CN115970519A - Polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane and preparation method thereof - Google Patents
Polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane and preparation method thereof Download PDFInfo
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- CN115970519A CN115970519A CN202310044333.3A CN202310044333A CN115970519A CN 115970519 A CN115970519 A CN 115970519A CN 202310044333 A CN202310044333 A CN 202310044333A CN 115970519 A CN115970519 A CN 115970519A
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- 239000012528 membrane Substances 0.000 title claims abstract description 86
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 83
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 70
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 70
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 58
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 238000005266 casting Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 238000005191 phase separation Methods 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 5
- 239000003607 modifier Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 26
- 238000007711 solidification Methods 0.000 claims description 22
- 230000008023 solidification Effects 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 13
- 230000000996 additive effect Effects 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 238000004804 winding Methods 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 230000004907 flux Effects 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 238000009987 spinning Methods 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- -1 polyoxyethylene Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 4
- 235000010981 methylcellulose Nutrition 0.000 claims 1
- 239000003651 drinking water Substances 0.000 abstract description 2
- 235000020188 drinking water Nutrition 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- 239000008399 tap water Substances 0.000 abstract description 2
- 235000020679 tap water Nutrition 0.000 abstract description 2
- 238000001891 gel spinning Methods 0.000 abstract 1
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 229940113088 dimethylacetamide Drugs 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 5
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 4
- 238000011085 pressure filtration Methods 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- Artificial Filaments (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the field of porous membrane manufacturing, in particular to a polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane and a preparation method thereof. The invention adds polyvinylidene fluoride into polyvinyl chloride for blending, adds macromolecule pore-forming agent, hydrophilic modifier, solvent and the like to prepare membrane casting liquid, and adopts a non-solvent induced phase separation method, namely a dry-wet spinning process to prepare the polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane. The addition of polyvinylidene fluoride improves the flexibility of polyvinyl chloride, so that the polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane has better flexibility; the polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane is filtered by adopting an external pressure mode, has good hydrophilicity and low cost, and can be applied to the aspects of drinking water filtration, municipal tap water, sewage treatment and the like.
Description
Technical Field
The invention relates to the field of porous membrane manufacturing, in particular to a polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane and a preparation method thereof by a non-solvent induced phase separation method.
Background
The hollow fiber membrane has the characteristics of low energy consumption, simple process, no pollution to the environment and the like in the using process, and is widely applied to civil and industrial water treatment at present. The polyvinyl chloride has high rigidity, higher strength, good chemical stability and acid and alkali resistance; compared with other membrane materials, the polyvinyl chloride material has wide sources and low price, and the polyvinyl chloride hollow fiber membrane has wide application prospect in the water treatment industry.
Polyvinyl chloride has high rigidity but poor flexibility, and a polyvinyl chloride hollow fiber membrane generally adopts an internal pressure filtration mode. When external pressure filters, certain deformation can take place during the hollow fiber membrane surface pressurized, because the pliability is poor, the deformation is difficult to resume, along with the service pressure increase, live time increases, and hollow fiber membrane can slowly be flattened, loses filtering capability.
Disclosure of Invention
Aiming at the poor flexibility of the polyvinyl chloride, the polyvinylidene fluoride is added for blending, the polyvinylidene fluoride has good flexibility, the flexibility of the polyvinyl chloride hollow fiber membrane is improved, and the polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane with excellent performance is prepared. The polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane prepared by the method adopts an external pressure filtration mode, changes a consistent internal pressure filtration mode of the polyvinyl chloride hollow fiber membrane, has higher packing density and lower cost price, and has very large application prospect.
The invention aims to provide a polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane. The hollow fiber membrane is filtered by adopting an external pressure mode, has higher strength and better flexibility, and has lower cost.
A polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane comprises the following components in percentage by weight:
polyvinyl chloride: 70 to 90 percent
Polyvinylidene fluoride: 0 to 20 percent
High-molecular additive: 0 to 20 percent.
A preparation method of a polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane comprises the following components in percentage by weight:
polyvinyl chloride: 13 to 20 percent
Polyvinylidene fluoride: 0 to 5
High-molecular additive: 5 to 25 percent
Water: 0 to 2 percent
Solvent: 50 to 80 percent.
Preferably, the polymerization degree of the polyvinyl chloride is 700-2000, more preferably 800-1500; the molecular weight of polyvinylidene fluoride is 15 to 100 ten thousand, more preferably 20 to 80 ten thousand.
Preferably, the polymer additive is selected from one or more of polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylene and methylcellulose, more preferably from one or two of polyethylene glycol and polyvinylpyrrolidone, the molecular weight of polyethylene glycol is 200-10000, more preferably 400-6000, and the K value of polyvinylpyrrolidone is 15-90, more preferably 30-80. The polymer additive plays a role in hydrophilic modification and also plays a role in a pore-forming agent, and the polymer additive playing a role in the pore-forming agent in the polymer additive can be separated out in the preparation process, so that micropores are formed in the membrane; the polymer additive functioning as a hydrophilic modifier is left inside the hollow fiber membrane to provide hydrophilicity to the hollow fiber membrane.
Preferably, the water is deionized water.
Preferably, the solvent is selected from one or more of dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, trimethyl phosphate and triethyl phosphate.
The invention also aims to provide a preparation method of the polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane, which is prepared by adopting a non-solvent induced phase separation method, namely a dry-wet process, and comprises the following preparation steps:
step (1): firstly, putting polyvinyl chloride, polyvinylidene fluoride, a polymer additive, water and a solvent into a dissolving kettle according to a certain proportion, and stirring for more than 20 hours at the temperature of 50-80 ℃ to fully and uniformly dissolve;
step (2): then stopping stirring, filtering, vacuumizing, defoaming and cooling to obtain a casting solution at 40-70 ℃;
and (3): then, conveying the casting solution to a bushing type spinning nozzle with the temperature of 40-70 ℃ through a metering pump under the action of nitrogen pressure, introducing internal solidification liquid into an inner hole of the spinning nozzle to form an inner hole of a hollow fiber, and extruding the inner hole of the hollow fiber into a hollow fiber shape;
and (4): and finally, allowing the hollow fiber to pass through an air distance of 10-120 mm, allowing the hollow fiber to enter an external solidification liquid at the temperature of 30-60 ℃ for solidification and molding, allowing the hollow fiber to be subjected to phase separation, allowing the hollow fiber to enter a cleaning liquid at the temperature of 30-60 ℃, and finally winding the hollow fiber through a winding wheel at the speed of 20-60 m/min to obtain the polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane.
In a preferred embodiment of the present invention, step (5) may be further included: and (3) soaking the polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane obtained in the step (4) in deionized water at the temperature of 30-60 ℃ for 2-6 h, and further removing the pore-forming agent and the solvent through soaking to stabilize the structure and the size of the membrane.
Preferably, the internal solidification liquid is a mixed solution of water and a solvent, the concentration of the solvent is 0-90%, and the concentration of the solvent is more preferably 10-70%; the external solidification liquid is a mixed solution of water and a solvent, the concentration of the solvent is 0-50%, more preferably 10-40%, and the cleaning liquid is deionized water. The water is deionized water, and the solvent is dimethylacetamide.
The invention has the following advantages:
according to the invention, polyvinylidene fluoride and polyvinyl chloride are blended, so that the flexibility of polyvinyl chloride is improved, and the prepared polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane has better flexibility and higher strength.
At present, the polyvinyl chloride hollow fiber membrane is basically filtered by adopting an internal pressure mode, and liquid to be filtered firstly enters an inner hole of the hollow fiber membrane and then permeates from the inner surface of the hollow fiber membrane to the outer surface through a membrane wall. In order to prevent the inner hole from being easily blocked, the inner diameter of the internal pressure hollow fiber membrane is made larger, and the inner diameter and the outer diameter of the internal pressure membrane are made larger than those of the external pressure membrane; when the internal pressure of the membrane is too high, the membrane can break and lose the filtering function. The filtration flux of the hollow fiber membrane is calculated by the size of the membrane area, the area of the internal pressure membrane is calculated by the inner surface, the area of the external pressure membrane is calculated by the outer surface, the loading density of the internal pressure membrane is smaller than that of the external pressure membrane, and the cost of the internal pressure membrane made of the same material is higher than that of the external pressure membrane. The polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane prepared by the method adopts an external pressure filtration mode, the filling density of membrane filaments is higher than that of an internal pressure polyvinyl chloride hollow fiber membrane, and the volume space and the installation and use space of a membrane module product can be saved; the external pressure polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane prepared by the method is low in price, is lower in price than the external pressure polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane, and has a very large application prospect.
The polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane prepared by the invention has the inner diameter of 0.4-0.9 mm, the outer diameter of 0.8-1.5 mm, the tensile breaking strength of 3.0-6.0 MPa, the breaking elongation of 70-150 percent and the pure water flux of 300-2800L/M 2 H (0.1 MPa, 25 ℃). The polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane prepared by the method can be applied to the aspects of drinking water filtration treatment, municipal tap water treatment, sewage treatment and the like.
Detailed description of the preferred embodiments
The present invention will be further described with reference to the following examples, which are intended to be part of the present invention, not to be construed as limiting the invention, and any modifications, substitutions, improvements and the like within the scope of the present invention shall be included.
The present invention will be described in detail below with reference to specific examples.
Example 1: weighing 16% of polyvinyl chloride with polymerization degree of 1000, 2% of polyvinylidene fluoride with molecular weight of 32 ten thousand, 10% of polyethylene glycol 400, 5% of polyvinylpyrrolidone K45, 1% of deionized water and 66% of dimethylacetamide according to weight percentage, putting the materials into a reaction kettle, stirring the materials at 70 ℃ for 20 hours, stopping stirring, filtering, vacuumizing, defoaming and cooling the materials to obtain casting solution at 60 ℃, conveying the casting solution to a bushing type spinning nozzle at 60 ℃ through a metering pump under the action of nitrogen pressure, introducing internal solidification solution of 50 ℃ and 50% of dimethylacetamide aqueous solution into the bushing, extruding the casting solution into hollow fibers, and passing the hollow fibers through 50mm of airAnd (2) allowing the mixture to enter an external solidification solution of deionized water at 40 ℃ for solidification and formation, allowing the mixture to undergo phase separation, allowing the mixture to enter a cleaning solution at 40 ℃, winding the mixture by a winding wheel at a speed of 50m/min, and soaking the collected membrane filaments in the deionized water at 50 ℃ for 3 hours to obtain the polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane. The prepared polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane has the inner diameter of 0.52mm, the outer diameter of 1.02mm and the pure water flux of 950L/M 2 H (0.1 MPa, 25 ℃), tensile breaking strength of 4.2MPa, elongation at break of 100%.
Comparative example 1: weighing 18 percent of polyvinyl chloride with polymerization degree of 1000, 10 percent of polyethylene glycol 400, 5 percent of polyvinylpyrrolidone K30, 1 percent of water and 66 percent of dimethylacetamide according to the weight percentage, putting the polyvinyl chloride, the polyethylene glycol and the polyvinylpyrrolidone into a reaction kettle, and preparing the polyvinyl chloride hollow fiber membrane by adopting the preparation process of the embodiment 1, wherein the inner diameter of the hollow fiber membrane is 0.51mm, the outer diameter of the hollow fiber membrane is 1.00mm, and the pure water flux of the hollow fiber membrane is 890L/M 2 H (0.1 MPa, 25 ℃), tensile breaking strength of 4.6MPa, elongation at break of 65%.
Example 2: weighing 16% of polyvinyl chloride with polymerization degree of 1000, 3% of polyvinylidene fluoride with molecular weight of 32 ten thousand, 10% of polyethylene glycol 400, 5% of polyvinylpyrrolidone K30, 1% of deionized water and 65% of dimethylacetamide according to weight percentage, putting the materials into a reaction kettle, stirring for 20 hours at 75 ℃, stopping stirring, filtering, vacuumizing, defoaming and cooling to obtain a casting solution at 70 ℃, conveying the casting solution to a bushing type spinning nozzle at 70 ℃ through a metering pump under the action of nitrogen pressure, introducing an internal solidification solution of a dimethyl acetamide aqueous solution at 50 ℃ and 60% into the bushing, extruding into a hollow fiber shape, then entering an external solidification solution of deionized water at 40 ℃ for solidification and forming through an air distance of 50mm, simultaneously carrying out phase separation, then entering a cleaning solution at 40 ℃, finally rolling through a wire winding wheel at a speed of 50m/min, and then soaking the collected film filaments in deionized water at 50 ℃ for 3 hours to obtain the polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane. The prepared polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane has the inner diameter of 0.50mm, the outer diameter of 1.02mm and the pure water flux of 780L/M 2 H (0.1 MPa, 25 ℃), tensile breaking strength of 5.1MPa, elongation at break of 95%.
Example 3: weighing 15% of polyvinyl chloride with polymerization degree of 1000, 1.7% of polyvinylidene fluoride with molecular weight of 48 ten thousand, 13% of polyethylene glycol 400, 4% of polyvinylpyrrolidone K30, 1% of deionized water and 65.3% of dimethylacetamide according to weight percentage, putting the materials into a reaction kettle, stirring for 20 hours at 70 ℃, then stopping stirring, filtering, vacuumizing, defoaming and cooling to obtain a casting solution with the temperature of 60 ℃, conveying the casting solution to a bushing type spinning nozzle with the temperature of 60 ℃ through a metering pump under the action of nitrogen pressure, introducing an internal solidification solution with 50 ℃ and 50% of dimethylacetamide aqueous solution into the bushing, extruding into a hollow fiber shape, then passing through an air distance of 50mm, entering an external solidification solution with deionized water with the temperature of 40 ℃ for solidification and forming, simultaneously carrying out phase separation, then entering a cleaning solution with the temperature of 40 ℃, finally rolling up through a wire winding wheel at the speed of 50m/min, and then putting the collected membrane wires into deionized water with the temperature of 40 ℃ for soaking for 3 hours to obtain the polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane. The prepared polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane has the inner diameter of 0.52mm, the outer diameter of 0.80mm and the pure water flux of 1380L/M 2 H (0.1 MPa, 25 ℃), tensile breaking strength of 3.8MPa, elongation at break of 130%.
Example 4: weighing 14% of polyvinyl chloride with the polymerization degree of 1300, 1.5% of polyvinylidene fluoride with the molecular weight of 58 ten thousand, 15% of polyethylene glycol 400, 4% of polyvinylpyrrolidone K30, 1% of deionized water and 64.5% of dimethylacetamide according to weight percentage, putting the materials into a reaction kettle, stirring for 20 hours at the temperature of 70 ℃, stopping stirring, filtering, vacuumizing, defoaming and cooling to obtain a casting solution at the temperature of 60 ℃, conveying the casting solution to a bushing type spinning nozzle at the temperature of 60 ℃ through a metering pump under the action of nitrogen pressure, introducing an internal solidification solution of 50 ℃ and 50% of dimethylacetamide aqueous solution into the bushing, extruding into a hollow fiber shape, then passing through an air distance of 50mm, entering an external solidification solution of 40 ℃ deionized water for solidification and forming, simultaneously carrying out phase separation, then entering a cleaning solution at the temperature of 40 ℃, finally rolling by a wire winding wheel at the speed of 50m/min, and then soaking collected membrane wires in the deionized water at the temperature of 50 ℃ for 3 hours to obtain the polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane. The prepared polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane has the inner diameter of 0.52mm, the outer diameter of 0.82mm and the pure water flux of 1700L/M 2 H (0.1 MPa, 25 ℃), tensile breaking strength of 3.5MPa, elongation at break of 140%.
Claims (10)
1. A polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane is characterized by comprising the following components in percentage by weight:
polyvinyl chloride: 80 to 100 percent
Polyvinylidene fluoride: 0 to 20 percent
High-molecular additive: 0 to 20 percent.
2. The polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane of claim 1, wherein the hollow fiber membrane has an inner diameter of 0.4 to 0.9mm, an outer diameter of 0.8 to 1.5mm, a tensile break strength of 3.0 to 6.0MPa, an elongation at break of 70 to 150%, a pure water flux of 300 to 2800L/M 2 ·H（0.1MPa、25℃）。
3. The polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane according to claim 1 or 2, characterized in that the preparation raw material comprises the following components by weight percent:
polyvinyl chloride: 13 to 20 percent
Polyvinylidene fluoride: 0 to 5
High-molecular additive: 5 to 25 percent
Water: 0 to 2 percent
Solvent: 50 to 80 percent.
4. The raw material for preparing the polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane according to claim 1 or 3, wherein the polymerization degree of the polyvinyl chloride is 700 to 2000, and the molecular weight of the polyvinylidene fluoride is 15 to 100 ten thousand.
5. The raw material for preparing the polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane according to claim 1 or 3, wherein the polymer additive is one or more selected from polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylene, and methyl cellulose, and the polymer additive functions as both a pore-forming agent and a hydrophilic modifier.
6. The polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane preparation material according to claim 3, wherein the water is deionized water.
7. The polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane preparation raw material according to claim 3, wherein the solvent is one or more selected from dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, trimethyl phosphate and triethyl phosphate.
8. A preparation method of a polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane is characterized in that the hollow fiber membrane is prepared by a non-solvent induced phase separation method, namely a dry-wet process, and the preparation method comprises the following steps:
step (1): firstly, putting polyvinyl chloride, polyvinylidene fluoride, a high-molecular additive, water and a solvent into a dissolving kettle according to a certain proportion, and stirring for more than 20 hours at the temperature of 50-80 ℃ to fully and uniformly dissolve;
step (2): then stopping stirring, filtering, vacuumizing, defoaming and cooling to obtain a casting solution at 40-70 ℃;
and (3): then, conveying the casting solution to a bushing type spinning nozzle with the temperature of 40-70 ℃ through a metering pump under the action of nitrogen pressure, introducing internal solidification liquid into an inner hole of the spinning nozzle to form an inner hole of a hollow fiber, and extruding the inner hole of the hollow fiber into a hollow fiber shape;
and (4): and finally, allowing the hollow fiber to pass through an air distance of 10-120 mm, allowing the hollow fiber to enter external solidification liquid at the temperature of 30-60 ℃ for solidification and forming, simultaneously performing phase separation, then allowing the hollow fiber to enter cleaning liquid at the temperature of 30-60 ℃, and finally winding the hollow fiber through a winding wheel at the speed of 20-60 m/min to obtain the polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane.
9. The method for preparing a polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane according to claim 8, wherein: may further comprise step (5): and (3) soaking the polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane obtained in the step (4) in deionized water at the temperature of 30-60 ℃ for 2-6 h.
10. The preparation method of the polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane according to claim 8, characterized in that the internal solidification liquid is a mixed solution of water and a solvent, and the concentration of the solvent is 0-90%; the external solidification liquid is a mixed solution of water and a solvent, and the concentration of the solvent is 0-50%; the cleaning solution is deionized water. The water is deionized water, and the solvent is dimethylacetamide.
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| CN202310044333.3A CN115970519A (en) | 2023-01-30 | 2023-01-30 | Polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane and preparation method thereof |
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| CN202310044333.3A CN115970519A (en) | 2023-01-30 | 2023-01-30 | Polyvinyl chloride/polyvinylidene fluoride blended hollow fiber membrane and preparation method thereof |
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