, the temperature is adjusted to be 60 ℃, and the receiving distance of the coagulation bath is 12 cm.
(4) Soaking membrane filaments in 60 deg.C ethanol for 48 hr, soaking in distilled water for 24 hr, freeze drying, and storing. The inner surface, the outer surface and the section of the material are analyzed by an electron microscope to have fine crystal particles which are not dissolved benzophenone, the inner diameter and the outer diameter are respectively 0.8mm and 1.3mm, no hole is found on the outer surface, long-strip-shaped micropores are uniformly distributed on the inner surface, and a uniform dendritic structure is found on the section.
Example 4
(1) The materials (PPS: BP: BZ 40%: 30%: 30%) are pulverized and mixed uniformly by a pulverizer, the heating temperature of each section (220 ℃, 260 ℃, 263 ℃, 262 ℃, 250 ℃, 250 ℃), the temperature of a spinning nozzle and the temperature of a metering pump (238 ℃ ) are set, and the rotating speed of a main machine, the rotating speed of the feeding and the rotating speed of the metering pump are adjusted after the temperatures are stable.
(2) The nitrogen flow rate of the nozzle is adjusted to be 0.1NI/min by adopting a nitrogen-introducing hollow mode.
(3) In the spinning process, mixed liquid compounded according to the weight ratio of water to ethylene glycol of 1:1 is used as coagulation bath, the temperature is adjusted to be 60 ℃, and the receiving distance of the coagulation bath is 12 cm.
(4) Soaking membrane filaments in 60 deg.C ethanol for 48 hr, soaking in distilled water for 24 hr, freeze drying, and storing. The inner surface and the outer surface of the diaphragm are analyzed by an electron microscope, uneven holes are formed in the inner surface and the outer surface, the outer surface has an aperture phenomenon, namely holes are formed in the aperture, the inner diameter and the outer diameter are respectively 0.9mm and 1.4mm, no obvious holes exist outside the aperture, an even dendritic structure is found on the section, but the film is found to be brittle and low in strength.
Example 5
(1) The preparation method comprises the following steps of preparing materials (PPS: BP: BZ: DBS: 50%: 22.5%: 22.5%: 5%), crushing a solid material by a crusher, uniformly mixing, adding a liquid component in a dropwise manner by using a constant speed injection pump, calculating the feeding rotation speed to match with the dropwise adding speed, namely, completing the dropwise adding of the liquid material simultaneously when the solid material is added at the constant speed. Setting the heating temperature of each section (220 ℃, 262 ℃, 265 ℃, 262 ℃, 252 ℃ and 252 ℃), the temperature of a spinning nozzle and the temperature of a metering pump (240 ℃ and 240 ℃), and adjusting the rotating speed of a main machine, the feeding rotating speed and the rotating speed of the metering pump after the temperatures are stable.
(2) The nitrogen flow rate of the nozzle is adjusted to be 0.1NI/min by adopting a nitrogen-introducing hollow mode.
(3) In the spinning process, mixed liquid compounded according to the weight ratio of water to ethylene glycol of 1:1 is used as coagulation bath, the temperature is adjusted to be 60 ℃, and the receiving distance of the coagulation bath is 12 cm.
(4) Soaking membrane filaments in 60 deg.C ethanol for 48 hr, soaking in distilled water for 24 hr, freeze drying, and storing. The inner surface and the outer surface of the membrane do not have a cortex layer through electron microscope analysis, the inner diameter and the outer diameter are respectively 0.9mm and 1.4mm, the inner surface and the outer surface of the membrane all have micropores which are uniformly distributed, the aperture is 100-140nm, the cross section finds a uniform dendritic structure, and the membrane is found to have better toughness and strength.
Example 6
(1) The preparation method comprises the following steps of preparing materials (PPS: BP: BZ: DBS: 40%: 25%: 25%: 10%), crushing solid materials by a crusher, uniformly mixing, adding liquid components in a manner of dropwise adding by using a constant speed injection pump, calculating the feeding rotating speed to match with the dropwise adding speed, namely, completing the dropwise adding of the liquid materials simultaneously when the solid materials are added at the constant speed. Setting the heating temperature of each section (220 ℃, 260 ℃, 263 ℃, 262 ℃, 250 ℃ and 250 ℃), the temperature of a spinning nozzle and the temperature of a metering pump (240 ℃ and 240 ℃), and adjusting the rotating speed of a main machine, the feeding rotating speed and the rotating speed of the metering pump after the temperatures are stable.
(2) The nitrogen flow rate of the nozzle is adjusted to be 0.1NI/min by adopting a nitrogen-introducing hollow mode.
(3) In the spinning process, mixed liquid compounded according to the weight ratio of water to ethylene glycol of 1:1 is used as coagulation bath, the temperature is adjusted to be 60 ℃, and the receiving distance of the coagulation bath is 12 cm.
(4) Soaking membrane filaments in 60 deg.C ethanol for 48 hr, soaking in distilled water for 24 hr, freeze drying, and storing. The inner surface and the outer surface of the membrane are analyzed by an electron microscope to be free from cortex, the inner diameter and the outer diameter are respectively 1.0mm and 1.3mm, uniformly distributed micropores are arranged on the inner surface and the outer surface, the aperture is 200-300nm, and the cross section shows a uniform dendritic structure, but the membrane is found to be better in toughness but low in strength.
Example 7
(1) The materials (PPS: BP: BZ: DBS: 40%: 25%: 25%: 10%) are pulverized and mixed uniformly by a pulverizer, the heating temperatures of the sections (220 ℃, 260 ℃, 263 ℃, 262 ℃, 250 ℃, 250 ℃), the temperatures of a spinning nozzle and a metering pump (238 ℃ ), and the rotating speed of a main machine, the rotating speed of the feeding and the rotating speed of the metering pump are adjusted after the temperatures are stabilized.
(2) The nitrogen flow rate of the nozzle is adjusted to be 0.1NI/min by adopting a nitrogen-introducing hollow mode.
(3) In the spinning process, mixed liquid compounded according to the weight ratio of water to ethylene glycol of 1:1 is used as coagulation bath, the temperature is adjusted to be 60 ℃, and the receiving distance of the coagulation bath is 12 cm.
(4) Soaking membrane filaments in 60 deg.C ethanol for 48 hr, soaking in distilled water for 24 hr, freeze drying, and storing. The viscosity of the casting solution is found to be high in the process of extruding the casting solution by the twin screw, and the fiber membrane obtained by analysis of an electron microscope shows that no cortex layer exists on the inner surface and the outer surface, and the inner diameter and the outer diameter are respectively 0.7mm and 1.2 mm. Micropores are uniformly distributed on the inner surface and the outer surface, but the distribution size of the micropores is not uniform, the pore diameter is 2400nm, and the fiber membrane has defects, so that the membrane has better toughness and low strength.
Example 8
(1) The preparation method comprises the following steps of preparing materials (PPS: BP: BZ: DBS: 50%: 22.5%: 22.5%: 5%), adding Graphene Oxide (GO) accounting for 0.1% of the total amount of the materials, crushing a solid material by a crusher, uniformly mixing, adding a liquid component in a constant-speed injection pump dropwise adding mode, calculating the feeding rotating speed to match with the dropwise adding speed, and finishing the dropwise adding of the liquid material when the solid material is added at the constant speed. Setting the heating temperature of each section (220 ℃, 262 ℃, 265 ℃, 262 ℃, 252 ℃ and 252 ℃), the temperature of a spinning nozzle and the temperature of a metering pump (240 ℃ and 240 ℃), and adjusting the rotating speed of a main machine, the feeding rotating speed and the rotating speed of the metering pump after the temperatures are stable.
(2) The nitrogen flow rate of the nozzle is adjusted to be 0.1NI/min by adopting a nitrogen-introducing hollow mode.
(3) In the spinning process, mixed liquid compounded according to the weight ratio of water to ethylene glycol of 1:1 is used as coagulation bath, the temperature is adjusted to be 60 ℃, and the receiving distance of the coagulation bath is 12 cm.
(4) Soaking membrane filaments in 60 deg.C ethanol for 48 hr, soaking in distilled water for 24 hr, freeze drying, and storing. The inner surface and the outer surface of the membrane are not provided with a cortex layer through electron microscope analysis, the inner diameter and the outer diameter are respectively 0.9mm and 1.3mm, micropores which are uniformly distributed exist on the inner surface and the outer surface, the aperture is 90-140nm, the cross section finds a uniform dendritic structure, GO sheets are uniformly distributed in a matrix and holes of the membrane, and the membrane is found to have excellent toughness and strength.
Example 9
(1) Adding silicon dioxide nano particles accounting for 0.2 percent of the total amount of the ingredients into the ingredients (PPS: BP: BZ: DBS: 50%: 22.5%: 22.5%: 5%), crushing the solid ingredients by a crusher and mixing uniformly, adding the liquid ingredients in a manner of dripping by using a constant speed injection pump, and calculating the feeding speed to match with the dripping speed, namely when the solid ingredients are added at the constant speed, dripping the liquid ingredients at the same time. Setting the heating temperature of each section (220 ℃, 262 ℃, 265 ℃, 262 ℃, 252 ℃ and 252 ℃), the temperature of a spinning nozzle and the temperature of a metering pump (240 ℃ and 240 ℃), and adjusting the rotating speed of a main machine, the feeding rotating speed and the rotating speed of the metering pump after the temperatures are stable.
(2) The nitrogen flow rate of the nozzle is adjusted to be 0.1NI/min by adopting a nitrogen-introducing hollow mode.
(3) In the spinning process, mixed liquid compounded according to the weight ratio of water to ethylene glycol of 1:1 is used as coagulation bath, the temperature is adjusted to be 60 ℃, and the receiving distance of the coagulation bath is 12 cm.
(4) Soaking membrane filaments in 60 deg.C ethanol for 48 hr, soaking in distilled water for 24 hr, freeze drying, and storing. The inner surface and the outer surface of the rubber pipe are analyzed by an electron microscope to have no cortex, and the inner diameter and the outer diameter are respectively 1.1mm and 1.5 mm. The inner surface and the outer surface are provided with micropores which are uniformly distributed, the aperture is 100-150nm, the cross section shows a uniform dendritic structure, the silica nanoparticles are uniformly distributed in the matrix and the holes of the film, and the film is found to have excellent toughness and strength.
Example 10
(1) Adding 50 percent of polyethylene glycol and 0.2 percent of silicon dioxide nano particles in the total amount of the ingredients (PPS: BP: BZ: DBS: 22.5 percent: 5 percent), crushing the solid ingredients by a crusher, uniformly mixing, adding the liquid ingredients in a manner of dropwise adding by using a uniform speed injection pump, and calculating the feeding rotating speed to match with the dropwise adding speed, namely, when the solid ingredients are completely added at a uniform speed, the liquid ingredients are completely dripped at the same time. Setting the heating temperature of each section (220 ℃, 261 ℃, 264 ℃, 261 ℃, 251 ℃ and 251 ℃), the temperature of a spinning nozzle and the temperature of a metering pump (240 ℃ and 240 ℃), and adjusting the rotating speed of a main machine, the feeding rotating speed and the rotating speed of the metering pump after the temperatures are stable.
(2) The nitrogen flow rate of the nozzle is adjusted to be 0.1NI/min by adopting a nitrogen-introducing hollow mode.
(3) In the spinning process, mixed liquid compounded according to the weight ratio of water to ethylene glycol of 1:1 is used as coagulation bath, the temperature is adjusted to be 60 ℃, and the receiving distance of the coagulation bath is 12 cm.
(4) Soaking membrane filaments in 60 deg.C ethanol for 48 hr, soaking in distilled water for 24 hr, freeze drying, and storing. The inner surface and the outer surface of the rubber pipe are analyzed by an electron microscope to have no cortex, and the inner diameter and the outer diameter are respectively 1.2mm and 1.6 mm. The inner surface and the outer surface are provided with micropores which are uniformly distributed, the aperture is 140-200nm, the cross section shows a uniform dendritic structure, the silica nanoparticles are uniformly distributed in the matrix and the holes of the film, and the film is found to have excellent toughness and strength.
Nothing in this specification is said to apply to the prior art.
Claims (8)
1. A preparation method of a microporous polyphenylene sulfide hollow fiber membrane is characterized by comprising the following steps:
1) uniformly mixing a diluent accounting for 20-60% of the total mass, a pore-forming agent accounting for 0-2% of the total mass, inorganic nano particles accounting for 0-2% of the total mass and polyphenylene sulfide accounting for 40-80% of the total mass to obtain a homogeneous polyphenylene sulfide casting solution; the sum of the four is 100%;
the diluent is a benign diluent and an auxiliary diluent; the benign diluent is at least one of caprolactam, benzophenone, diphenyl ether, benzoin or diphenyl sulfone; the auxiliary diluent is dibutyl sebacate, dibutyl phthalate, dioctyl phthalate or dioctyl isophthalate;
2) adjusting the feeding speed of the screw machine, the rotating speed of the main machine, the rotating speed of the metering pump and the heating temperature of each part; then throwing the polyphenylene sulfide casting solution obtained in the step 1) into a screw machine;
the screw machine adopts a sectional heating double-screw machine, the temperature of the screw section is 220-; the rotating speed of the metering pump is 15-30 r/min;
3) setting the gas flow rate or core liquid flow rate of a nozzle of the screw machine, setting the temperature and the receiving distance of the coagulation bath, and spinning; the core liquid is at least one of water, an alcohol solvent, a halogenated hydrocarbon solvent, an ether solvent, an ester solvent, a hydrocarbon solvent or an amide solvent; the coagulating bath is at least one of water, alcohol solvent, halogenated hydrocarbon solvent, ether solvent, ester solvent, hydrocarbon solvent or amide solvent;
the gas is nitrogen; the gas flow rate is 0.1-0.5 NI/Min; the core liquid flow is 0.2-2 times of the casting film liquid flow, and the casting film liquid flow is related to the rotating speed of the metering pump;
4) immersing the membrane wires obtained in the step 3) in an extracting agent heated to 50-80 ℃ for 24-48h, and drying to remove the organic solvent to obtain the microporous polyphenylene sulfide hollow fiber membrane; the extracting agent is at least one of an alcohol solvent, a halogenated hydrocarbon solvent, an ether solvent, an ester solvent, a hydrocarbon solvent or an amide solvent.
2. The method for preparing microporous polyphenylene sulfide hollow fiber membrane according to claim 1, wherein the pore-forming agent is polyethylene glycol or nano salt.
3. The method of claim 1, wherein the inorganic nanoparticles are graphene oxide, silicon dioxide, titanium dioxide, carbon nanotubes, or fullerenes.
4. The method of claim 1, wherein the polyphenylene sulfide is dried at 80 ℃ for 12 hours before use.
5. The preparation method of the microporous polyphenylene sulfide hollow fiber membrane as claimed in claim 1, wherein the feeding speed in step 2) is 40-80r/min, and the main engine speed is 20-60 r/min.
6. The method for preparing microporous polyphenylene sulfide hollow fiber membrane according to claim 1, wherein the coagulation bath temperature in step 3) is 25-60 ℃; the receiving distance of the coagulating bath is 5cm-15 cm.
7. The method for preparing microporous polyphenylene sulfide hollow fiber membrane according to claim 1, wherein the alcohol solvent in step 3) is at least one of propanol, isopropanol, butanol, isobutanol, or benzyl alcohol; the halogenated hydrocarbon solvent is at least one of tetrachloromethane, 1, 2-dichloroethane or tetrahydropalmiran; the ether solvent is butyl ether; the ester solvent is at least one of ethyl acetate, butyl acetate, ethyl benzoate, ethyl formate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate or dipropyl carbonate; the hydrocarbon solvent is at least one of cyclohexane, benzene or toluene; the amide solvent is N, N-dimethylformamide or N, N-diethylacetamide.
8. The method for preparing microporous polyphenylene sulfide hollow fiber membrane according to claim 1, wherein the alcohol solvent in step 4) is at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol or benzyl alcohol; the halogenated hydrocarbon solvent is at least one of tetrachloromethane, 1, 2-dichloroethane or tetrahydropalmiran; the ether solvent is butyl ether; the ester solvent is at least one of ethyl acetate, butyl acetate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate or dipropyl carbonate; the hydrocarbon solvent is at least one of cyclohexane, benzene or toluene; the amide solvent is N, N-dimethylformamide, N-methylpyrrolidone or N, N-diethylacetamide.
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