CN112337322A - Poly 4-methyl-1-pentene hollow fiber membrane and preparation method thereof - Google Patents
Poly 4-methyl-1-pentene hollow fiber membrane and preparation method thereof Download PDFInfo
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- CN112337322A CN112337322A CN202011251980.4A CN202011251980A CN112337322A CN 112337322 A CN112337322 A CN 112337322A CN 202011251980 A CN202011251980 A CN 202011251980A CN 112337322 A CN112337322 A CN 112337322A
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0016—Coagulation
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- 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
Abstract
The invention provides a preparation method of a poly 4-methyl-1-pentene hollow fiber membrane, which adopts a thermal phase separation method, obtains a homogeneous solution by controlling the mixing temperature of 4-methyl-1-pentene resin and a diluent, takes the homogeneous solution as a spinning solution to be extruded together with a core solution, enters a coagulating bath through an air layer to carry out solid-liquid phase separation, can control the aperture and porosity of the hollow fiber membrane by controlling the temperature of the coagulating bath, and finally removes the diluent by soaking to obtain the poly 4-methyl-1-pentene hollow fiber membrane with uniform aperture distribution. The results of the examples show that the porosity of the support layer in the poly-4-methyl-1-pentene hollow fiber membrane provided by the present invention is 37%, and the pore size distribution20 to 200nm, O of a hollow fiber membrane2Transmission coefficient of 142Barrer, N2Transmittance of 156Barrer, CO2The transmission factor was 138 Barrer.
Description
Technical Field
The invention relates to the technical field of fiber membrane materials, in particular to a poly (4-methyl-1-pentene) hollow fiber membrane and a preparation method thereof.
Background
The gas membrane separation has the advantages of high separation effect, low energy consumption, simple operation and the like, and shows unique advantages in competition with the traditional separation technology such as adsorption, absorption, cryogenic separation and the like. At present, the separation membrane can be divided into four structures, namely a hollow fiber type structure, a hollow tube type structure, a flat plate type structure and a roll type structure according to the structural form of the separation membrane, wherein the hollow fiber type structure has a self-supporting structure, the preparation process of a component is simple, the amplification effect is small, a larger membrane area can be provided in a unit volume, the stacking density is larger than that of a tubular membrane, and the pretreatment and maintenance are simpler than that of other membranes.
The poly-4-methyl-1 pentene serving as an excellent gas separation membrane material has the advantages of good heat resistance, high gas selective separation performance, large permeation quantity, good mechanical strength and the like, and is widely applied to the technical fields of chemical industry, environmental protection, medical treatment and the like. However, the poly 4-methyl-1 pentene hollow fiber gas separation membrane prepared in the prior art still has the defect of uneven pore size distribution, which further causes low membrane separation performance, for example, patent CN101623600A discloses a poly 4-methyl-1 pentene hollow fiber gas separation membrane, which utilizes the fact that the lamellar crystal structure of the fiber is pulled apart to form micropores under the stretching state, but the stretching distance of the lamellar crystal is difficult to control in the stretching process, so that the pore size distribution of the membrane is uneven, which further affects the separation performance of the membrane.
Disclosure of Invention
The invention aims to provide a poly 4-methyl-1-pentene hollow fiber membrane and a preparation method thereof, and the poly 4-methyl-1-pentene hollow fiber membrane provided by the invention has the advantages of uniform pore size distribution, good separation performance and better mechanical performance.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a poly 4-methyl-1-pentene hollow fiber membrane, which comprises the following steps:
(1) mixing 4-methyl-1-pentene resin, a diluent, a water-soluble additive and a water-insoluble additive to obtain a spinning solution; the mixing temperature is 130-180 ℃;
(2) extruding the spinning solution obtained in the step (1) and core solution together, and allowing the extruded spinning solution and core solution to enter a coagulating bath through an air layer to obtain a nascent poly (4-methyl-1-pentene) hollow fiber membrane; the temperature of the coagulating bath is 30-50 ℃;
(3) and (3) soaking the nascent poly-4-methyl-1-pentene hollow fiber membrane obtained in the step (2) in a soaking solution to obtain a poly-4-methyl-1-pentene hollow fiber membrane.
Preferably, in the step (1), the spinning solution contains 25 to 55 mass% of 4-methyl-1-pentene resin, 35 to 65 mass% of diluent, 5 to 12 mass% of water-soluble additive and 3 to 10 mass% of water-insoluble additive.
Preferably, the diluent in the step (1) comprises one or more of diethyl phthalate, dioctyl phthalate, epoxidized soybean oil, dioctyl adipate and N-methyldipryrolidone.
Preferably, the water-soluble additive in step (1) comprises polyethylene glycol-400 and/or small molecule salts.
Preferably, the water-insoluble additive in the step (1) includes silica and/or a polymer resin.
Preferably, the core liquid in step (2) comprises one or more of water, diethyl phthalate, dioctyl phthalate, epoxidized soybean oil, octyl adipate and N-methyl dipyrrolidone.
Preferably, the length of the air layer in the step (2) is 3-10 cm.
Preferably, the soaking solution in the step (3) is a mixed solution of a water-soluble additive and absolute ethyl alcohol.
The invention provides a poly 4-methyl-1-pentene hollow fiber membrane prepared by the preparation method in the technical scheme, which comprises an outer compact layer and an inner supporting layer, wherein the porosity of the supporting layer is 20-55%, and the pore size distribution is 20-200 nm.
Preferably, the thickness of the compact layer is 10-200 nm; the thickness of the supporting layer is 150-600 mu m; the outer diameter of the poly 4-methyl-1-pentene hollow fiber membrane is 500 to 1500 μm.
The invention provides a preparation method of a poly 4-methyl-1-pentene hollow fiber membrane, which comprises the following steps: mixing 4-methyl-1-pentene resin, a diluent, a water-soluble additive and a water-insoluble additive to obtain a spinning solution; the mixing temperature is 130-180 ℃; extruding the spinning solution and the core solution together, and allowing the extruded spinning solution and the core solution to enter a coagulating bath through an air layer to obtain a nascent poly (4-methyl-1-pentene) hollow fiber membrane; the temperature of the coagulating bath is 30-50 ℃; and soaking the nascent poly-4-methyl-1-pentene hollow fiber membrane to obtain the poly-4-methyl-1-pentene hollow fiber membrane. The invention adopts a thermally induced phase separation method, obtains homogeneous solution by controlling the mixing temperature of 4-methyl-1-pentene resin and a diluent, takes the homogeneous solution as spinning solution to be extruded together with core solution, enters a coagulating bath through an air layer to carry out solid-liquid phase separation, can control the aperture and porosity of a hollow fiber membrane by controlling the temperature of the coagulating bath, and finally removes the diluent by soaking, thereby obtaining the poly-4-methyl-1-pentene hollow fiber membrane with uniform aperture distribution. The results of the examples show that the porosity of the support layer in the poly-4-methyl-1-pentene hollow fiber membrane provided by the invention is 37%, the pore size distribution is 20-200 nm, and the O content of the hollow fiber membrane2Transmission coefficient of 142Barrer, N2Transmittance of 156Barrer, CO2Transmission coefficient of 138Barrer, O2/N2A transmittance of 69, CO2/N2The selection coefficient is 56, the tensile strength is 10-20 MPa, and the impact strength is 5-15 MPa.
The preparation method of the poly 4-methyl-1-pentene hollow fiber membrane provided by the invention is simple to operate, the preparation process is easy to be continuous, and the industrial implementation is convenient.
Drawings
FIG. 1 is a cross-sectional electron microscope image of a poly-4-methyl-1-pentene hollow fiber membrane prepared in example 1 of the present invention;
FIG. 2 is a partial cross-sectional electron microscope image of a poly-4-methyl-1-pentene hollow fiber membrane prepared in example 1 of the present invention.
Detailed Description
The invention provides a preparation method of a poly 4-methyl-1-pentene hollow fiber membrane, which comprises the following steps:
(1) mixing 4-methyl-1-pentene resin, a diluent, a water-soluble additive and a water-insoluble additive to obtain a spinning solution; the mixing temperature is 130-180 ℃;
(2) extruding the spinning solution obtained in the step (1) and core solution together, and allowing the extruded spinning solution and core solution to enter a coagulating bath through an air layer to obtain a nascent poly (4-methyl-1-pentene) hollow fiber membrane; the temperature of the coagulating bath is 30-50 ℃;
(3) and (3) soaking the nascent poly-4-methyl-1-pentene hollow fiber membrane obtained in the step (2) in a soaking solution to obtain a poly-4-methyl-1-pentene hollow fiber membrane.
The spinning solution is obtained by mixing 4-methyl-1-pentene resin, a diluent, a water-soluble additive and a water-insoluble additive.
In the invention, the mass content of the 4-methyl-1-pentene resin in the spinning solution is preferably 25-55%, and more preferably 45-55%. The invention takes 4-methyl-1-pentene resin as a raw material, and prepares the poly-4-methyl-1-pentene hollow fiber membrane with uniform pore size distribution by adopting a thermally induced phase separation method. In the present invention, the source of the 4-methyl-1-pentene resin is not particularly limited, and a commercially available product may be used.
In the invention, the mass content of the diluent in the spinning solution is preferably 35-65%, more preferably 35-55%, and most preferably 35-45%. In the present invention, the diluent preferably comprises one or more of diethyl phthalate, dioctyl phthalate, epoxidized soybean oil, octyl adipate and N-methyl dipyrrolidone, more preferably one or more of diethyl phthalate, dioctyl phthalate and octyl adipate, and most preferably diethyl phthalate or dioctyl phthalate. In the invention, the diluent and the 4-methyl-1-pentene resin form a homogeneous solution, solid-liquid phase separation is carried out by cooling in a coagulating bath, and finally the diluent is removed by soaking, thereby obtaining the poly-4-methyl-1-pentene hollow fiber membrane with uniform pore size distribution.
In the invention, the mass content of the water-soluble additive in the spinning solution is preferably 5-12%, more preferably 6-10%, and most preferably 7-9%. In the present invention, the water-soluble additive preferably includes polyethylene glycol-400 and/or small molecule salts. In the present invention, the small-molecule salt is preferably calcium chloride, sodium chloride or lithium chloride, and more preferably calcium chloride or lithium chloride. In the invention, the use of the water-soluble additive is beneficial to reducing the viscosity of the spinning solution so as to facilitate the smooth extrusion of the spinning solution.
In the invention, the mass content of the water-insoluble additive in the spinning solution is preferably 3-10%, more preferably 3-8%, and most preferably 3-5%. In the present invention, the water-insoluble additive preferably includes silica and/or a polymer resin, more preferably silica. In the present invention, the polymer resin is preferably perfluoroethylene propylene or polytetrafluoroethylene, more preferably perfluoroethylene propylene. In the invention, the addition of the water-insoluble additive is beneficial to obtaining stable and uniform spinning solution so as to facilitate the subsequent spinning process.
In the invention, the mixing temperature is 130-180 ℃, and preferably 150-170 ℃. The invention controls the mixing temperature in the range, is beneficial to uniformly mixing the 4-methyl-1-pentene resin, the diluent, the water-soluble additive and the water-insoluble additive to obtain a uniform solution as a spinning solution, and further finally obtains the poly-4-methyl-1-pentene hollow fiber membrane with uniform pore size distribution.
After the mixing is completed, the invention preferably defoams the mixed product to obtain the spinning solution. In the present invention, the defoaming is preferably performed under constant temperature and vacuum conditions; the defoaming temperature is preferably 100-150 ℃, and more preferably 110-120 ℃; the time for defoaming is preferably 3-6 h, and more preferably 5-6 h. In the invention, bubbles contained in the spinning solution are removed through defoaming so as to ensure the normal operation of the subsequent spinning process.
After the spinning solution is obtained, the spinning solution and the core solution are extruded together, and enter a coagulating bath through an air layer to obtain the nascent poly-4-methyl-1-pentene hollow fiber membrane.
In the present invention, the bore fluid preferably includes one or more of water, diethyl phthalate, dioctyl phthalate, epoxidized soybean oil, octyl adipate, and N-methyldipryrolidone, more preferably one or more of water, diethyl phthalate, and dioctyl phthalate. By controlling the type of the core liquid, the invention effectively avoids the adverse effects generated by the dynamics and thermodynamics of the membrane material, and is beneficial to ensuring the separation performance of the poly 4-methyl-1-pentene hollow fiber membrane.
In the present invention, the extrusion manner preferably includes twin-screw extrusion or autoclave pressure extrusion, and more preferably twin-screw extrusion. In the invention, the speed of the main machine for extruding the screw is preferably 4-12 r/min, and more preferably 6-12 r/min. In the present invention, the extrusion temperature is preferably controlled by five zones, and the temperature of each zone is preferably: the temperature of the zone 1 is 100-120 ℃, the temperature of the zone 2 is 120-140 ℃, the temperature of the zone 3 is 130-150 ℃, the temperature of the zone 4 is 150-170 ℃, and the temperature of the zone 5 is 160-180 ℃.
In the present invention, the process of co-extruding the spinning solution and the core solution is specifically preferably: the spinning solution is extruded out through the annular hole of the spinning nozzle, and the core solution is extruded out through the inner hole of the spinning nozzle. In the present invention, the spinneret is preferably an insertion tube spinneret; the outer diameter of the spinning nozzle is preferably 500-1700 mu m, and more preferably 700-1500 mu m; the inner diameter of the spinneret is preferably 100-400 μm, and more preferably 200-300 μm; the source of the spinneret is preferably a spinneret manufactured by Tianjin New three-dimensional Membrane technology, Inc.
In the present invention, the spinning solution and the core solution are preferably injected into the spinneret through a metering pump. In the invention, the temperature of the metering pump is preferably 170-190 ℃, and more preferably 175-185 ℃. The temperature of the metering pump is controlled within the range, the temperature of the spinning solution can be kept, and then the spinning solution enters the coagulating bath to undergo solid-liquid phase separation due to temperature reduction, so that the poly 4-methyl-1-pentene hollow fiber membrane is obtained.
In the invention, the dosage of the spinning solution is preferably 1000-3000 mL/m3More preferably 1200 to 1800mL/m3. In the invention, the dosage of the core liquid is preferably 200-1000 mL/m3More preferably 400E800mL/m3. The invention controls the dosage of the spinning solution and the core solution within the range, and is beneficial to obtaining the poly 4-methyl-1-pentene hollow fiber membrane with excellent separation performance.
In the present invention, the length of the air layer is preferably 3 to 10cm, and more preferably 3 to 8 cm. The present invention controls the length of the air layer within the above range, and is advantageous for obtaining a poly 4-methyl-1-pentene hollow fiber membrane having excellent separation performance.
In the invention, the spinning solution and the core solution are extruded and enter a coagulating bath through an air layer, and the solid-liquid phase separation is carried out by cooling, thereby obtaining the nascent poly-4-methyl-1-pentene hollow fiber membrane. The present invention preferably uses an aqueous solution as the coagulation bath. In the invention, the temperature of the coagulating bath is 30-50 ℃, and preferably 30-40 ℃. The invention can control the aperture and porosity of the hollow fiber membrane by controlling the temperature of the coagulating bath, is beneficial to obtaining the poly 4-methyl-1-pentene hollow fiber membrane with uniform aperture distribution, and solves the problems of nonuniform aperture distribution and uncontrollable thickness of a compact layer of the poly 4-methyl-1-pentene hollow fiber membrane.
After the nascent poly-4-methyl-1-pentene hollow fiber membrane is obtained, the poly-4-methyl-1-pentene hollow fiber membrane is soaked in the soaking solution to obtain the poly-4-methyl-1-pentene hollow fiber membrane.
In the present invention, the soaking solution is preferably a mixed solution of a water-soluble additive and absolute ethyl alcohol. In the invention, the mass content of the water-soluble additive in the soaking solution is preferably 10-30%, and more preferably 15-25%; the mass content of the absolute ethyl alcohol in the soaking solution is preferably 50-90%, and more preferably 75-85%. The invention removes the diluent by soaking, and then obtains the poly 4-methyl-1-pentene hollow fiber membrane. In the present invention, the water-soluble additive preferably includes polyethylene glycol-400 and/or small molecule salts. In the present invention, the small-molecule salt is preferably calcium chloride, sodium chloride or lithium chloride, and more preferably calcium chloride or lithium chloride.
In the present invention, the soaking is preferably performed at room temperature; the soaking time is preferably 24-48 hours, and more preferably 24-36 hours.
The invention adopts a thermally induced phase separation method, obtains homogeneous solution by controlling the mixing temperature of 4-methyl-1-pentene resin and a diluent, takes the homogeneous solution as spinning solution to be extruded together with core solution, enters a coagulating bath through an air layer to carry out solid-liquid phase separation, can control the aperture and porosity of a hollow fiber membrane by controlling the temperature of the coagulating bath, and finally removes the diluent by soaking, thereby obtaining the poly-4-methyl-1-pentene hollow fiber membrane with uniform aperture distribution.
The invention provides a poly 4-methyl-1-pentene hollow fiber membrane prepared by the preparation method in the technical scheme, which comprises an outer compact layer and an inner supporting layer.
In the invention, the porosity of the supporting layer is 20-55%, preferably 35-45%; the pore size distribution of the support layer is 20-200 nm, preferably 50-110 nm.
In the invention, the thickness of the dense layer is preferably 10-200 nm, and more preferably 50-150 nm; the thickness of the support layer is preferably 150-600 μm, and more preferably 200-500 μm; the outer diameter of the poly 4-methyl-1-pentene hollow fiber membrane is preferably 500 to 1500 μm, and more preferably 600 to 1400 μm.
In the present invention, O of the poly-4-methyl-1-pentene hollow fiber membrane2The transmission coefficient is preferably 70 to 230Barrer, and more preferably 100 to 200 Barrer; n is a radical of2The transmission coefficient is preferably 85 to 310Barrer, and more preferably 150 to 200 Barrer; CO 22The transmission coefficient is preferably 80 to 260Barrer, and more preferably 120 to 180 Barrer; o is2/N2The transmission selection coefficient is preferably 20 to 85, more preferably 50 to 75; CO 22/N2The transmission selection coefficient is preferably 40 to 90, and more preferably 50 to 70.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Preparing a spinning solution: mixing 4-methyl-1-pentene resin, diethyl phthalate, calcium chloride and silicon dioxide at 150 ℃, and then defoaming at constant temperature of 120 ℃ for 5 hours to obtain spinning solution; wherein the mass content of the 4-methyl-1-pentene resin in the spinning solution is 45%; the mass content of diethyl phthalate is 43 percent; the mass content of calcium chloride is 7 percent, and the mass content of silicon dioxide is 5 percent;
(2) preparation of nascent hollow fiber membrane: injecting the spinning solution into an annular hole of an inserted tubular spinneret through a metering pump, taking water as core solution, injecting the core solution into an inner hole of the inserted tubular spinneret through the metering pump, simultaneously extruding the spinning solution and the core solution in a screw extrusion mode, and then entering a 30 ℃ aqueous solution through an air layer of 4cm for cooling and forming to obtain a nascent hollow fiber membrane; wherein the outer diameter of the spinneret is 1200 μm, and the inner diameter of the spinneret is 300 μm; the temperature of the metering pump was 175 ℃; the dosage of the spinning solution is 1500mL/m3The dosage of the core liquid is 500mL/m3(ii) a The speed of a main machine for screw extrusion is 8r/min, and the temperature of each zone is as follows: zone 1 at 100 ℃, zone 2 at 125 ℃, zone 3 at 130 ℃, zone 4 at 150 ℃, and zone 5 at 165 ℃;
(3) preparation of hollow fiber membrane: taking a mixed solution of calcium chloride and absolute ethyl alcohol as a soaking solution, and soaking the nascent hollow fiber membrane for 24 hours at room temperature (25 ℃) to obtain a poly 4-methyl-1-pentene hollow fiber membrane; wherein the mass content of the calcium chloride in the soak solution is 15%, and the mass content of the absolute ethyl alcohol is 85%.
The thickness of the dense layer of the poly 4-methyl-1-pentene hollow fiber membrane prepared in the embodiment is 100nm, the thickness of the supporting layer is 400 μm, the porosity is 41%, and the pore size distribution is 80-100 nm; the outer diameter of the hollow fiber membrane was 1100 μm, and the O content of the hollow fiber membrane2Transmission coefficient of 153Barrer, N2A transmittance of 182Barrer, CO2A transmittance of 141Barrer, O2/N2A transmission selection coefficient of 65, CO2/N2The transmission selection coefficient is 52, the tensile strength is 12MPa, and the impact strength is 7 MPa.
FIG. 1 is a cross-sectional electron microscope image of the hollow fiber membrane of poly-4-methyl-1-pentene prepared in this example, and it can be seen from FIG. 1 that the hollow fiber membrane of poly-4-methyl-1-pentene is hollow and comprises a dense layer as an outer layer and a supporting layer as an inner layer.
FIG. 2 is a partial cross-sectional electron microscope image of the hollow fiber membrane of poly-4-methyl-1-pentene prepared in this example, and it can be seen from FIG. 2 that the pore size distribution of the prepared hollow fiber membrane of poly-4-methyl-1-pentene is uniform.
Example 2
(1) Preparing a spinning solution: mixing 4-methyl-1-pentene resin, dioctyl phthalate, polyethylene glycol-400 and silicon dioxide at 160 ℃, and then defoaming at 125 ℃ for 6 hours at constant temperature to obtain spinning solution; wherein the mass content of the 4-methyl-1-pentene resin in the spinning solution is 50 percent; the mass content of the dioctyl phthalate is 40 percent; the mass content of the polyethylene glycol-400 is 6 percent, and the mass content of the silicon dioxide is 4 percent;
(2) preparation of nascent hollow fiber membrane: injecting the spinning solution into an annular hole of an inserted tubular spinneret through a metering pump, taking water as core solution, injecting the core solution into an inner hole of the inserted tubular spinneret through the metering pump, simultaneously extruding the spinning solution and the core solution in a screw extrusion mode, and then entering into 40 ℃ aqueous solution through an air layer of 6cm for cooling and forming to obtain a nascent hollow fiber membrane; wherein the outer diameter of the spinneret is 1300 μm, and the inner diameter of the spinneret is 350 μm; the temperature of the metering pump is 180 ℃; the dosage of the spinning solution is 1600mL/m3The dosage of the core liquid is 600mL/m3(ii) a The speed of a main machine for screw extrusion is 8r/min, and the temperature of each zone is as follows: zone 1 110 ℃, zone 2 125 ℃, zone 3, zone 4, 150 ℃, and zone 5 of 170 ℃;
(3) preparation of hollow fiber membrane: taking a mixed solution of polyethylene glycol-400 and absolute ethyl alcohol as a soaking solution, and soaking the nascent hollow fiber membrane for 24 hours at room temperature (25 ℃) to obtain a poly 4-methyl-1-pentene hollow fiber membrane; wherein the mass content of the polyethylene glycol-400 in the soaking solution is 20%, and the mass content of the absolute ethyl alcohol is 80%.
The thickness of the dense layer of the hollow fiber membrane of poly-4-methyl-1-pentene prepared in this example was 120nm, and the thickness of the support layerThe thickness is 350 mu m, the porosity is 36%, and the pore size distribution is 70-120 nm; the outer diameter of the hollow fiber membrane was 1250. mu.m, and O of the hollow fiber membrane2Transmission coefficient of 137Barrer, N2Transmission coefficient 161Barrer, CO2A transmittance of 141Barrer, O2/N2A transmission selection coefficient of 71, CO2/N2The transmission selection coefficient is 46, the tensile strength is 13MPa, and the impact strength is 9 MPa.
Example 3
(1) Preparing a spinning solution: mixing 4-methyl-1-pentene resin, dioctyl phthalate, sodium chloride and polytetrafluoroethylene at 170 ℃, and then defoaming at 125 ℃ for 4 hours at constant temperature to obtain spinning solution; wherein the mass content of the 4-methyl-1-pentene resin in the spinning solution is 55%; the mass content of the dioctyl phthalate is 35 percent; the mass content of sodium chloride is 7 percent, and the mass content of polytetrafluoroethylene is 3 percent;
(2) preparation of nascent hollow fiber membrane: injecting the spinning solution into an annular hole of an inserted tubular spinneret through a metering pump, taking water as core solution, injecting the core solution into an inner hole of the inserted tubular spinneret through the metering pump, simultaneously extruding the spinning solution and the core solution in a screw extrusion mode, and then entering into 40 ℃ aqueous solution through an air layer of 6cm for cooling and forming to obtain a nascent hollow fiber membrane; wherein the outer diameter of the spinneret is 1450 μm, and the inner diameter of the spinneret is 400 μm; the temperature of the metering pump was 175 ℃; the dosage of the spinning solution is 1700mL/m3The dosage of the core liquid is 800mL/m3(ii) a The speed of a main machine for screw extrusion is 8r/min, and the temperature of each zone is as follows: zone 1100 ℃, zone 2 120 ℃, zone 3 130 ℃, zone 4 150 ℃, and zone 5 ℃ 160 ℃;
(3) preparation of hollow fiber membrane: soaking the nascent hollow fiber membrane for 24 hours at room temperature (25 ℃) by taking a mixed solution of sodium chloride and absolute ethyl alcohol as a soaking solution to obtain a poly 4-methyl-1-pentene hollow fiber membrane; wherein the mass content of sodium chloride in the soaking solution is 18 percent, and the mass content of absolute ethyl alcohol is 82 percent.
The thickness of the dense layer of the poly 4-methyl-1-pentene hollow fiber membrane prepared in this example was 140nm, the thickness of the support layer was 500 μm, the porosity was 29%, and the pores were formedThe diameter distribution is 90-110 nm; the outer diameter of the hollow fiber membrane was 1300 μm, and the O content of the hollow fiber membrane2Transmission coefficient of 112Barrer, N2Transmittance of 143Barrer, CO2Transmission coefficient of 109Barrer, O2/N2A transmission selection coefficient of 75, CO2/N2The transmission selection coefficient is 48, the tensile strength is 16MPa, and the impact strength is 10 MPa.
Example 4
(1) Preparing a spinning solution: mixing 4-methyl-1-pentene resin, octanediol adipate, lithium chloride and polyfluorinated ethylene propylene at 170 ℃, and then defoaming at the constant temperature of 130 ℃ for 6 hours to obtain a spinning solution; wherein the mass content of the 4-methyl-1-pentene resin in the spinning solution is 52 percent; the mass content of the adipic acid octyl diester is 35 percent; the mass content of lithium chloride is 9 wt%, and the mass content of polyperfluorinated ethylene propylene is 4%;
(2) preparation of nascent hollow fiber membrane: injecting the spinning solution into an annular hole of an inserted tubular spinneret through a metering pump, taking water as core solution, injecting the core solution into an inner hole of the inserted tubular spinneret through the metering pump, simultaneously extruding the spinning solution and the core solution in a screw extrusion mode, and then entering into 40 ℃ aqueous solution through an air layer of 7cm for cooling and forming to obtain a nascent hollow fiber membrane; wherein the outer diameter of the spinneret is 1500 μm, and the inner diameter of the spinneret is 500 μm; the temperature of the metering pump is 185 ℃; the amount of the spinning solution used was 2000mL/m3The dosage of the core liquid is 400mL/m3(ii) a The speed of a main machine for screw extrusion is 8r/min, and the temperature of each zone is as follows: zone 1 120 ℃, zone 2 140 ℃, zone 3, zone 150 ℃, zone 4 170 ℃, and zone 5 ℃ 180 ℃;
(3) preparation of hollow fiber membrane: taking a mixed solution of lithium chloride and absolute ethyl alcohol as a soaking solution, and soaking the nascent hollow fiber membrane for 24 hours at room temperature (25 ℃) to obtain a poly 4-methyl-1-pentene hollow fiber membrane; wherein the mass content of lithium chloride in the soaking solution is 22%, and the mass content of absolute ethyl alcohol is 78%.
The thickness of the dense layer of the poly 4-methyl-1-pentene hollow fiber membrane prepared in the embodiment is 110nm, the thickness of the supporting layer is 550 μm, the porosity is 37%, and the pore size distribution is 50-80 nm; outside of hollow fiber membraneDiameter of 1400 μm, O of hollow fiber membrane2Transmission coefficient of 142Barrer, N2Transmittance of 156Barrer, CO2Transmission factor of 136Barrer, O2/N2A transmittance of 69, CO2/N2The transmission selection coefficient is 48, the tensile strength is 17MPa, and the impact strength is 11 MPa.
As can be seen from the above examples, the hollow fiber membrane of poly-4-methyl-1-pentene prepared by the invention has uniform pore size distribution, excellent separation performance and better mechanical property.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a poly 4-methyl-1-pentene hollow fiber membrane comprises the following steps:
(1) mixing 4-methyl-1-pentene resin, a diluent, a water-soluble additive and a water-insoluble additive to obtain a spinning solution; the mixing temperature is 130-180 ℃;
(2) extruding the spinning solution obtained in the step (1) and core solution together, and allowing the extruded spinning solution and core solution to enter a coagulating bath through an air layer to obtain a nascent poly (4-methyl-1-pentene) hollow fiber membrane; the temperature of the coagulating bath is 30-50 ℃;
(3) and (3) soaking the nascent poly-4-methyl-1-pentene hollow fiber membrane obtained in the step (2) in a soaking solution to obtain a poly-4-methyl-1-pentene hollow fiber membrane.
2. The preparation method according to claim 1, wherein in the step (1), the spinning solution contains 25 to 55% by mass of the 4-methyl-1-pentene resin, 35 to 65% by mass of the diluent, 5 to 12% by mass of the water-soluble additive, and 3 to 10% by mass of the water-insoluble additive.
3. The method according to claim 1 or 2, wherein the diluent in the step (1) comprises one or more of diethyl phthalate, dioctyl phthalate, epoxidized soybean oil, octyl adipate and N-methyldipropyrrolidone.
4. The method according to claim 1 or 2, wherein the water-soluble additive in step (1) comprises polyethylene glycol-400 and/or small molecule salts.
5. The production method according to claim 1 or 2, wherein the water-insoluble additive in the step (1) comprises silica and/or a polymer resin.
6. The method of claim 1, wherein the core liquid in step (2) comprises one or more of water, diethyl phthalate, dioctyl phthalate, epoxidized soybean oil, octyl adipate, and N-methyldipropyrrolidone.
7. The method according to claim 1, wherein the length of the air layer in the step (2) is 3 to 10 cm.
8. The method according to claim 1, wherein the soaking solution in the step (3) is a mixture of a water-soluble additive and absolute ethanol.
9. The poly-4-methyl-1-pentene hollow fiber membrane prepared by the preparation method of any one of claims 1 to 8, which comprises an outer dense layer and an inner support layer, wherein the porosity of the support layer is 20-55%, and the pore size distribution is 20-200 nm.
10. The poly 4-methyl-1-pentene hollow fiber membrane according to claim 9, wherein the dense layer has a thickness of 10 to 200 nm; the thickness of the supporting layer is 150-600 mu m; the outer diameter of the poly 4-methyl-1-pentene hollow fiber membrane is 500 to 1500 μm.
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