CN115430295B - Preparation method of composite reinforced polypropylene hollow fiber microporous membrane - Google Patents
Preparation method of composite reinforced polypropylene hollow fiber microporous membrane Download PDFInfo
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- CN115430295B CN115430295B CN202211087618.7A CN202211087618A CN115430295B CN 115430295 B CN115430295 B CN 115430295B CN 202211087618 A CN202211087618 A CN 202211087618A CN 115430295 B CN115430295 B CN 115430295B
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 85
- -1 polypropylene Polymers 0.000 title claims abstract description 84
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 83
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 239000012982 microporous membrane Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000012528 membrane Substances 0.000 claims abstract description 65
- 238000005266 casting Methods 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 239000002667 nucleating agent Substances 0.000 claims abstract description 23
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- 239000000835 fiber Substances 0.000 claims abstract description 16
- 239000011256 inorganic filler Substances 0.000 claims abstract description 15
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 15
- 239000003549 soybean oil Substances 0.000 claims abstract description 12
- 235000012424 soybean oil Nutrition 0.000 claims abstract description 12
- 238000005516 engineering process Methods 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 10
- 238000009987 spinning Methods 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 230000002787 reinforcement Effects 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 12
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- 239000001110 calcium chloride Substances 0.000 claims description 10
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 239000005995 Aluminium silicate Substances 0.000 claims description 7
- 235000012211 aluminium silicate Nutrition 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- 229920000728 polyester Polymers 0.000 claims description 7
- 230000003014 reinforcing effect Effects 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 5
- 239000005543 nano-size silicon particle Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 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 2
- 238000009954 braiding Methods 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 claims description 2
- 238000005345 coagulation Methods 0.000 claims description 2
- 230000015271 coagulation Effects 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 235000013773 glyceryl triacetate Nutrition 0.000 claims description 2
- 239000001087 glyceryl triacetate Substances 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229960002622 triacetin Drugs 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 230000035699 permeability Effects 0.000 abstract description 4
- 238000000605 extraction Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 27
- 230000004907 flux Effects 0.000 description 22
- 239000000243 solution Substances 0.000 description 21
- 238000009826 distribution Methods 0.000 description 12
- 238000004804 winding Methods 0.000 description 11
- 230000009172 bursting Effects 0.000 description 10
- 239000002904 solvent Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- BVXGBMBOZMRULW-UHFFFAOYSA-N 1-n,4-n-dicyclohexylbenzene-1,4-dicarboxamide Chemical compound C=1C=C(C(=O)NC2CCCCC2)C=CC=1C(=O)NC1CCCCC1 BVXGBMBOZMRULW-UHFFFAOYSA-N 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
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- 239000002033 PVDF binder Substances 0.000 description 2
- 238000011001 backwashing Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
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- 238000010586 diagram Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013385 inorganic framework Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000003361 porogen Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000002145 thermally induced phase separation Methods 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
-
- 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
- B01D69/087—Details relating to the spinning process
- B01D69/088—Co-extrusion; Co-spinning
-
- 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
- B01D71/26—Polyalkenes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
Abstract
The invention discloses a preparation method of a composite reinforced polypropylene hollow fiber microporous membrane, which takes a braided tube as a reinforcement, and comprises the steps of mixing completely dried polypropylene resin, a nucleating agent, an inorganic filler, an organic solvent and a pore-forming agent into soybean oil, and obtaining a casting solution after stirring and vacuum defoaming; uniformly coating the casting solution on the outer surface of a hollow braided tube through an annular spinneret by adopting a chemical fiber sheath/core composite spinning technology, and fully curing to obtain a nascent polypropylene hollow fiber membrane; the primary hollow fiber membrane is subjected to extraction and drying treatment to prepare the composite reinforced polypropylene hollow fiber microporous membrane. The prepared hollow fiber microporous membrane has better permeability, stability, lower production cost and good application prospect.
Description
Technical Field
The invention belongs to the technical field of water treatment filtering membranes, and particularly relates to a preparation method of a composite reinforced polypropylene hollow fiber microporous membrane.
Background
Along with the development of social economy and the increasing prominence of environmental problems, the preparation and application technology of a water treatment filtering membrane is taken as an important separation technology, and has been widely applied to various aspects of food and beverage, surface water purification, industrial and domestic sewage treatment, high-purity water preparation and the like, and plays an increasingly important role. The pore size of the microporous membrane is usually between 0.05 and 10 mu m, is mainly used for trapping particles, suspended matters and other pollutants from gas and liquid, is the earliest industrial membrane variety, and is the most commonly applied and most sold industrial membrane.
The preparation methods of the polypropylene hollow fiber microporous membrane reported in the prior art comprise a melting-cold stretching method and a thermally induced phase separation method. The microporous membrane prepared by the stretching method has low permeability, is easy to pollute and is difficult to clean; the membrane prepared by the thermotropic phase method has the advantages of good permeability, adjustable pore diameter, narrow pore diameter distribution, adjustable outer diameter of hollow fiber and the like, and can be used for preparing other types of porous membranes, such as dialysis membranes and the like besides microporous membranes. The raw materials of the sewage treatment filtering membrane which are widely used at present are fluoropolymer materials, but the raw materials are expensive, so that the development of the filtering membrane from raw materials to membrane preparation with low cost has great significance.
Polypropylene is insoluble in organic solvent at normal temperature, has good acid and alkali resistance and biological erosion resistance, is a film-forming polymer with high cost performance, and has raw material price far lower than polysulfone and polyvinylidene fluoride, but the polypropylene film material prepared by the thermal induced phase separation method has the problems of molding shrinkage and low strength.
Disclosure of Invention
The invention provides a preparation method of a composite reinforced polypropylene hollow fiber microporous membrane, which overcomes the defects of low flux, easy pollution, difficult backwashing recovery and the like of a polypropylene filter membrane prepared by the existing stretching method and the defects of insufficient strength and dimensional stability of the polypropylene filter membrane prepared by a thermotropic phase.
As one aspect of the invention, the invention provides a preparation method of a composite reinforced polypropylene hollow fiber microporous membrane, which comprises the following steps,
(1) Mixing the dried polypropylene resin, the nucleating agent, the inorganic filler, the organic solvent and the pore-forming agent into soybean oil at 180-210 ℃, stirring for 3-5 hours to obtain a uniform solution, and vacuum defoaming to obtain a casting solution;
(2) Adopting a coextrusion chemical fiber sheath/core composite spinning technology, and taking a hollow braided tube as a reinforcing body; uniformly coating the casting solution prepared in the step (1) on the outer surface of a hollow braided tube through an annular spinneret, and then cooling and forming through an air gap and a water solidifying bath, and fully solidifying to obtain a nascent polypropylene hollow fiber membrane;
(3) Immersing the nascent polypropylene hollow fiber membrane in an extractant for 24 hours, taking out and immersing in water for 24 hours, and then drying to prepare the composite reinforced polypropylene hollow fiber microporous membrane consisting of the reinforcement and the polypropylene surface separation layer.
As a preferable scheme of the preparation method of the composite reinforced polypropylene hollow fiber microporous membrane, the invention has the following advantages: in the step (1), the nucleating agent is one of aromatic diamide, adipic acid and benzoic acid.
As a preferable scheme of the preparation method of the composite reinforced polypropylene hollow fiber microporous membrane, the invention has the following advantages: in the step (1), the inorganic filler is one or more of nano silicon dioxide, glass fiber, wollastonite and kaolin.
As a preferable scheme of the preparation method of the composite reinforced polypropylene hollow fiber microporous membrane, the invention has the following advantages: in the step (1), the organic solvent is one or more of glyceryl triacetate, dibutyl phthalate or dioctyl phthalate.
As a preferable scheme of the preparation method of the composite reinforced polypropylene hollow fiber microporous membrane, the invention has the following advantages: the pore-forming agent is polyethylene glycol and/or calcium chloride.
As a preferable scheme of the preparation method of the composite reinforced polypropylene hollow fiber microporous membrane, the invention has the following advantages: in the step (1), the mass fraction of the casting solution is as follows: 10-25% of polypropylene resin, 0.1-0.5% of nucleating agent, 1-2.5% of inorganic filler, 0-10% of organic solvent, 5-10% of pore-forming agent and 52-83.9% of soybean oil, wherein the sum of the components is 100%.
As a preferable scheme of the preparation method of the composite reinforced polypropylene hollow fiber microporous membrane, the invention has the following advantages: in the step (2), the braiding material of the hollow braided tube is one of polyester fiber, polyamide fiber, polyacrylonitrile fiber or cellulose acetate fiber.
As a preferable scheme of the preparation method of the composite reinforced polypropylene hollow fiber microporous membrane, the invention has the following advantages: in the step (2), the spinning temperature is 180-210 ℃, the air gap distance is 10-20cm, and the coagulation bath temperature is 25 ℃.
As a preferable scheme of the preparation method of the composite reinforced polypropylene hollow fiber microporous membrane, the invention has the following advantages: in the step (3), the extractant is dichloromethane or n-hexane.
The invention has the beneficial effects that: compared with polyvinylidene fluoride and polytetrafluoroethylene films in the market, the polypropylene hollow fiber film prepared by the invention has the advantages that the cost is obviously reduced, and the solvent and the extractant can be recycled; compared with the polypropylene hollow fiber membrane prepared by a stretching method, the polypropylene hollow fiber membrane has higher permeability and better backwashing performance, and compared with the pure polypropylene hollow fiber membrane prepared by a thermotropic phase, the polypropylene hollow fiber membrane has better strength and dimensional stability. The reinforced hollow fiber membrane prepared by the invention can be used in the field of membrane separation, for example, filtration, sterilization and purification of product materials and water in industrial production, such as medical and health, biological products, sewage treatment and the like, and has good application prospect.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, in which:
FIG. 1 is a schematic diagram of the preparation flow of a polypropylene hollow fiber membrane.
FIG. 2 is a physical diagram of the polypropylene hollow fiber membrane prepared in example 4.
FIG. 3 is a cross-sectional SEM image of a polypropylene hollow-fiber membrane prepared in example 4.
FIG. 4 is a graph showing the filtration effect of the polypropylene hollow fiber membrane prepared in example 4 on 500 nm silica.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1:
the preparation method of the composite reinforced polypropylene hollow fiber membrane comprises the following steps:
(1) Mixing the dried T30s polypropylene resin, a nucleating agent, a pore-forming agent and soybean oil according to the mass ratio of 10 percent to 0.3 percent to 5 percent to 84.9 percent, wherein the nucleating agent and the pore-forming agent are respectively N, N' -dicyclohexyl terephthalamide, polyethylene glycol (70 percent) and calcium chloride (30 percent), stirring for 4 hours at 180 ℃ to obtain a uniformly mixed solution, and carrying out vacuum defoaming to obtain a casting solution;
(2) Adopting a coextrusion chemical fiber sheath/core composite spinning technology, and weaving a hollow braided tube with the outer diameter of 1.8mm by using polyester yarns with the linear density of 30tex according to the pitch of 0.4mm as a reinforcing body; uniformly coating the casting solution prepared in the step (1) on the outer surface of a hollow woven tube through an annular spinneret with the aperture of 1.9mm, winding at the speed of 5m/min, cooling and forming through an air gap of 15cm and a water solidifying bath at the temperature of 25 ℃, and fully solidifying to obtain a nascent polypropylene hollow fiber membrane;
(3) Immersing the primary hollow fiber membrane in dichloromethane for 24h, taking out, immersing in water for 24h, removing pore-forming agent and solvent in the primary hollow fiber membrane, and drying to obtain the composite reinforced polypropylene hollow fiber microporous membrane composed of the reinforcement and the polypropylene surface separation layer.
The experiments were repeated and tested, and the hollow fiber microporous membrane prepared in this example had an average porosity of 78.2%, a membrane average pore diameter of 0.68 μm, a pore diameter distribution range of 0.06 to 1.2 μm, and an initial water flux of 2508.6 L.m -2 ·h -1 ·bar -1 After testing for 100 hours by pure water, the flux average attenuation is 19.8%, the tensile strength is 156.2Mpa, and the bursting strength is 0.43Mpa.
Example 2
The preparation method of the composite reinforced polypropylene hollow fiber membrane comprises the following steps:
(1) Mixing the dried T30s polypropylene resin, a nucleating agent, a pore-forming agent and soybean oil according to the mass ratio of 15% to 0.3% to 5% to 79.7%, wherein the nucleating agent and the pore-forming agent are respectively N, N' -dicyclohexyl terephthalamide, polyethylene glycol (70%) and calcium chloride (30%), stirring for 4 hours at 190 ℃ to obtain a uniformly mixed solution, and carrying out vacuum defoaming to obtain a casting solution;
(2) Adopting a coextrusion chemical fiber sheath/core composite spinning technology, and weaving a hollow braided tube with the outer diameter of 1.8mm by using polyester yarns with the linear density of 30tex according to the pitch of 0.4mm as a reinforcing body; uniformly coating the casting solution prepared in the step (1) on the outer surface of a hollow woven tube through an annular spinneret with the aperture of 1.9mm, winding at the speed of 5m/min, cooling and forming through an air gap of 15cm and a water solidifying bath at the temperature of 25 ℃, and fully solidifying to obtain a nascent polypropylene hollow fiber membrane;
(3) Immersing the nascent polypropylene hollow fiber membrane in dichloromethane for 24 hours, taking out and immersing in water for 24 hours, removing pore-forming agent and solvent in the nascent hollow fiber membrane, and drying to prepare the composite reinforced polypropylene hollow fiber microporous membrane consisting of the reinforcement and the polypropylene surface separation layer. The experiments were repeated and tested, and the hollow fiber microporous membrane prepared in this example had an average porosity of 71.8%, an average membrane pore size of 0.31. Mu.m, a pore size distribution range of 0.05 to 0.76. Mu.m, and an initial water flux of 1465.7 L.m -2 ·h -1 ·bar -1 After 100h of pure water test, the flux average attenuation is 16.7%, the tensile strength is 163.4MPa, and the bursting strength is 0.56MPa.
The solid content of the casting solution of example 2 was increased compared with example 1, resulting in an increase in viscosity of the casting solution, and thus the heating temperature was increased, so that the components of the casting solution could be uniformly mixed and have sufficient fluidity. Since the improvement of the solid content leads to the reduction of the porosity of the membrane material and the corresponding water flux is reduced, but the tensile strength and the bursting strength are improved, and the research experiments show that the improvement of the solid content is beneficial to the improvement of the mechanical property of the membrane, but the reduction of the porosity of the membrane is caused at the same time, so that when the solid content is too low, the mechanical property cannot meet the use requirement, and when the solid content is high, the water flux is reduced, thereby reducing the efficiency of water treatment, and the preference of proper solid content is important.
Example 3
The preparation method of the composite reinforced polypropylene hollow fiber membrane comprises the following steps:
(1) Mixing the dried T30s polypropylene resin, a nucleating agent, an inorganic filler, a pore-forming agent and soybean oil according to the mass ratio of 15 to 0.3 to 1.5 to 5 to 78.2, wherein the nucleating agent, the inorganic filler and the pore-forming agent are respectively N, N' -dicyclohexyl terephthalamide, nano silicon dioxide (50 percent) and kaolin (50 percent), polyethylene glycol (70 percent) and calcium chloride (30 percent), stirring for 4 hours at 190 ℃ to obtain a uniformly mixed solution, and carrying out vacuum defoaming to obtain a casting solution;
(2) Adopting a coextrusion chemical fiber sheath/core composite spinning technology, and weaving a hollow braided tube with the outer diameter of 1.8mm by using polyester yarns with the linear density of 30tex according to the pitch of 0.4mm as a reinforcing body; uniformly coating the casting solution prepared in the step (1) on the outer surface of a hollow woven tube through an annular spinneret with the aperture of 1.9mm, winding at the speed of 5m/min, cooling and forming through an air gap of 15cm and a water solidifying bath at the temperature of 25 ℃, and fully solidifying to obtain a nascent polypropylene hollow fiber membrane;
(3) Immersing the nascent polypropylene hollow fiber membrane in normal hexane for 24 hours, taking out and immersing in water for 24 hours, removing pore-forming agent and solvent in the nascent hollow fiber membrane, and drying to prepare the composite reinforced polypropylene hollow fiber microporous membrane consisting of the reinforcement and the polypropylene surface separation layer. The experiments were repeated and tested, and the average porosity of the hollow fiber microporous membrane prepared in this example was 72.3%, the average pore diameter of the membrane was 0.33. Mu.m, the pore diameter distribution range was 0.05 to 0.81. Mu.m, and the initial water flux was 1548.7 L.m -2 ·h -1 ·bar -1 After 100h of pure water test, the average flux attenuation is 11.8%, the tensile strength is 165.6MPa, and the bursting strength is 0.58MPa.
According to the embodiment, on the basis of the embodiment 2, the kaolin is added as the inorganic framework of the membrane material, and the inorganic silica and the kaolin are distributed in the membrane material, so that the mechanical property of the membrane is improved, and the problems of porosity and pore diameter reduction of the membrane material caused by PP shrinkage in the use process are solved, so that the flux attenuation value is smaller than that of the embodiment 1 and the embodiment 2, and the stability of the membrane material is improved on the basis of improving the mechanical property.
Example 4
The preparation method of the composite reinforced polypropylene hollow fiber membrane comprises the following steps:
(1) Mixing the dried T30s polypropylene resin, a nucleating agent, an inorganic filler, an organic solvent, a pore-forming agent and soybean oil according to the mass fraction of 15 percent to 0.3 percent to 1.5 percent to 5 percent to 73.2 percent, wherein the nucleating agent, the inorganic filler, the organic solvent and the pore-forming agent are respectively N, N' -dicyclohexyl terephthalamide (nucleating agent), nano silicon dioxide (50 weight percent) and kaolin (50 weight percent) (inorganic filler), dibutyl phthalate (organic solvent), polyethylene glycol (70 weight percent) and calcium chloride (30 weight percent) (pore-forming agent), stirring for 4 hours at 190 ℃ to obtain a uniformly mixed solution, and carrying out vacuum defoaming to obtain a casting film liquid;
(2) Adopting a coextrusion chemical fiber sheath/core composite spinning technology, and weaving a hollow braided tube with the outer diameter of 1.8mm by using polyester yarns with the linear density of 30tex according to the pitch of 0.4mm as a reinforcing body; uniformly coating the casting solution prepared in the step (1) on the outer surface of a hollow woven tube through an annular spinneret with the aperture of 1.9mm, winding at the speed of 5m/min, cooling and forming through an air gap of 15cm and a water solidifying bath at the temperature of 25 ℃, and fully solidifying to obtain a nascent polypropylene hollow fiber membrane;
(3) Immersing the nascent polypropylene hollow fiber membrane in normal hexane for 24 hours, taking out and immersing in water for 24 hours, removing pore-forming agent and solvent in the nascent polypropylene hollow fiber membrane, and drying to prepare the composite reinforced polypropylene hollow fiber microporous membrane consisting of the reinforcement and the polypropylene surface separation layer.
The hollow fiber microporous membrane prepared in this example was tested to have a porosity of 72.7%, an average pore diameter of 0.32 μm, a pore diameter distribution range of 0.05 to 0.59 μm, and an initial water flux of 1388.7 L.m -2 ·h -1 ·bar -1 After testing for 100 hours by pure water, the flux decays by 10.4%, the tensile strength is 164.8MPa, and the bursting strength is 0.57MPa.
In the embodiment, on the basis of the embodiment 3, the dibutyl phthalate serving as an organic solvent is added, and a small amount of dibutyl phthalate is distributed in the casting film liquid as a poor solvent of polypropylene, so that on one hand, the growth of polypropylene spherulites can be inhibited, and on the other hand, the pore size distribution range can be reduced, and on the basis of ensuring the mechanical property and the stability, the use of the organic solvent can improve the filtration precision of the hollow fiber membrane, and the sewage treatment efficiency is higher.
Example 5:
the preparation method of the composite reinforced polypropylene hollow fiber membrane comprises the following steps:
(1) Mixing the dried T30s polypropylene resin, a nucleating agent, an inorganic filler, an organic solvent, a pore-forming agent and soybean oil according to the mass fraction of 15 percent to 0.3 percent to 1.5 percent to 5 percent to 73.2 percent, wherein the nucleating agent, the inorganic filler, the organic solvent and the pore-forming agent are respectively N, N' -dicyclohexyl terephthalamide (nucleating agent), nano silicon dioxide (50 percent) and kaolin (50 percent) (inorganic filler), dibutyl phthalate (organic solvent), polyethylene glycol (70 percent) and calcium chloride (30 percent) (pore-forming agent), stirring for 4 hours at 190 ℃ to obtain a uniformly mixed solution, and carrying out vacuum deaeration to obtain a casting solution;
(2) Adopting a coextrusion chemical fiber sheath/core composite spinning technology, and weaving a hollow braided tube with the outer diameter of 1.8mm by using polyester yarns with the linear density of 30tex according to the pitch of 0.4mm as a reinforcing body; uniformly coating the casting solution prepared in the step (1) on the outer surface of a hollow woven tube through an annular spinneret with the aperture of 1.9mm, winding at the speed of 15m/min, cooling and forming through an air gap of 5cm and a water solidifying bath at the temperature of 25 ℃, and fully solidifying to obtain a nascent polypropylene hollow fiber membrane;
(3) Immersing the nascent polypropylene hollow fiber membrane in normal hexane for 24 hours, taking out and immersing in water for 24 hours, removing pore-forming agent and solvent in the nascent hollow fiber membrane, and drying to prepare the composite reinforced polypropylene hollow fiber microporous membrane consisting of the reinforcement and the polypropylene surface separation layer.
The hollow fiber microporous membrane prepared in this example was tested to have a porosity of 71.2%, the membraneThe average pore diameter is 0.34 μm, the pore diameter distribution range is 0.05-0.67 μm, and the initial water flux is 1502.5 L.m -2 ·h -1 ·bar -1 After testing for 100 hours by pure water, the flux attenuation is 11.3%, the tensile strength is 152Mpa, and the bursting strength is 0.33Mpa.
In this example, compared with example 4, the winding speed was high, the air gap was short, so that the bonding time between the woven tube and the casting solution was short, the bonding strength at the interface between the woven tube and the polypropylene film was low, and the tensile strength and burst pressure were low, so that the bonding strength between the woven tube and the film was low due to the excessive winding speed.
In addition, it was found during experimental exploration that the braided tube was deformed and even broken when the winding speed was too slow, and the time during which the braided tube was subjected to high temperature was increased when the winding speed was too slow, and the raw material of the braided tube was softened at a higher temperature and even broken under a certain winding tension. The length of the air gap is selected through early-stage experimental exploration, and when the air gap is overlong, the temperature of the casting film liquid is reduced slowly, so that the crystallization time of the polypropylene is prolonged, the crystallinity of the polypropylene film is increased, the pores are more prone to shrinkage, and the dimensional stability is reduced. The preferred proper winding speed and air gap are therefore important for product dimensional stability and mechanical properties.
Comparative example 1:
compared to example 4, the nucleating agent content of 0.3% was replaced by 0.05%, and the soybean oil content of 73.2% was correspondingly increased to 73.45%. The other conditions and preparation methods were the same as in example 4.
The hollow fiber microporous membrane prepared in this example was tested to have a porosity of 70.6%, an average pore diameter of 0.33 μm, a pore diameter distribution range of 0.05 to 0.59 μm, and an initial water flux of 1158.7 L.m -2 ·h -1 ·bar -1 After testing for 100 hours by pure water, the flux decays by 13.4%, the tensile strength is 161.2MPa, and the bursting strength is 0.51MPa.
Because the addition amount of the nucleating agent is small, spherulites are easy to generate when the polymer is crystallized, on one hand, the crystallinity is high, the contractibility is strong in the use process, the dimensional stability is poor, and on the other hand, stress concentration can be generated at the interface between the spherulites, and the tensile strength and the bursting strength are reduced, so that the mechanical property of the film is reduced; in addition, after the usage amount of the nucleating agent exceeds a certain value, the performance of the polypropylene film tends to be stable, and various performances are not improved along with the increase of the usage amount of the nucleating agent.
Comparative example 2:
compared to example 4, the organic solvent content of 5% was replaced by 15%, and the soybean oil content of 73.2% was correspondingly reduced to 63.2%. The other conditions and preparation methods were the same as in example 4.
The hollow fiber microporous membrane prepared in this example was tested to have a porosity of 76.7%, an average pore diameter of 0.38 μm, a pore diameter distribution range of 0.05 to 0.64 μm, and an initial water flux of 1388.7 L.m -2 ·h -1 ·bar -1 After testing for 100 hours by pure water, the flux attenuation is 11.2%, the tensile strength is 159.8MPa, and the bursting strength is 0.48MPa.
When the organic solvent content is high, the organic solvent is poor solvent of PP, so that the gap between polymers is increased, the acting force between polymer molecular chains is reduced, the film forming continuity is reduced, and the mechanical property is reduced, so that the organic solvent can be only added in a small amount within a certain range to be beneficial to the improvement of the film performance.
Comparative example 3:
in comparison to example 4, the porogens were replaced by polyethylene glycol (70 wt%) and calcium chloride (30 wt%) and polyethylene glycol (30 wt%) and calcium chloride (70 wt%). The other conditions and preparation methods were the same as in example 4.
The hollow fiber microporous membrane prepared in this example was tested to have a porosity of 74.7%, an average pore diameter of 0.51 μm, a pore diameter distribution range of 0.05 to 0.78 μm, and an initial water flux of 1673.2 L.m -2 ·h -1 ·bar -1 After 100h of pure water test, the flux decays by 10.2%, the tensile strength is 165.3MPa, and the bursting strength is 0.61MPa.
The method has the advantages that the pore size is larger and the pore size distribution range is larger when the calcium chloride addition amount is high, the membrane flux is improved, but the membrane separation precision is also reduced, and in addition, the experimental exploration shows that when the polyethylene glycol addition amount is large, the pore size is smaller, the membrane flux is also smaller, and the proportion of the pore-foaming agent directly influences the pore size and the pore size distribution of the membrane.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.
Claims (4)
1. A preparation method of a composite reinforced polypropylene hollow fiber microporous membrane is characterized by comprising the following steps: is composed of the following steps of the method,
(1) Mixing the dried polypropylene resin, the nucleating agent, the inorganic filler, the organic solvent and the pore-forming agent into soybean oil at 180-210 ℃, stirring for 3-5 hours to obtain a uniform solution, and vacuum defoaming to obtain a casting solution; the nucleating agent is one of aromatic diamide, adipic acid and benzoic acid; the inorganic filler is one or more of nano silicon dioxide, glass fiber, wollastonite and kaolin; the organic solvent is one or more of glyceryl triacetate, dibutyl phthalate or dioctyl phthalate; the pore-forming agent is polyethylene glycol and/or calcium chloride; the mass fraction of the casting film liquid is as follows: 10-25% of polypropylene resin, 0.1-0.5% of nucleating agent, 1-2.5% of inorganic filler, 0-10% of organic solvent, 5-10% of pore-forming agent and 52-83.9% of soybean oil, wherein the sum of the components is 100%;
(2) Adopting a coextrusion chemical fiber sheath/core composite spinning technology, and taking a hollow braided tube as a reinforcing body; uniformly coating the casting solution prepared in the step (1) on the outer surface of a hollow braided tube through an annular spinneret, and then cooling and forming through an air gap and a water solidifying bath, and fully solidifying to obtain a nascent polypropylene hollow fiber membrane;
(3) Immersing the nascent polypropylene hollow fiber membrane in an extractant for 24 hours, taking out and immersing in water for 24 hours, and then drying to prepare the composite reinforced polypropylene hollow fiber microporous membrane consisting of the reinforcement and the polypropylene surface separation layer.
2. The method for preparing the composite reinforced polypropylene hollow fiber microporous membrane according to claim 1, wherein the method comprises the following steps: in the step (2), the braiding material of the hollow braided tube is one of polyester fiber, polyamide fiber, polyacrylonitrile fiber or cellulose acetate fiber.
3. The method for preparing the composite reinforced polypropylene hollow fiber microporous membrane according to claim 1 or 2, wherein the method comprises the following steps of: in the step (2), the spinning temperature is 180-210 ℃, the air gap distance is 10-20cm, and the coagulation bath temperature is 25 ℃.
4. The method for preparing the composite reinforced polypropylene hollow fiber microporous membrane according to claim 1 or 2, wherein the method comprises the following steps of: in the step (3), the extractant is dichloromethane or n-hexane.
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