CN107899435A - A kind of preparation method of polyvinylidene fluoride dewatering hollow-fibre membrane - Google Patents
A kind of preparation method of polyvinylidene fluoride dewatering hollow-fibre membrane Download PDFInfo
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- CN107899435A CN107899435A CN201711143021.9A CN201711143021A CN107899435A CN 107899435 A CN107899435 A CN 107899435A CN 201711143021 A CN201711143021 A CN 201711143021A CN 107899435 A CN107899435 A CN 107899435A
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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
- B01D69/085—Details relating to the spinneret
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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
- B01D69/087—Details relating to the spinning process
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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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Abstract
The embodiment of the invention discloses a kind of preparation method of polyvinylidene fluoride dewatering hollow-fibre membrane, comprise the following steps：Weigh following raw material respectively by mass percentage：The sum of 25%~45% Kynoar, 20%~60% nano-particle, 15%~35% diluent, above-mentioned raw materials are 100%；By load weighted nano-particle and diluent after mixing, load weighted Kynoar is added, is uniformly mixed again, obtains casting film powder；Gained casting film powder is melted with extruder and is extruded through spinning head, fiber film wire is obtained, gained fiber film wire is cooled down through coagulation bath, obtain hollow-fibre membrane runic, spinning head dry-spinning path is 2~30cm；The nano-particle and diluent in gained hollow-fibre membrane runic are removed, polyvinylidene fluoride dewatering hollow-fibre membrane is made.By polyvinylidene fluoride dewatering hollow-fibre membrane made from present invention method, even aperture distribution is consistent, has good hydrophobicity and structural strength.
Description
Technical field
The present invention relates to tunica fibrosa preparing technical field, more particularly to a kind of system of polyvinylidene fluoride dewatering hollow-fibre membrane
Preparation Method.
Background technology
Hydrophobic hollow fiber membrane is that one kind has hydrophobic film, with the development of hydrophobic hollow fiber membrane technology, is dredged
Moisture film can be applied in all Alternatives such as membrane distillation, film evaporation, membrane extraction, membrane crystallization, film degassing, film aeration, its application neck
Domain is further extensive.
Existing hydrophobic hollow fiber membrane is usually made by polypropylene, polytetrafluoroethylene (PTFE) or Kynoar.Wherein, poly- third
The alkene prices of raw materials are cheap, and pulling method film-forming process is simple, but institute's made membrane mechanical strength, weatherability and chemical stability compared with
Difference；Polytetrafluoroethylene (PTFE) hydrophobicity is excellent, but the hydrophobic film surface obtained by adding the film forming manufacture of finish drawing by high temperature is in fracture
Hole, aperture is usually other in the micron-scale, and porosity is relatively low, generally below 50%, limits its application；Kynoar has excellent
Good hydrophobicity, film forming, chemical resistance and weatherability, is had wide range of applications by its obtained hydrophobic hollow fiber membrane.
The preparation method of existing polyvinylidene fluoride dewatering hollow-fibre membrane, is generally prepared using thermally induced phase separation, its
Technological principle is on the fusing point of polymer, is dissolved a polymer in the diluent of higher boiling, low volatility, and formation mixes
Liquid, and then cooling down, make solution system that phase process occur, are formed using polymer as continuous phase, and diluent is dispersed phase
Two phase structure, reuses extractant extraction diluent, you can polyvinylidene fluoride dewatering hollow-fibre membrane is made.But inventor
It was found that the polyvinylidene fluoride dewatering hollow-fibre membrane prepared using above-mentioned thermally induced phase separation, intensity and hydrophobicity are relatively low, film
In easily there is excessive and too small hole, pore-size distribution homogeneity is relatively low；And for polyvinylidene fluoride dewatering hollow-fibre membrane and
Speech, its pore-size distribution homogeneity is higher, and cutoff performance is better, therefore, how to further improve the hollow fibre of polyvinylidene fluoride dewatering
The pore-size distribution homogeneity of film is tieed up, just becomes those skilled in the art's urgent problem to be solved.
The content of the invention
The embodiment of the invention discloses a kind of preparation method of polyvinylidene fluoride dewatering hollow-fibre membrane, gathers inclined fluorine to improve
The pore-size distribution homogeneity of ethene hydrophobic hollow fiber membrane.Technical solution is as follows：
Step A：Weigh following raw material respectively by mass percentage：25%~45% Kynoar, 20%~60%
Nano-particle, 15%~35% diluent, the sum of above-mentioned raw materials are 100%；
Step B：By load weighted nano-particle and diluent after mixing, load weighted Kynoar is added,
It is uniformly mixed again, obtains casting film powder；
Step C：Gained casting film powder is melted with extruder and is extruded through spinning head, obtains fiber film wire, gained is fine
Dimension film wire is cooled down through coagulation bath, obtains hollow-fibre membrane runic, wherein, the dry-spinning path of spinning head is 2~30cm；
Step D：The nano-particle and diluent in gained hollow-fibre membrane runic are removed, is made in polyvinylidene fluoride dewatering
Empty fiber membrane.
Wherein, the diluent includes strong diluent and weak diluent, wherein, the matter between strong diluent and weak diluent
Measuring ratio is：1：0.2~6.
Wherein, the strong diluent is selected from：Diethyl phthalate, dibutyl phthalate, phthalic acid two
Cyclohexyl, triacetyl glycerine, at least one of triethyl phosphate and 1,4-butyrolactone；The weak diluent is selected from：The last of the ten Heavenly stems two
Dioctyl phthalate, dibutyl sebacate, at least one of o-phthalic acid dibutyl ester and adipic acid dibutyl ester.
Wherein, the weight average molecular weight of the Kynoar is 200,000~500,000.
Wherein, the nano-particle is nano-calcium carbonate or nano silicon dioxide.
Wherein, the nano-calcium carbonate surface is through stearic acid treatment, the average grain diameter of the nano-calcium carbonate for 70~
150nm；The nano-silica surface is handled through silane coupling agent, the average grain diameter of the nano silicon dioxide for 50~
200nm。
Wherein, in the step B, temperature when being mixed to Kynoar, nano-particle and diluent is 25~75 DEG C.
Wherein, in the step D, nano-particle and diluent in gained hollow-fibre membrane runic is removed, is specifically included：
The hollow-fibre membrane runic is immersed into 4~8h of ethanol, 20~60 DEG C of ethanol temperature；
When the nano-particle is nano-calcium carbonate, by the hollow-fibre membrane runic after ethanol soaks through pickling processes
1~3 time, then 4~8h of immersion in deionized water is immersed, polyvinylidene fluoride dewatering hollow-fibre membrane is obtained after drying.
Wherein, in the step D, nano-particle and diluent in gained hollow-fibre membrane runic is removed, is specifically included：
The hollow-fibre membrane runic is immersed into 4~8h of ethanol, 20~60 DEG C of ethanol temperature；
When the nano-particle is nano silicon dioxide, by the hollow-fibre membrane runic after ethanol soaks through alkali cleaning at
Reason 1~3 time, then 4~8h of immersion in pure water is immersed, polyvinylidene fluoride dewatering hollow-fibre membrane is obtained after drying.
An embodiment of the present invention provides a kind of preparation method of polyvinylidene fluoride dewatering hollow-fibre membrane, by the feed
Nano-particle is added, nano-particle has the characteristics that particle is small, specific surface area is big, on the one hand, nano-particle is with particle diameter point
The characteristics of cloth is uniform, after the nano-particle in removing hollow-fibre membrane runic, can form the more homogeneous micropore of shape, so that
The pore-size distribution homogeneity of obtained polyvinylidene fluoride dewatering hollow-fibre membrane is improved, is correspondingly also obtained preferably hydrophobic
Property；On the other hand, can be that more nucleating points are provided in Kynoar crystallization process, help forms more stable poly- inclined fluorine
Ethene crystalline structure, so as to improve the structural strength of obtained polyvinylidene fluoride dewatering hollow-fibre membrane.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is attached drawing needed in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, without creative efforts, can be with
Other attached drawings are obtained according to these attached drawings.
Fig. 1 is to break through polyvinylidene fluoride dewatering hollow-fibre membrane made from the embodiment of the present invention 1,2,000 times of enlargement ratio
Face electromicroscopic photograph；
Fig. 2 is to break through polyvinylidene fluoride dewatering hollow-fibre membrane made from the embodiment of the present invention 1,20,000 times of enlargement ratio
Face electromicroscopic photograph；
Fig. 3 be through polyvinylidene fluoride dewatering hollow-fibre membrane made from the embodiment of the present invention 1,20,000 times of enlargement ratio it is interior
Surface electromicroscopic photograph；
Fig. 4 be through polyvinylidene fluoride dewatering hollow-fibre membrane made from the embodiment of the present invention 1,2,000 times of enlargement ratio it is outer
Surface electromicroscopic photograph；
Fig. 5 is through polyvinylidene fluoride dewatering hollow-fibre membrane, graph of pore diameter distribution made from the embodiment of the present invention 1；
Fig. 6 is through polyvinylidene fluoride dewatering hollow-fibre membrane made from the embodiment of the present invention 1, the test knot of surface contact angle
Fruit is schemed；
Fig. 7 is the polyvinylidene fluoride dewatering hollow-fibre membrane obtained by comparative example preparation method, 2,000 times of enlargement ratio
Section electromicroscopic photograph；
Fig. 8 is the polyvinylidene fluoride dewatering hollow-fibre membrane obtained by comparative example preparation method, amplifies 20,000 times of section
Electromicroscopic photograph；
Fig. 9 is the polyvinylidene fluoride dewatering hollow-fibre membrane obtained by comparative example preparation method, 10,000 times of enlargement ratio
Inner surface electromicroscopic photograph.
Embodiment
Below in conjunction with the attached drawing in the embodiment of the present invention, the technical solution in the embodiment of the present invention is carried out clear, complete
Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained every other without creative efforts
Embodiment, belongs to the scope of protection of the invention.
An embodiment of the present invention provides a kind of preparation method of polyvinylidene fluoride dewatering hollow-fibre membrane, including following step
Suddenly：
Step A：Weigh following raw material respectively by mass percentage：25%~45% Kynoar, 20%~60%
Nano-particle, 15%~35% diluent, the sum of above-mentioned raw materials are 100%.
In the present invention, the weight average molecular weight of Kynoar is 200,000~500,000, is preferably 250,000~350,000, inventor
It has been investigated that when the weight average molecular weight of Kynoar is higher than 250,000, obtained polyvinylidene fluoride dewatering hollow-fibre membrane
Structural strength will improve, when Kynoar weight average molecular weight be less than 350,000 when, obtained polyvinylidene fluoride dewatering is hollow
The pore-creating character of tunica fibrosa will improve, thus when Kynoar weight average molecular weight between 250,000~350,000 when, can make obtained
Polyvinylidene fluoride dewatering hollow-fibre membrane both there is excellent structural strength, also with good pore-creating character.
In the present invention, diluent can include strong diluent and weak diluent, wherein, strong diluent and weak diluent it
Between mass ratio be：1：0.2~6.In the preferred embodiment of the present invention, strong diluent can be selected from phthalic acid
Diethylester, dibutyl phthalate, dicyclohexyl phthalate, triacetyl glycerine, triethyl phosphate and Isosorbide-5-Nitrae-Ding Nei
At least one of ester；Weak diluent can be selected from di-n-octyl sebacate, dibutyl sebacate, o-phthalic acid dibutyl ester and oneself
At least one of diacid dibutyl ester.
In the present invention, nano-particle can be nano-calcium carbonate or nano silicon dioxide.Implement preparing the present invention
During the polyvinylidene fluoride dewatering hollow-fibre membrane of example, temperature would generally occur more than 200 degrees Celsius, if selecting other raw materials
Because of pyrolytic or the situation of reunion, polyvinylidene fluoride dewatering hollow-fibre membrane can not even be made when serious.Inventor's discovery,
When nano-calcium carbonate or nano silicon dioxide are applied to prepare polyvinylidene fluoride dewatering hollow-fibre membrane, they are in high temperature ring
It is not easily decomposed or reunites in border, also, particle diameter distribution is uniform, specific surface area is big, good hydrophobic spy since they also have
Point, therefore when preparing polyvinylidene fluoride dewatering hollow-fibre membrane for the present invention, obtained Kynoar can not only be improved
The pore-size distribution homogeneity of hydrophobic hollow fiber membrane, moreover it is possible to improve its structural strength, and further improve polyvinylidene fluoride dewatering
The hydrophobicity of hollow-fibre membrane.
Preferably, above-mentioned nano-calcium carbonate surface can through stearic acid treatment, the average grain diameter of nano-calcium carbonate for 70~
150nm；Above-mentioned nano-silica surface can be handled through silane coupling agent, the average grain diameter of nano silicon dioxide for 50~
200nm。
Step B：By load weighted nano-particle and diluent after mixing, load weighted Kynoar is added,
It is uniformly mixed again, obtains casting film powder.
In the present invention, when mixing to Kynoar, nano-particle and diluent, controlled at 25~
75 DEG C, it is possible to increase the mobility of diluent, so as to promote above-mentioned raw materials uniformly to mix.
Step C：Gained casting film powder is melted with extruder and is extruded through spinning head, obtains fiber film wire, gained is fine
Dimension film wire is cooled down through coagulation bath, obtains hollow-fibre membrane runic, wherein, the dry-spinning path of spinning head is 2~30cm.
In the present invention, double screw extruder heating melting casting film powder can be selected；It is 2~30cm to control dry-spinning path, excellent
Elect 5~20cm as, make the fiber film wire of extrusion Slow cooling in atmosphere.In the preferred embodiment of the present invention, may be used
Fiber film wire is collected using wire wrapping wheel, the draw speed of fiber film wire is 10~50m/min, is preferably 20~40m/min.
Step D：The nano-particle and diluent in gained hollow-fibre membrane runic are removed, is made in polyvinylidene fluoride dewatering
Empty fiber membrane.
In the present invention, ethanol can be used to remove the diluent in hollow-fibre membrane runic, specifically, can will be hollow
Tunica fibrosa runic immersion 4~8h of ethanol, 20~60 DEG C of ethanol temperature, afterwards：
Alternatively, when nano-particle is nano-calcium carbonate, by the hollow-fibre membrane runic after ethanol soaks through dilute salt
Sour pickling processes 1~3 time, then 4~8h of immersion in deionized water is immersed, polyvinylidene fluoride dewatering doughnut is obtained after drying
Film, wherein, dilute hydrochloric acid mass percentage concentration is 5~10%；
Alternatively, when nano-particle is nano silicon dioxide, by the hollow-fibre membrane runic after ethanol soaks through hydrogen
Sodium hydroxide solution alkali cleaning is handled 1~3 time, then immerses 4~8h of immersion in pure water, and the hollow fibre of polyvinylidene fluoride dewatering is obtained after drying
Film is tieed up, wherein, sodium hydroxide solution mass percentage concentration is 5~10%.
Using above-mentioned preparation method, after the nano-particle in removing hollow-fibre membrane runic, it is more equal shape can be formed
One micropore, so as to improve the pore-size distribution homogeneity of obtained polyvinylidene fluoride dewatering hollow-fibre membrane；In film forming procedure
In, nano-particle can promote to form more stable Kynoar crystalline structure, be dredged so as to improve obtained Kynoar
The structural strength of water hollow-fibre membrane.
Technical scheme is described below in conjunction with specific embodiment, described embodiment is only this
Invention part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art exist
All other embodiments obtained under the premise of creative work are not made, belong to the scope of protection of the invention.
Embodiment 1
Weigh following raw material respectively by mass percentage：The Kynoar of 250g, the nano-particle of 400g, 350g's is dilute
Agent is released, wherein, nano-particle selects nano-calcium carbonate, and nano-calcium carbonate surface is averaged through stearic acid treatment, nano-calcium carbonate
Particle diameter is 70nm；Strong diluent is diethyl phthalate, and weak diluent is di-n-octyl sebacate, wherein, strong diluent
290g, weak diluent 60g, the weight average molecular weight of Kynoar is 200,000；Load weighted nano-calcium carbonate and diluent are mixed
Close uniformly, mixing temperature is 25 DEG C, adds load weighted Kynoar, is uniformly mixed again, obtains casting film powder；By institute
Obtain casting film powder to be melted with extruder, 180 DEG C of melting temperature, and extruded through spinning head, obtain fiber film wire, wherein, spinning head
Dry-spinning path be 10cm；Gained fiber film wire is cooled down through coagulation bath, obtains hollow-fibre membrane runic；By hollow-fibre membrane runic
Immerse ethanol 4h, 20 DEG C of ethanol temperature, by the hollow-fibre membrane runic after ethanol soaks through dilute hydrochloric acid pickling processes 1 time, then
Immerse in deionized water and soak 4h, polyvinylidene fluoride dewatering hollow-fibre membrane is obtained after drying, wherein, dilute hydrochloric acid quality percentage is dense
Spend for 5%, remove nano-calcium carbonate and diluent in gained hollow-fibre membrane runic, the hollow fibre of polyvinylidene fluoride dewatering is made
Tie up film.Gained polyvinylidene fluoride dewatering hollow-fibre membrane internal diameter 0.8mm, outside diameter 1.4mm, porosity 75%, permeable pressure
0.54MPa, pure water flux 1600L/m2.h.bar.25 DEG C, flux of membrane distillation 52kg/m2.h, monofilament pull-off force 12N, elongation percentage
120%.
Embodiment 2
Weigh following raw material respectively by mass percentage：The Kynoar of 450g, the nano-particle of 200g, 350g's is dilute
Agent is released, wherein, nano-particle selects nano-calcium carbonate, and nano-calcium carbonate surface is through stearic acid treatment, the particle diameter of nano-calcium carbonate
For 100nm；Strong diluent is dibutyl phthalate, and weak diluent is dibutyl sebacate, strong diluent 175g, weak dilution
Agent 175g, the weight average molecular weight of Kynoar is 300,000；Load weighted nano-calcium carbonate and diluent are uniformly mixed, mixed
Temperature is 45 DEG C, adds load weighted Kynoar, is uniformly mixed again, obtains casting film powder；By gained casting film powder
Melted with extruder, 200 DEG C of melting temperature, and extruded through spinning head, obtain fiber film wire, wherein, the dry-spinning path of spinning head is
2cm；Gained fiber film wire is cooled down through coagulation bath, obtains hollow-fibre membrane runic；Hollow-fibre membrane runic is immersed into ethanol 6h,
30 DEG C of ethanol temperature, by the hollow-fibre membrane runic after ethanol soaks through dilute hydrochloric acid pickling processes 2 times, then immerses deionized water
Middle immersion 6h, obtains polyvinylidene fluoride dewatering hollow-fibre membrane after drying, wherein, dilute hydrochloric acid mass percentage concentration is 8%, is removed
Nano-calcium carbonate and diluent in gained hollow-fibre membrane runic, are made polyvinylidene fluoride dewatering hollow-fibre membrane.
Embodiment 3
Weigh following raw material respectively by mass percentage：The Kynoar of 250g, the nano-particle of 600g, 150g's is dilute
Agent is released, wherein, nano-particle selects nano-calcium carbonate, and nano-calcium carbonate surface is through stearic acid treatment, the particle diameter of nano-calcium carbonate
For 150nm；Strong diluent is triacetyl glycerine, and weak diluent is o-phthalic acid dibutyl ester, strong diluent 30g, weak dilution
Agent 120g, the weight average molecular weight of Kynoar is 400,000；Load weighted nano-calcium carbonate and diluent are uniformly mixed, mixed
Temperature is 55 DEG C, adds load weighted Kynoar, is uniformly mixed again, obtains casting film powder；By gained casting film powder
Melted with extruder, 210 DEG C of melting temperature, and extruded through spinning head, obtain fiber film wire, wherein, the dry-spinning path of spinning head is
15cm；Gained fiber film wire is cooled down through coagulation bath, obtains hollow-fibre membrane runic；Hollow-fibre membrane runic is immersed into ethanol
8h, ethanol temperature 50 C, by the hollow-fibre membrane runic after ethanol soaks through dilute hydrochloric acid pickling processes 3 times, then immerse from
8h is soaked in sub- water, polyvinylidene fluoride dewatering hollow-fibre membrane is obtained after drying, wherein, dilute hydrochloric acid mass percentage concentration is
10%, nano-calcium carbonate and diluent in gained hollow-fibre membrane runic are removed, polyvinylidene fluoride dewatering doughnut is made
Film.
Embodiment 4
Weigh following raw material respectively by mass percentage：The Kynoar of 450g, the nano-particle of 200g, 350g's is dilute
Agent is released, wherein, nano-particle selects nano silicon dioxide, and nano-silica surface is handled through silane coupling agent processing, nanometer
The average grain diameter of silica is 50nm；Strong diluent is dibutyl phthalate, and weak diluent is di-n-octyl sebacate, by force
Diluent 87.5g, weak diluent 262.5g, the weight average molecular weight of Kynoar is 350,000；By load weighted nanometer titanium dioxide
Silicon and diluent are uniformly mixed, and mixing temperature is 25 DEG C, adds load weighted Kynoar, is uniformly mixed again, obtains
Casting film powder；Gained casting film powder is melted with extruder, 190 DEG C of melting temperature, and extruded through spinning head, obtain tunica fibrosa
Silk, wherein, the dry-spinning path of spinning head is 30cm；Gained fiber film wire is cooled down through coagulation bath, obtains hollow-fibre membrane runic；Will
Hollow-fibre membrane runic immerses ethanol 4h, 20 DEG C of ethanol temperature, by the hollow-fibre membrane runic after ethanol soaks through hydroxide
Sodium solution, which subtracts, washes processing 2 times, then immerses and 4h is soaked in deionized water, and polyvinylidene fluoride dewatering hollow-fibre membrane is obtained after drying,
Wherein, sodium hydroxide solution mass percentage concentration is 5%, removes the nano silicon dioxide and dilute in gained hollow-fibre membrane runic
Agent is released, polyvinylidene fluoride dewatering hollow-fibre membrane is made.Gained polyvinylidene fluoride dewatering hollow-fibre membrane internal diameter 1.0mm, outside diameter
1.8mm, porosity 70%, permeable pressure 0.50MPa, pure water flux 1000L/m2.h.bar.25 DEG C, flux of membrane distillation 40kg/m2.h
Monofilament pull-off force 15N, elongation percentage 100%, most probable pore size 380nm, 102 degree of surface contact angle.
Embodiment 5
Weigh following raw material respectively by mass percentage：The Kynoar of 250g, the nano-particle of 600g, 150g's is dilute
Agent is released, wherein, nano-particle selects nano silicon dioxide, and nano-silica surface is handled through silane coupling agent processing, nanometer
The average grain diameter of silica is 150nm；Strong diluent is the triethyl phosphate and 1,4-butyrolactone of equivalent, and weak diluent is the last of the ten Heavenly stems
Adipate, strong diluent 30g, weak diluent 120g, the weight average molecular weight of Kynoar is 400,000；Received load weighted
Rice silica and diluent are uniformly mixed, and mixing temperature is 60 DEG C, adds load weighted Kynoar, and mixing is equal again
It is even, obtain casting film powder；Gained casting film powder is melted with extruder, 210 DEG C of melting temperature, and extruded through spinning head, obtained
Fiber film wire, wherein, the dry-spinning path of spinning head is 20cm；Gained fiber film wire is cooled down through coagulation bath, obtains hollow-fibre membrane
Runic；Hollow-fibre membrane runic is immersed into ethanol 6h, 40 DEG C of ethanol temperature, the hollow-fibre membrane runic after ethanol soaks is passed through
Sodium hydroxide solution, which subtracts, washes processing 1 time, then immerses and 6h is soaked in deionized water, and the hollow fibre of polyvinylidene fluoride dewatering is obtained after drying
Film is tieed up, wherein, sodium hydroxide solution mass percentage concentration is 8%, removes the nanometer titanium dioxide in gained hollow-fibre membrane runic
Silicon and diluent, are made polyvinylidene fluoride dewatering hollow-fibre membrane.
Embodiment 6
Weigh following raw material respectively by mass percentage：The Kynoar of 300g, the nano-particle of 500g, 200g's is dilute
Agent is released, wherein, nano-particle selects nano silicon dioxide, and nano-silica surface is handled through silane coupling agent processing, nanometer
The average grain diameter of silica is 200nm；Strong diluent is triacetyl glycerine, and weak diluent is o-phthalic acid dibutyl ester,
Strong diluent 28.5g, weak diluent 171.5g, the weight average molecular weight of Kynoar is 500,000；By load weighted nano-silica
SiClx and diluent are uniformly mixed, and mixing temperature is 75 DEG C, adds load weighted Kynoar, is uniformly mixed again, obtains
To casting film powder；Gained casting film powder is melted with extruder, 220 DEG C of melting temperature, and extruded through spinning head, obtain tunica fibrosa
Silk, wherein, the dry-spinning path of spinning head is 25cm；Gained fiber film wire is cooled down through coagulation bath, obtains hollow-fibre membrane runic；Will
Hollow-fibre membrane runic immerses ethanol 8h, ethanol temperature 60 C, by the hollow-fibre membrane runic after ethanol soaks through hydroxide
Sodium solution, which subtracts, washes processing 2 times, then immerses and 8h is soaked in deionized water, and polyvinylidene fluoride dewatering hollow-fibre membrane is obtained after drying,
Wherein, sodium hydroxide solution mass percentage concentration be 10%, remove gained hollow-fibre membrane runic in nano silicon dioxide and
Diluent, is made polyvinylidene fluoride dewatering hollow-fibre membrane.
Comparative example polyvinylidene fluoride dewatering doughnut membrane preparation method, its preparation process are generally：300g is chosen to gather partially
Vinyl fluoride and 700g diluents, wherein diluent are made of equivalent diethyl phthalate and di-n-octyl sebacate, will be above-mentioned
Two kinds of raw materials are granulated after mixing, and (purpose of granulation is to be able to make Kynoar and diluent more fully be blended in
Together), gained particle input extruder melting then will be granulated, and will be extruded through spinning head, obtains fiber film wire, then extract fiber
The diluent in film wire is tieed up, polyvinylidene fluoride dewatering hollow-fibre membrane is made.
Fig. 1 is to break through polyvinylidene fluoride dewatering hollow-fibre membrane made from the embodiment of the present invention 1,2,000 times of enlargement ratio
Face electromicroscopic photograph；Fig. 2 is through polyvinylidene fluoride dewatering hollow-fibre membrane made from the embodiment of the present invention 1,20,000 times of enlargement ratio
Section electromicroscopic photograph.As depicted in figs. 1 and 2, obtained polyvinylidene fluoride dewatering hollow-fibre membrane, the distribution of section mesopore
Uniformly, each pore size is basically identical, and section is in co-continuous cavernous structure.
Fig. 3 be through polyvinylidene fluoride dewatering hollow-fibre membrane made from the embodiment of the present invention 1,20,000 times of enlargement ratio it is interior
Surface electromicroscopic photograph.As shown in figure 3, obtained polyvinylidene fluoride dewatering hollow-fibre membrane, the distribution of pores in its inner surface
Uniformly, each pore size is basically identical.
Fig. 4 be through polyvinylidene fluoride dewatering hollow-fibre membrane made from the embodiment of the present invention 1,2,000 times of enlargement ratio it is outer
Surface electromicroscopic photograph；As shown in figure 4, obtained polyvinylidene fluoride dewatering hollow-fibre membrane, its outer surface separate pore size distribution compared with
Uniformly, percent opening is higher.
Fig. 5 is through polyvinylidene fluoride dewatering hollow-fibre membrane made from the embodiment of the present invention 1, graph of pore diameter distribution, such as Fig. 5 institutes
Show, most probable pore size (most probable probability aperture) is 0.21um, has the characteristics that narrow pore-size distribution.
Fig. 6 is through polyvinylidene fluoride dewatering hollow-fibre membrane made from the embodiment of the present invention 1, the test knot of surface contact angle
Fruit is schemed, as shown in fig. 6, the surface contact angle surveyed is 107.55 degree, illustrates that the polyvinylidene fluoride dewatering hollow-fibre membrane has
Excellent hydrophobicity.
Fig. 7 is the polyvinylidene fluoride dewatering hollow-fibre membrane obtained by comparative example preparation method, 2,000 times of enlargement ratio
Section electromicroscopic photograph, Fig. 8 are the section electromicroscopic photograph of 20,000 times of amplification.As shown in Figure 7 and Figure 8, obtained Kynoar
Hydrophobic hollow fiber membrane, section mesopore distribution uniform, but pore size difference is obvious.
Fig. 9 is the polyvinylidene fluoride dewatering hollow-fibre membrane obtained by comparative example preparation method, 10,000 times of enlargement ratio
Inner surface electromicroscopic photograph, its inner surface distribution of pores is not uniform enough, and each pore size difference is larger.
A kind of preparation method of polyvinylidene fluoride dewatering hollow-fibre membrane provided by the present invention has been carried out in detail above
Introduce.Specific embodiment used herein is set forth the principle of the present invention and embodiment, and above example is said
It is bright to be only intended to help the method and its central idea for understanding the present invention.It should be pointed out that for those of ordinary skill in the art
For, without departing from the principle of the present invention, some improvement and modification can also be carried out to the present invention, these improve and repair
Decorations also fall into the protection of the claims in the present invention.
It should be noted that herein, term " comprising ", "comprising" or its any other variant are intended to non-row
His property includes, so that process, method, article or equipment including a series of elements not only include those key elements, and
And other elements that are not explicitly listed are further included, or further include as this process, method, article or equipment institute inherently
Key element.In the absence of more restrictions, the key element limited by sentence "including a ...", it is not excluded that including institute
State in process, method, article or the equipment of key element that also there are other identical element.
Each embodiment in this specification is described using relevant mode, identical similar portion between each embodiment
Divide mutually referring to what each embodiment stressed is the difference with other embodiment.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the scope of the present invention.It is all
Any modification, equivalent replacement, improvement and so within the spirit and principles in the present invention, are all contained in protection scope of the present invention
It is interior.
Claims (9)
1. a kind of preparation method of polyvinylidene fluoride dewatering hollow-fibre membrane, it is characterised in that comprise the following steps：
Step A：Weigh following raw material respectively by mass percentage：25%~45% Kynoar, 20%~60% receives
The sum of rice corpuscles, 15%~35% diluent, above-mentioned raw materials are 100%；
Step B：By load weighted nano-particle and diluent after mixing, load weighted Kynoar is added, again
It is uniformly mixed, obtains casting film powder；
Step C：Gained casting film powder is melted with extruder and is extruded through spinning head, fiber film wire is obtained, by gained tunica fibrosa
Silk is cooled down through coagulation bath, obtains hollow-fibre membrane runic, wherein, the dry-spinning path of spinning head is 2~30cm；
Step D：The nano-particle and diluent in gained hollow-fibre membrane runic are removed, the hollow fibre of polyvinylidene fluoride dewatering is made
Tie up film.
2. the preparation method of polyvinylidene fluoride dewatering hollow-fibre membrane according to claim 1, it is characterised in that described dilute
Releasing agent includes strong diluent and weak diluent, wherein, the mass ratio between strong diluent and weak diluent is：1：0.2~6.
3. the preparation method of polyvinylidene fluoride dewatering hollow-fibre membrane according to claim 2, it is characterised in that described strong
Diluent is selected from：Diethyl phthalate, dibutyl phthalate, dicyclohexyl phthalate, acetoglyceride, phosphorus
At least one of triethylenetetraminehexaacetic acid ester and 1,4- butyrolactone；The weak diluent is selected from：Di-n-octyl sebacate, dibutyl sebacate,
At least one of o-phthalic acid dibutyl ester and adipic acid dibutyl ester.
4. the preparation method of polyvinylidene fluoride dewatering hollow-fibre membrane according to claim 1, it is characterised in that described poly-
The weight average molecular weight of vinylidene is 200,000~500,000.
5. the preparation method of polyvinylidene fluoride dewatering hollow-fibre membrane according to claim 1, it is characterised in that described to receive
Rice corpuscles is nano-calcium carbonate or nano silicon dioxide.
6. the preparation method of polyvinylidene fluoride dewatering hollow-fibre membrane according to claim 5, it is characterised in that described to receive
For rice calcium carbonate surface through stearic acid treatment, the average grain diameter of the nano-calcium carbonate is 70~150nm；The nano silicon dioxide
Surface is handled through silane coupling agent, and the average grain diameter of the nano silicon dioxide is 50~200nm.
7. the preparation method of polyvinylidene fluoride dewatering hollow-fibre membrane according to claim 1, it is characterised in that the step
In rapid B, temperature when being mixed to Kynoar, nano-particle and diluent is 25~75 DEG C.
8. the preparation method of polyvinylidene fluoride dewatering hollow-fibre membrane according to claim 5, it is characterised in that the step
In rapid D, nano-particle and diluent in gained hollow-fibre membrane runic are removed, is specifically included：
The hollow-fibre membrane runic is immersed into 4~8h of ethanol, 20~60 DEG C of ethanol temperature；
When the nano-particle is nano-calcium carbonate, by the hollow-fibre membrane runic after ethanol soaks through pickling processes 1~3
It is secondary, then 4~8h of immersion in deionized water is immersed, polyvinylidene fluoride dewatering hollow-fibre membrane is obtained after drying.
9. the preparation method of polyvinylidene fluoride dewatering hollow-fibre membrane according to claim 5, it is characterised in that the step
In rapid D, nano-particle and diluent in gained hollow-fibre membrane runic are removed, is specifically included：
The hollow-fibre membrane runic is immersed into 4~8h of ethanol, 20~60 DEG C of ethanol temperature；
When the nano-particle is nano silicon dioxide, the hollow-fibre membrane runic after ethanol soaks is handled 1 through alkali cleaning
~3 times, then 4~8h of immersion in pure water is immersed, polyvinylidene fluoride dewatering hollow-fibre membrane is obtained after drying.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110003591A (en) * | 2019-03-29 | 2019-07-12 | 华中科技大学 | A kind of preparation method and flexible fiber of flexible fiber |
| CN110935331A (en) * | 2019-12-31 | 2020-03-31 | 北京中环膜材料科技有限公司 | Polyvinylidene fluoride ultrafiltration membrane prepared by thermally induced phase separation method and preparation method |
| CN111167317A (en) * | 2020-01-15 | 2020-05-19 | 上海翊科精密挤出技术有限公司 | Preparation of high-hydrophobicity hollow fiber membrane and desulfurization wastewater treatment method thereof |
| CN115558344A (en) * | 2022-10-27 | 2023-01-03 | 江苏厚生新能源科技有限公司 | PVDF hollow porous nanoparticle coating slurry, preparation method and composite diaphragm modified by same |
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| CN102179187A (en) * | 2010-12-10 | 2011-09-14 | 顾方明 | Polyvinylidene fluoride ultrafiltration membrane and preparation method thereof |
| CN104607061A (en) * | 2014-12-18 | 2015-05-13 | 东华大学 | A method of preparing a poly(ethene-co-tetrafluoroethene) film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102179187A (en) * | 2010-12-10 | 2011-09-14 | 顾方明 | Polyvinylidene fluoride ultrafiltration membrane and preparation method thereof |
| CN104607061A (en) * | 2014-12-18 | 2015-05-13 | 东华大学 | A method of preparing a poly(ethene-co-tetrafluoroethene) film |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110003591A (en) * | 2019-03-29 | 2019-07-12 | 华中科技大学 | A kind of preparation method and flexible fiber of flexible fiber |
| CN110935331A (en) * | 2019-12-31 | 2020-03-31 | 北京中环膜材料科技有限公司 | Polyvinylidene fluoride ultrafiltration membrane prepared by thermally induced phase separation method and preparation method |
| CN111167317A (en) * | 2020-01-15 | 2020-05-19 | 上海翊科精密挤出技术有限公司 | Preparation of high-hydrophobicity hollow fiber membrane and desulfurization wastewater treatment method thereof |
| CN115558344A (en) * | 2022-10-27 | 2023-01-03 | 江苏厚生新能源科技有限公司 | PVDF hollow porous nanoparticle coating slurry, preparation method and composite diaphragm modified by same |
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Application publication date: 20180413 |