CN110180401A - A kind of preparation method of (per) fluoropolymer hollow-fibre membrane - Google Patents
A kind of preparation method of (per) fluoropolymer hollow-fibre membrane Download PDFInfo
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- CN110180401A CN110180401A CN201910576063.4A CN201910576063A CN110180401A CN 110180401 A CN110180401 A CN 110180401A CN 201910576063 A CN201910576063 A CN 201910576063A CN 110180401 A CN110180401 A CN 110180401A
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
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- 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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
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- 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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
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Abstract
The invention discloses a kind of preparation methods of (per) fluoropolymer hollow-fibre membrane.This method by water-soluble polymer pore-foaming agent, water-soluble inorganic pore-foaming agent and auxiliary additive using obtaining Water Soluble Compound pore-foaming agent after ball milling mixing, then with film forming polymer ball milling, obtain uniformly mixed material.Uniformly mixed particle is obtained by squeezing out, being granulated again, by particle through hollow spinning pack squeezing out quantitative, component internal is passed through inert gas, through spinneret draft, after spinning melt solidifies in air bath, online stretching and winding is carried out in air, and extraction is washed away except water-soluble composite pore-forming, obtains hollow-fibre membrane.Polyethylene glycol oxide and film forming polymer compatibility are preferable in composite pore-forming, improve dispersibility and mobility of the inorganic particulate in film forming polymer, while the addition of inorganic particulate avoids polyethylene glycol oxide during the spinning process into fibre.Using melt spinning pulling method, any solvent, diluent or plasticizer is not used, it is environmentally protective.
Description
Technical field
The present invention relates to technical field of membrane, the preparation method of specifically a kind of (per) fluoropolymer hollow-fibre membrane.
Background technique
Hollow-fibre membrane is one of principal mode of seperation film, due to the special superiority of hollow-fibre membrane, increasingly by
To the attention of people, it is widely used to the every field such as water process, food, petrochemical industry, medicine, steel, electric power at present.
Typical doughnut membrane preparation method has solution spinning (such as solution phase inversion) and melt spinning method.So
And hollow-fibre membrane there are the intensity low, film of solwution method preparation is easy the disadvantages of shrinking, while preparation process in the drying process
It is middle to use a large amount of solvents, it also needs to recycle dicyandiamide solution, separated and be recycled, easily causes environmental pollution and deteriorate labour
Condition, therefore be unfavorable for further developing.Thermally induced phase separation is easier to control compared with non-solvent phase separation method, the fenestra of preparation
Diameter is evenly distributed, voidage is high, intensity is high, but usually used diluent is most of to environment nocuousness, or even has to human body
Carcinogenicity has biggish security risk and environment hidden danger.Melt spinning stretching (MSCS) film-forming method can be effectively improved above-mentioned
The deficiency of solwution method spinning membrane system, stretches it after polymer melting is formed a film, to make the crystal phase and amorphous of polymer
It is radially separated between phase along fiber, forms microcellular structure, but the fenestra permeability being usually formed is poor, shows as hollow fibre
Tie up that porous membrane flux is not high, this method is mainly used in the high material such as polypropylene of hardness, is not suitable for that hardness is lower, elastic height
Material such as perfluoroethylene-propylene, Kynoar etc..
In existing method, in order to preferably solve the above problems inorganic particulate can be added and have in film forming co-mixing system
Gas is added if the document of application number 02800552.X discloses a kind of method for manufacturing hollow-fiber film in machine liquid in system
The hollow fiber film thread that aperture is small, porosity is high, water flux is big is made in aerosil inorganic particulate.But what this method used
Fumed silica is expensive, and slow with silicon dioxde reaction with lye, takes long time, and extraction organic liquid uses
Methylene chloride is easy to volatilize since fusing point is low, and energy consumption is high when recycling, and the rate of recovery is low.The document of application number 201710447581.7
A kind of perfluoroethylene-propylene hollow-fibre membrane and preparation method thereof is disclosed, but this method need to be by being passed through supercritical CO2, increase
The series of steps such as pressure, release, etching, step is relatively complicated and the high requirements on the equipment.Therefore, exploitation environmental pollution it is few,
Environmentally protective doughnut membrane preparation method has great importance.
Summary of the invention
In view of the deficiencies of the prior art, the technical issues of present invention intends to solve is to provide a kind of hollow fibre of (per) fluoropolymer
Tie up the preparation method of film.
The technical solution that the present invention solves the technical problem is to provide a kind of preparation of (per) fluoropolymer hollow-fibre membrane
Method, it is characterised in that method includes the following steps:
The preparation of step 1, film formula: water-soluble polymer pore-foaming agent, water-soluble inorganic pore-foaming agent and auxiliary are added
Agent obtains Water Soluble Compound pore-foaming agent after using ball milling mixing, then with film forming polymer ball milling, obtain uniformly mixed material；
The preparation of step 2, hollow-fibre membrane: uniformly mixed particle is obtained by squeezing out, being granulated, by particle through hollow spray
Silk component squeezing out quantitative, component internal is passed through inert gas, through spinneret draft, after spinning melt solidifies in air bath,
Online stretching and winding is carried out in air, extraction is washed away except water-soluble composite pore-forming, obtains hollow-fibre membrane.
Compared with prior art, the beneficial effects of the invention are that:
(1) this method is using water-soluble poly ethylene oxide and water-soluble inorganic particle as composite pore-forming.Using ball milling
Method obtains composite pore-forming for polyethylene glycol oxide and inorganic particulate are compound first, polyethylene glycol oxide and film forming polymer compatibility compared with
It is good, good peptizaiton is played to water-soluble inorganic pore-foaming agent, improves dispersibility of the inorganic particulate in film forming polymer
And mobility, while the addition of inorganic particulate avoids polyethylene glycol oxide during the spinning process into fibre.Using water-soluble polymer/
Inorganic particulate composite pore-forming, compound pore former can wash out completely in water-washing process after spinning moulding.It is added in formula few
Functional auxiliary additive is measured, film hydrophobicity, lipophilicity, hydrophily and resistance tocrocking etc. are assigned.
(2) melt spinning pulling method, the online stretching-washing of spinning-, one-pass molding, preparation method simple process, spinning are used
Silk is high-efficient.
(3) any solvent, diluent or plasticizer are not used during the spinning process, avoids solvent, diluent etc. and exists
Environmental pollution caused by volatilization in high temperature spinning and the injury to human body, while reducing the cost recovery of solvent, diluent,
And any organic extractant is not used, it is suitble to industrialized production.
(4) hollow fiber membrane surface of this method preparation is transversal in stretchable holes, the multiple pore structure in dissolution hole and interface cavity
Face is uniform three-dimensional network pore structure；And there is good resistance to pressure, permeability, mechanical strength, it can be used as seperation film and answer
For the separation under the fields such as water process, medicine, derived energy chemical, medicine bioengineering, especially harsh environment.
(5) make porosity and the aperture of hollow-fibre membrane adjustable by the way of post-tensioning, porosity is higher, and aperture is more
Greatly.
Detailed description of the invention
Fig. 1 is the hollow-fibre membrane cross-sectional scans electron microscope that the embodiment of the present invention 1 obtains；
Fig. 2 is the hollow-fibre membrane cross section partial enlargement electron microscope that the embodiment of the present invention 1 obtains；
Fig. 3 is the doughnut film outer surface scanning electron microscope (SEM) photograph that the embodiment of the present invention 1 obtains；
Fig. 4 is the doughnut film outward appearance digital photograph figure that the embodiment of the present invention 1 obtains；
Specific embodiment
Specific embodiments of the present invention are given below.Specific embodiment is only used for that present invention be described in more detail, unlimited
The protection scope of the claim of this application processed.
The present invention provides a kind of preparation method of (per) fluoropolymer hollow-fibre membrane (abbreviation methods), it is characterised in that should
Method the following steps are included:
The preparation of step 1, film formula: water-soluble polymer pore-foaming agent, water-soluble inorganic pore-foaming agent and auxiliary are added
Agent using obtaining Water Soluble Compound pore-foaming agent after ball milling mixing, then with film forming polymer ball milling, obtain uniformly mixed object
Material；Wherein 60~75wt% of film forming polymer, 10~20wt% of water-soluble polymer pore-foaming agent, water-soluble inorganic pore-foaming agent 10~
0~10wt% of 20wt% and auxiliary additive, the sum of each component are 100wt%；
The ball milling use dry milling processes, 25~40 DEG C of temperature, 300~600r/min of revolving speed, 3~12h of ball milling duration；
The film forming polymer is perfluoroethylene-propylene (FEP), Kynoar (PVDF) or Kynoar-hexafluoro
One of propylene copolymer (PVDF-HFP)；Perfluoroethylene-propylene (FEP) excellent with high temperature performance, resistant to chemical etching is
It is preferred that；
The water-soluble polymer pore-foaming agent is polyethylene glycol oxide (PEO), and molecular weight is 100,000~4,000,000, poly- with film forming
It is preferable to close object compatibility, good peptizaiton is played to water-soluble inorganic pore-foaming agent, decomposition temperature is high at 420 DEG C or so
In spinning temperature, and it is water-soluble polymer, can be washed out completely in water-washing process；
The water-soluble inorganic pore-foaming agent is inorganic salts of the solubility at room temperature in water greater than 300g/L, including anhydrous
Calcium chloride (CaCl2), anhydrous sodium chloride (NaCl), at least one in anhydrous potassium chloride (KCl) or anhydrous lithium chloride (LiCl) etc.
Kind, it can be washed out completely in water-washing process, obtained membrane permeability can increase, and porosity is higher；
The auxiliary additive is in functional particle, including graphene, polytetrafluoroethylene (PTFE), silica or titanium dioxide
At least one；Graphene can assign the stronger hydrophobicity of film and lipophilicity, and titanium dioxide can assign film resistance tocrocking, parent
Water silica can assign film hydrophily, and polytetrafluoroethylene (PTFE), hydrophobic silica can assign film hydrophobicity, can be according to need
It wants, adds different functional particles；The average grain diameter of graphene, silica and titanium dioxide is 0.01-5 μm；
The preparation of step 2, hollow-fibre membrane: obtaining uniformly mixed particle by double screw extruder extrusion, granulation, will
Particle is through hollow spinning pack squeezing out quantitative at 180~330 DEG C, and component internal is passed through inert gas, and (the present embodiment is nitrogen
Gas), through spinneret draft, after spinning melt solidifies in air bath, online stretching and winding is carried out in air, extraction washes away water removal
Dissolubility composite pore-forming, obtains hollow-fibre membrane；
Specifically: uniformly mixed particle being obtained by double screw extruder extrusion, granulation, by particle at 180~330 DEG C
Lower through hollow spinning pack squeezing out quantitative, component internal is passed through inert gas (the present embodiment is nitrogen), through spinneret draft, spins
Silk melt enters first of winding after 20~50cm air layer, and spinneret draft ratio is 1~2 times；It is sufficiently solid in air bath
After change, online stretching and winding is carried out in air, and online draw ratio is 2~5 times；Then extraction washes 12- in 25-50 DEG C of water
48h removes Water Soluble Compound pore-foaming agent, obtains hollow-fibre membrane.
Preferably, this method further includes step 3；The post-tensioning of step 3, hollow-fibre membrane: the hollow fibre that step 2 is obtained
Film to be tieed up in 80~180 DEG C of oven heat stretching-machine and hot-stretch is carried out with the rate of extension of 1~20mm/min, draw ratio is 10~
200%, 10~60min of fixed length thermal finalization.
Embodiment 1
The anhydrous calcium chloride of the polyethylene glycol oxide (molecular weight 1,000,000) of 15wt%, 15wt% are used ball mill by step 1
(model: Xqm2-6) at 38 DEG C with 500r/min ball milling 6h after, then perfluoroethylene-propylene (FEP) powder ball milling with 70wt%
It is uniformly mixed.
Step 2, will blends described above feed double screw extruder in squeeze out, be granulated obtain uniformly mixed particle, through feed
Hopper auto feed is fed into double screw extruder at 290 DEG C through hollow spinning pack squeezing out quantitative, and component internal is passed through
Nitrogen, through spinneret draft, spinning melt enters first of winding after 20cm air layer, and spinneret draft ratio is 1.2 times；?
After sufficiently solidifying in air bath, online stretching and winding is carried out in air, online draw ratio is 3 times, then after washing 12h,
Obtain FEP hollow-fibre membrane.
Embodiment 2
The preparation method of the FEP hollow-fibre membrane of the embodiment is identical as the step 1 of embodiment 1 and step 2.
Step 3, the FEP hollow-fibre membrane for obtaining step 2 stretch speed in 140 DEG C of oven heat stretching-machines with 1mm/min
Rate carries out hot-stretch, draw ratio 30%, fixed length thermal finalization 30min.
Embodiment 3
Step 1, by the potassium chloride of the polyethylene glycol oxide (molecular weight 100,000) of 15wt%, 15wt% using ball mill (model:
Xqm2-6 after) at 38 DEG C with 400r/min ball milling 6h, then Kynoar (PVDF, model the SOLEF PVDF with 70wt%
6010) powder ball milling mixing is uniform；
Step 2, will blends described above feed double screw extruder in squeeze out, be granulated obtain uniformly mixed particle, through feed
Hopper auto feed is fed into double screw extruder at 210 DEG C through hollow spinning pack squeezing out quantitative, and component internal is passed through
Nitrogen, through spinneret draft, spinning melt enters first of winding after 30cm air layer, and spinneret draft ratio is 1.5 times；?
After sufficiently solidifying in air bath, online stretching and winding is carried out in air, online draw ratio is 2 times, then after washing 12h,
Obtain PVDF hollow-fibre membrane.
Embodiment 4
Step 1, by the polyethylene glycol oxide (molecular weight 4,000,000) of 18wt%, the anhydrous calcium chloride of 18wt%, 3wt% dredge
After water silica uses ball mill (model: Xqm2-6) at 38 DEG C with 300r/min ball milling 8h, then it is poly- complete with 61wt%
Fluoro ethyl propene (FEP, model DS618B) powder ball milling mixing is uniform；
Step 2, will blends described above feed double screw extruder in squeeze out, be granulated obtain uniformly mixed particle, through feed
Hopper auto feed is fed into double screw extruder at 285 DEG C through hollow spinning pack squeezing out quantitative, and component internal is passed through
Nitrogen, through spinneret draft, spinning melt enters first of winding after 20cm air layer, and spinneret draft ratio is 1.4 times；?
After sufficiently solidifying in air bath, online stretching and winding is carried out in air, online draw ratio is 2 times, then after washing 12h,
Obtain FEP/SiO2Hollow-fibre membrane.
Pure water flux, breaking strength and opening size test are carried out to hollow-fibre membrane obtained by embodiment 1-4.
Pure water flux test is carried out using laboratory home-built equipment, test pressure is 0.1MPa；Using JBDL-2000N type
Electronic tensile test machine test film breaking strength；It is big that its average pore size is tested using 3H-2000PB fiber type membrane aperture distribution instrument
It is small.
Table 1
The doughnut membrane porosity obtained it can be seen from Fig. 1-4 is higher, and cross section is uniform three-dimensional network hole knot
Structure；As can be seen from the above table, the film obtained has good permeability, mechanical strength.
The present invention does not address place and is suitable for the prior art.
Claims (10)
1. a kind of preparation method of (per) fluoropolymer hollow-fibre membrane, it is characterised in that method includes the following steps:
The preparation of step 1, film formula: water-soluble polymer pore-foaming agent, water-soluble inorganic pore-foaming agent and auxiliary additive are adopted
With obtaining Water Soluble Compound pore-foaming agent after ball milling mixing, then with film forming polymer ball milling, obtain uniformly mixed material；
The preparation of step 2, hollow-fibre membrane: uniformly mixed particle is obtained by squeezing out, being granulated, by particle through hollow spinneret group
Part squeezing out quantitative, component internal are passed through inert gas, through spinneret draft, after spinning melt solidifies in air bath, in air
Middle to carry out online stretching and winding, extraction is washed away except water-soluble composite pore-forming, obtains hollow-fibre membrane.
2. the preparation method of (per) fluoropolymer hollow-fibre membrane according to claim 1, it is characterised in that the film of step 1
In formula, 60~75wt% of film forming polymer, 10~20wt% of water-soluble polymer pore-foaming agent, water-soluble inorganic pore-foaming agent 10 ~
0 ~ 10wt% of 20wt% and auxiliary additive, the sum of each component are 100wt%.
3. the preparation method of (per) fluoropolymer hollow-fibre membrane according to claim 1, it is characterised in that in step 1, ball
It grinds and uses dry milling processes, 25 ~ 40 DEG C of temperature, 300 ~ 600r/min of revolving speed, 3 ~ 12h of ball milling duration.
4. the preparation method of (per) fluoropolymer hollow-fibre membrane according to claim 1, it is characterised in that the film forming is poly-
Conjunction object is one of perfluoroethylene-propylene, Kynoar or Kynoar-hexafluoropropylene copolymer.
5. the preparation method of (per) fluoropolymer hollow-fibre membrane according to claim 1, it is characterised in that the water solubility
Polymer pore-foaming agent is polyethylene glycol oxide, and molecular weight is 100,000 ~ 4,000,000.
6. the preparation method of (per) fluoropolymer hollow-fibre membrane according to claim 1, it is characterised in that the water solubility
Inorganic pore-foaming agent is inorganic salts of the solubility at room temperature in water greater than 300g/L.
7. the preparation method of (per) fluoropolymer hollow-fibre membrane according to claim 6, it is characterised in that the water solubility
Inorganic pore-foaming agent is at least one of anhydrous calcium chloride, anhydrous sodium chloride, anhydrous potassium chloride or anhydrous lithium chloride.
8. the preparation method of (per) fluoropolymer hollow-fibre membrane according to claim 1, it is characterised in that the auxiliary adds
Adding agent is at least one of graphene, polytetrafluoroethylene (PTFE), silica or titanium dioxide；Graphene, silica and dioxy
The average grain diameter for changing titanium is 0.01-5 μm.
9. the preparation method of (per) fluoropolymer hollow-fibre membrane according to claim 1, it is characterised in that step 2 is specific
It is: obtains uniformly mixed particle by squeezing out, being granulated, by particle through hollow spinning pack squeezing out quantitative at 180 ~ 330 DEG C,
Component internal is passed through inert gas, and through spinneret draft, spinning melt enters first of winding, spray after 20~50cm air layer
Silk head draw ratio is 1 ~ 2 times；After sufficiently solidifying in air bath, online stretching and winding, online draw ratio are carried out in air
It is 2 ~ 5 times；Then extraction washes 12-48h removal Water Soluble Compound pore-foaming agent in 25-50 DEG C of water, obtains hollow-fibre membrane.
10. the preparation method of (per) fluoropolymer hollow-fibre membrane according to claim 1, it is characterised in that this method is also wrapped
Include step 3；The post-tensioning of step 3, hollow-fibre membrane: the hollow-fibre membrane that step 2 is obtained is drawn in 80 ~ 180 DEG C of oven heat
It stretches in machine and hot-stretch is carried out with the rate of extension of 1 ~ 20mm/min, draw ratio is 10 ~ 200%, 10 ~ 60min of fixed length thermal finalization.
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| CN110479122A (en) * | 2019-09-03 | 2019-11-22 | 贵州省材料产业技术研究院 | A kind of preparation method of porous polymer in-situ micro-fibril water-oil separating material |
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