CN109351209A - A kind of the film formula and preparation method of perfluoroethylene-propylene hollow-fibre membrane - Google Patents
A kind of the film formula and preparation method of perfluoroethylene-propylene hollow-fibre membrane Download PDFInfo
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- CN109351209A CN109351209A CN201811562709.5A CN201811562709A CN109351209A CN 109351209 A CN109351209 A CN 109351209A CN 201811562709 A CN201811562709 A CN 201811562709A CN 109351209 A CN109351209 A CN 109351209A
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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
- 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
- B01D69/08—Hollow fibre 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
- B01D2325/24—Mechanical properties, e.g. strength
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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
- B01D2325/30—Chemical resistance
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Abstract
The invention discloses a kind of film formula of perfluoroethylene-propylene hollow-fibre membrane and preparation methods.The group of the formula becomes 50~75wt% of perfluoroethylene-propylene, 0~10wt% of 20~40wt% of pore-foaming agent, 5~15wt% of plasticizer and auxiliary additive, and the sum of each component is 100wt%；The pore-foaming agent is calcium carbonate.This method is to be granulated the formula after mixing, by particle squeezing out quantitative, after spinning melt solidifies in air bath, carries out online stretching and winding, obtains nascent hollow-fibre membrane；Nascent hollow-fibre membrane is subjected to post-tensioning thermal finalization, then film wire is immersed in acid solution and washes out calcium carbonate；Then extraction is washed, then washes to obtain the perfluoroethylene-propylene hollow-fibre membrane of the multiple pore structure with stretchable holes, dissolution hole and interface cavity.Calcium carbonate is used in formula as pore-foaming agent, will not be decomposed in high temperature spinning process, after spinning moulding, can be washed out completely through peracid solutions.
Description
Technical field
The present invention relates to technical field of membrane, the film formula of specifically a kind of perfluoroethylene-propylene hollow-fibre membrane and preparation
Method.
Background technique
At the end of the 20th century at the beginning of 21 century, numerous resource-intensive industrial booms bring population and increase and life matter
Comprehensive raising of amount, but environmental problem becomes increasingly conspicuous in recent years, and haze locks city, shortage of water resources, marine pollution, Oil spills etc.
Problem highlights, and seriously hinders economy, policy, environment omnibearing integrated cooperative development.In recent years, membrane technology is as emerging height
New technology has become and solves one of common technologies of significant problems such as water resource, the energy, environment, is promoting China its people warp
Ji development, Industrial Technical Progress and environmental resource protection etc. play an important role.
Hollow-fibre membrane is one of principal mode of seperation film, and typical doughnut membrane preparation method has solution spinning
(such as solution phase inversion) and melt spinning method.However, solwution method prepares hollow-fibre membrane, a large amount of solvents need to be used (to account for about into
80% or so of film system), the mechanical property of gained hollow-fibre membrane is poor, also need to recycle dicyandiamide solution, separate and
It is recycled, easily causes environmental pollution and deteriorate working condition, therefore be unfavorable for further developing.Thermally induced phase separation is applicable in
Dissolubility is poor under room temperature, and even due to crystallizing undissolvable polymer, required control parameter is few in the process, microcellular structure
Control is accurately, it can be achieved that the diversity and controllability of structure.But it is still inevasible during this to use Macrodilution agent,
Easily cause environmental pollution, and can not recycling, therefore production cost is higher.Melt spinning stretches (MSCS) film-forming method
The deficiency of above-mentioned solwution method spinning membrane system can be effectively improved, since melt spinning does not need solvent substantially, can direct fabrics, without molten
Problem is recycled in agent, environmental-friendly, is suitble to large-scale industrial production, and pulling method lower production costs, be widely used, and prepares
Obtained film-strength is high, and the output value of the film produced with this method, yield are considerably beyond thermally induced phase separation.
(per) fluoropolymer mainly includes polytetrafluoroethylene (PTFE) (PTFE), perfluoroethylene-propylene (FEP), poly- perfluoro alkoxy
(PFA) etc., have the characteristics that chemical property is stable, high temperature performance is excellent, increasingly the concern by film researcher, especially
Its good corrosion resistance, the particulate separation being widely used under harsh conditions.The physical and chemical performance of FEP is similar to PTFE, tool
Have with PTFE almost same excellent temperature tolerance, resistant to chemical etching and electrical insulating property etc., FEP is by tetrafluoroethene (TFE) and six
Polymer made of fluoropropene (HFP) copolymerization, since the F atom on TFE macromolecular main chain is by-CF3Replace, destroys PTFE knot
The original regularity of structure, reduces crystallinity, is a kind of (per) fluoropolymer of most representative melt-processable forming, therefore
High-performance, recyclable FEP are the organic membrane materials of ideal suitable for separation such as Acid-Base System, liquid organic mixtures under high temperature
Material.
The document of application number 201010191837.0 discloses a kind of polypropylene hollow fiber microporous membrane and preparation method thereof,
The micropore film-strength being prepared is high, even aperture distribution, but has used 50~80% diluent, environmental pollution among these
It is more serious, and production cost is higher.The document of application number 201310507300.4 discloses a kind of polyacrylonitrile hollow fiber
Membrane preparation method prepares PAN base hollow-fibre membrane using melt spinning, effectively prevents the use of a large amount of toxic chemicals,
Film-strength is effectively improved, but obtained film resistance to acid and alkali and corrosion resistance are poor.
Summary of the invention
In view of the deficiencies of the prior art, it is hollow that the technical issues of present invention intends to solve is to provide a kind of perfluoroethylene-propylene
The film formula and preparation method of tunica fibrosa.
The present invention solves the problems, such as that the technical solution of the formula technique is to provide a kind of perfluoroethylene-propylene hollow-fibre membrane
Film formula, it is characterised in that the group of the formula become 50~75wt% of perfluoroethylene-propylene, 20~40wt% of pore-foaming agent, increasing
5~15wt% of agent and 0~10wt% of auxiliary additive is moulded, the sum of each component is 100wt%；The pore-foaming agent is calcium carbonate.
The technical solution that the present invention solves the method technical problem is to provide a kind of perfluoroethylene-propylene hollow-fibre membrane
Preparation method, it is characterised in that method includes the following steps:
Step 1, by claim 1-5 it is any it is described formula after mixing, it is uniformly mixed by squeezing out, being granulated to obtain
Particle, by particle through hollow spinning pack squeezing out quantitative at 260~380 DEG C, component internal is passed through inert gas, spinning melt
After solidifying in air bath, online stretching and winding is carried out, obtains nascent hollow-fibre membrane；
Nascent hollow-fibre membrane is carried out post-tensioning thermal finalization by step 2, and then film wire is immersed in acid solution and washes out carbon
Sour calcium；Then extraction is washed, then washes to obtain perfluoroethylene-propylene hollow-fibre membrane.
Compared with prior art, the beneficial effects of the invention are that:
(1) at low cost, high temperature resistant, acid-soluble calcium carbonate are used in formula as pore-foaming agent, in high temperature spinning
It will not decompose, after spinning moulding, can be washed out completely through peracid solutions in the process, greatly improve the porosity of film and penetrating
Property.It is added to a small amount of plasticizer in formula, plasticization is not only played during film extrusion molding, improves perfluoroethylene third
The melt flow property of alkene, and play the role of dispersing calcium carbonate in mixing, it is allowed to be uniformly mixed with perfluoroethylene-propylene,
It is not easy to reunite.It is added to a small amount of functional inorganic particle in formula, assigns film hydrophobicity, lipophilicity or hydrophily etc..
(2) during melt spinning, solvent is not used, greatly reduces the pollution to environment, while reducing solvent
The cost of recycling.Primary membrane process of setting is cooling using air, without using coagulating baths such as water, also reduces to water usage amount and dirt
Dye.
(3) post-tensioning of oven heat stretching-machine is used, so that deforming in doughnut drawing process uniformly, advantageous film stretching mistake
The uniformity of journey；Draft temperature and draw ratio are controllable, and membrane porosity is controllable, avoid the shrinkage phenomenon of film, draw ratio
Increase the connectivity that can improve membrane porosity and fenestra, flux can increase with it, and pore-size distribution also will increase.
(4) the preparation method simple process, spinning efficiency is high, and processing cost is lower, is convenient for production application.
(5) the perfluoroethylene-propylene hollow fiber membrane surface of this method preparation is in the more of stretchable holes, dissolution hole and interface cavity
Repeated hole structure, cross section are uniform three-dimensional network pore structure；And there is good resistance to pressure, permeability, mechanical strength and good
Acid-alkali-corrosive-resisting well, solvent resistance, improve the porosity of film.
Detailed description of the invention
Fig. 1 is perfluoroethylene-propylene doughnut film outer surface scanning electron microscope (SEM) photograph obtained in the embodiment of the present invention 1；
Fig. 2 is perfluoroethylene-propylene hollow-fibre membrane inner surface scanning electron microscope (SEM) photograph obtained in the embodiment of the present invention 1；
Fig. 3 is perfluoroethylene-propylene hollow-fibre membrane cross-sectional scans electron microscope obtained in the embodiment of the present invention 1；
Fig. 4 is the scanning electricity of perfluoroethylene-propylene hollow-fibre membrane cross section partial enlargement obtained in the embodiment of the present invention 1
Mirror figure；
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 film formulas of perfluoroethylene-propylene hollow-fibre membrane (to be referred to as formulated), it is characterised in that
The group of the formula becomes 50~75wt% of perfluoroethylene-propylene, 20~40wt% of pore-foaming agent, 5~15wt% of plasticizer and auxiliary and adds
Add 0~10wt% of agent, the sum of each component is 100wt%；
The pore-foaming agent is the calcium carbonate (CaCO that decomposition temperature is higher than its spinning processing temperature3), average grain diameter 0.3-8
μm；Film wire is in acid cleaning process, pore-foaming agent CaCO3It can wash out completely, so CaCO3Content it is higher, then the porosity of film is got over
Height, flux is bigger, but the support performance of mechanical performance and film can decline simultaneously；
The plasticizer is high boiling organic low molecular liquid, including dibutyl phthalate, phthalic acid two
At least one of ethyl ester or dioctyl phthalate；Plasticizer not only plays plasticization during film extrusion molding,
Improve the melt flow property of perfluoroethylene-propylene；And play the role of dispersing calcium carbonate in mixing, it is allowed to and poly- perfluor
Second propylene is uniformly mixed, not easy to reunite, pref-erable dioctyl phthalate (DOP)；
The auxiliary additive be functional inorganic particle, including in graphene, silica or titanium dioxide at least
It is a kind of；Graphene can assign the stronger hydrophobicity of film and lipophilicity, and titanium dioxide can assign film resistance tocrocking, hydrophilic dioxy
SiClx can assign film hydrophily, and hydrophobic silica can assign film hydrophobicity, can according to need, and add different functions
Property particle；The average grain diameter of graphene, silica and titanium dioxide is 0.01-5 μm；
Invention also provides a kind of preparation method of perfluoroethylene-propylene hollow-fibre membrane (abbreviation method), features
Be method includes the following steps:
The formula is used high-speed mixer after mixing by step 1, is squeezed out, is granulated by double screw extruder
To uniformly mixed particle, particle is fed into double screw extruder through feeding hopper auto feed in being passed through at 260~380 DEG C
Empty spinning pack squeezing out quantitative, component internal are passed through inert gas (the present embodiment is nitrogen), and spinning melt is solid in air bath
After change, after 100~150 DEG C of hot-rollings, online stretching and winding is carried out, online draw ratio is 1~2 times, is come into being
Empty fiber membrane；
Specifically: spinning melt enters first of winding after 20~250mm air layer, after air bath solidification, then passes through
After 100~150 DEG C of hot-rollings, online stretching and winding is carried out, online draw ratio is 1~2 times, obtains nascent hollow-fibre membrane；It is whole
It is carried out in air in a winding process；
Nascent hollow-fibre membrane is carried out post-tensioning thermal finalization by step 2 in 80~160 DEG C of oven heat stretching-machines, is stretched
Rate is 0.5-50mm/min, and draw ratio is 0.2~2, then film wire is immersed in acid solution by fixed length 10~60min of thermal finalization
Middle processing 1~7 day, washes out pore-foaming agent CaCO3；Then plasticizer extraction is come out with scrub solutions such as alcohol or ether, then washed
Obtain perfluoroethylene-propylene hollow-fibre membrane；
In step 1, it is 0.3~2.0m that air bath, which solidifies length,.
In step 2, acid solution is hydrochloric acid or aqueous acetic acid, and concentration is 5~30wt%, and calcium carbonate can be complete after pickling
Wash out, more preferable than acetic acid pickling effect with concentration hydrochloric acid, concentration is higher, and pickling time can shorten, preferred concentration be 8~
The aqueous hydrochloric acid solution of 12wt%.
Embodiment 1
By perfluoroethylene-propylene (FEP) powder of 55wt%, dioctyl phthalate (DOP), the 33wt% of 12wt%
Calcium carbonate (CaCO3) be uniformly mixed using high speed mixer, blends described above is fed in double screw extruder and squeezes out, be granulated
Uniformly mixed particle is obtained, is fed into double screw extruder at 305 DEG C through feeding hopper auto feed through hollow spinneret group
Part squeezing out quantitative, component internal are passed through nitrogen, and spinning melt is after air bath solidification, after 140 DEG C of hot-rollings, carry out online
Stretching and winding, online draw ratio are 1 times, obtain nascent hollow-fibre membrane；
Nascent hollow-fibre membrane is subjected to post-tensioning thermal finalization, rate of extension 1mm/ in 140 DEG C of oven heat stretching-machines
Then film wire is immersed in 10wt% aqueous hydrochloric acid solution and handles 5 days, so by min, draw ratio 0.4, fixed length thermal finalization 30min
Extraction is washed afterwards, and washing obtains perfluoroethylene-propylene hollow-fibre membrane.
Embodiment 2
By perfluoroethylene-propylene (FEP) powder of 55wt%, dioctyl phthalate (DOP), the 33wt% of 12wt%
Calcium carbonate (CaCO3) be uniformly mixed using high speed mixer, blends described above is fed in double screw extruder and squeezes out, be granulated
Uniformly mixed particle is obtained, is fed into double screw extruder at 310 DEG C through feeding hopper auto feed through hollow spinneret group
Part squeezing out quantitative, component internal are passed through nitrogen, and spinning melt is after air bath solidification, after 140 DEG C of hot-rollings, carry out online
Stretching and winding, online draw ratio are 1 times, obtain nascent hollow-fibre membrane；
Nascent hollow-fibre membrane carries out post-tensioning, and post-tensioning thermal finalization is carried out in 140 DEG C of oven heat stretching-machines, stretches speed
Rate is 2mm/min, draw ratio 0.2, then film wire is immersed in 10wt% aqueous hydrochloric acid solution by fixed length thermal finalization 30min, is located
Reason 5 days, then extraction is washed, and washing obtains perfluoroethylene-propylene hollow-fibre membrane.
Embodiment 3
By perfluoroethylene-propylene (FEP) powder of 60wt%, the dioctyl phthalate of 11.8wt%, 28wt% carbon
Sour calcium (CaCO3), 0.2wt% graphene using high speed mixer be uniformly mixed, blends described above is fed into double screw extruder
Middle extrusion, granulation obtain uniformly mixed particle, are fed into double screw extruder through feeding hopper auto feed and pass through at 290 DEG C
Hollow spinning pack squeezing out quantitative, component internal are passed through nitrogen, and spinning melt is after air bath solidification, using 120 DEG C of hot-rollings
Afterwards, online stretching and winding is carried out, online draw ratio is 1.5 times, obtains nascent hollow-fibre membrane；
Nascent hollow-fibre membrane carries out post-tensioning, and post-tensioning thermal finalization is carried out in 120 DEG C of oven heat stretching-machines, stretches speed
Rate is 1mm/min, draw ratio 0.4, then film wire is immersed in 30wt% aqueous acetic acid by fixed length thermal finalization 30min, is located
Reason 7 days, then extraction is washed, and washing obtains perfluoroethylene-propylene hollow-fibre membrane.
Embodiment 4
By perfluoroethylene-propylene (FEP) powder of 60wt%, the dioctyl phthalate (DOP) and adjacent benzene two of 10wt%
Calcium carbonate (the CaCO of formic acid dibutyl ester (DOP) mixed plasticizer (mass ratio 1:1), 28wt%3), 5wt% hydrophilic silicon dioxide
Using high speed mixer be uniformly mixed, will blends described above feed double screw extruder in squeeze out, be granulated obtain it is uniformly mixed
Particle is fed into double screw extruder at 290 DEG C through feeding hopper auto feed through hollow spinning pack squeezing out quantitative, component
Inside is passed through nitrogen, and spinning melt after 120 DEG C of hot-rollings, carries out online stretching and winding after air bath solidification, online to draw
Stretching multiple is 1.5 times, obtains nascent hollow-fibre membrane；
Nascent hollow-fibre membrane carries out post-tensioning, and post-tensioning thermal finalization is carried out in 120 DEG C of oven heat stretching-machines, stretches speed
Rate is 1mm/min, draw ratio 0.6, then film wire is immersed in 30wt% aqueous acetic acid by fixed length thermal finalization 30min, is located
Reason 7 days, then extraction is washed, and washing obtains perfluoroethylene-propylene hollow-fibre membrane.
Contact angle, pure water flux, breaking strength and resistance to are carried out to perfluoroethylene-propylene hollow-fibre membrane obtained by embodiment 1-4
Soda acid, organic solvent test.
Using the Static water contact angles of DSA100 type Static Contact angle tester test film at room temperature；Certainly using laboratory
Control equipment carries out pure water flux test, and test pressure is 0.2MPa；Using JBDL-2000N type electronic tensile test machine test film
Breaking strength；Film wire is separately immersed in the aqueous hydrochloric acid solution, sodium hydrate aqueous solution, acetone soln of 10wt% after 30 days,
It tests its mechanical strength conservation rate and characterizes its acid and alkali-resistance, organic solvent properties, test result is listed in Table 1 below.
Table 1
The perfluoroethylene-propylene hollow fiber membrane surface obtained it can be seen from Fig. 1-4 is in stretchable holes, dissolution hole and interface
The multiple pore structure in hole, cross section are uniform three-dimensional network pore structure；As can be seen from the above table, the film obtained has good logical
Permeability, mechanical strength and good acid-alkali-corrosive-resisting, solvent resistance.
The present invention does not address place and is suitable for the prior art.
Claims (10)
1. a kind of film formula of perfluoroethylene-propylene hollow-fibre membrane, it is characterised in that the group of the formula becomes perfluoroethylene third
50~75wt% of alkene, 0~10wt% of 20~40wt% of pore-foaming agent, 5~15wt% of plasticizer and auxiliary additive, the sum of each component
For 100wt%；The pore-foaming agent is calcium carbonate.
2. the film formula of perfluoroethylene-propylene hollow-fibre membrane according to claim 1, it is characterised in that the plasticising
Agent is at least one of dibutyl phthalate, diethyl phthalate or dioctyl phthalate.
3. the film formula of perfluoroethylene-propylene hollow-fibre membrane according to claim 2, it is characterised in that the plasticising
Agent is dioctyl phthalate.
4. the film formula of perfluoroethylene-propylene hollow-fibre membrane according to claim 1, it is characterised in that the auxiliary
Additive is at least one of graphene, silica or titanium dioxide；Graphene, silica and titanium dioxide are averaged
Partial size is 0.01-5 μm.
5. the film formula of perfluoroethylene-propylene hollow-fibre membrane according to claim 1, it is characterised in that calcium carbonate
Average grain diameter is 0.3-8 μm.
6. a kind of preparation method of perfluoroethylene-propylene hollow-fibre membrane, it is characterised in that method includes the following steps:
Step 1, by claim 1-5 it is any it is described formula after mixing, obtain uniformly mixed grain by squeezing out, being granulated
Son, by particle through hollow spinning pack squeezing out quantitative at 260~380 DEG C, component internal is passed through inert gas, and spinning melt exists
After solidifying in air bath, online stretching and winding is carried out, obtains nascent hollow-fibre membrane；
Nascent hollow-fibre membrane is carried out post-tensioning thermal finalization by step 2, and then film wire is immersed in acid solution and washes out carbonic acid
Calcium；Then extraction is washed, then washes to obtain perfluoroethylene-propylene hollow-fibre membrane.
7. the preparation method of perfluoroethylene-propylene hollow-fibre membrane according to claim 6, it is characterised in that in step 1,
Spinning melt after 100~150 DEG C of hot-rollings, carries out online stretching and winding after middleization is consolidated in air bath；Online draw ratio
It is 1~2 times；It is 0.3~2.0m that air bath, which solidifies length,.
8. the preparation method of perfluoroethylene-propylene hollow-fibre membrane according to claim 6, it is characterised in that in step 2,
Nascent hollow-fibre membrane carries out post-tensioning thermal finalization, rate of extension 0.5-50mm/ in 80~160 DEG C of oven heat stretching-machines
Min, draw ratio are 0.2~2,10~60min of fixed length thermal finalization.
9. the preparation method of perfluoroethylene-propylene hollow-fibre membrane according to claim 6, it is characterised in that in step 2,
Acid solution is hydrochloric acid or aqueous acetic acid, and concentration is 5~30wt%.
10. the preparation method of perfluoroethylene-propylene hollow-fibre membrane according to claim 9, it is characterised in that in step 2,
Acid solution is the aqueous hydrochloric acid solution of 8~12wt% of concentration.
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| CN110180401A (en) * | 2019-06-28 | 2019-08-30 | 天津工业大学 | A kind of preparation method of (per) fluoropolymer hollow-fibre membrane |
| CN110347895A (en) * | 2019-06-11 | 2019-10-18 | 重庆工商大学融智学院 | Ecological space data crawling method based on Web |
| CN115337796A (en) * | 2022-08-09 | 2022-11-15 | 烟台大学 | Polyfluorinated ethylene-based hollow fiber membrane |
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Application publication date: 20190219 |