CN105688692B - Polymer bear electrolemma and preparation method thereof - Google Patents
Polymer bear electrolemma and preparation method thereof Download PDFInfo
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- CN105688692B CN105688692B CN201610174329.9A CN201610174329A CN105688692B CN 105688692 B CN105688692 B CN 105688692B CN 201610174329 A CN201610174329 A CN 201610174329A CN 105688692 B CN105688692 B CN 105688692B
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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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
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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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
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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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0018—Thermally induced processes [TIPS]
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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
- B01D2325/16—Membrane materials having positively charged functional groups
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- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Water Supply & Treatment (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a kind of polymer bear electrolemmas and preparation method thereof.The perforated membrane is made using the bear electric polymer good with polymer material compatibility as polymer blend, using solid-liquid split-phase of the preparation method through Thermal inactive technology of melt spinning or coating rolling in the present invention, thus by adjusting the additive amount of the polymer blend, the perforated membrane formed with ultrafiltration pore diameter range, electric, the three-dimensional perforation networked pore structures of film surface bear relatively easily can be obtained or controlled；Since film preparation carries out under less than polymer material solidification temperature, the resolution problem of polymer blend under the conditions of previous spinodal phase separation film-making is avoided, while the preparation process of the perforated membrane is simple, adaptability is good, more new equipment is not needed to, convenient for promoting, there is good industrial prospect.
Description
Technical field
The present invention relates to technical field of polymer materials, especially a kind of polymer bear electrolemma and preparation method thereof.
Background technology
Kynoar and polysulfones are to be currently widely used for preparing porous film material, and be largely used to water process, film
The fields such as contactor, battery diaphragm and medical tissue engineering.It is to make at present that non-solvent, which causes phase technology and Thermal inactive technology,
Two kinds of common phase-inversion technologies of standby perforated membrane.Compared with non-solvent causes phase technology, Thermal inactive technology has pore structure
Easily regulation and control, film dynamic performance be high, film can dry state the advantages that preserving, it is especially suitable at room temperature without solvent polymeric object perforated membrane
Preparation, the method has been used to prepare polyethylene, polypropylene, polyvinylidene fluoride porous film at present.
Thermal inactive technology is Castro inventions in 1981（US Patent, 4247498,1981）, which is
Polymer and specific diluent are formed into homogeneous phase solution at high temperature, when the temperature decreases, solid-liquid or liquid-liquid occur for solution
Phase separation, after extraction removes diluent, diluent space shared in system is formed micropore.Thermal inactive technology is led to
The closing bee to form the very poor spherical particle structure of mechanical property, be formed through liquid-liquid phase separation that is separated through solid-liquid can often be obtained
It socket bore structure and is separated to form the networked pore structures of perforation through spinodal, wherein networked pore structures are most suitable as seperation film.
Thermal inactive technology preparative separation film is primarily present three problems at present：（1）Can only obtain aperture is 0.08-0.2 microns
Microfiltration membranes can not obtain the ultrafiltration membrane that aperture is less than 0.05 micron；（2）Can not be obtained in film-forming process surface lotus positive electricity or
The film of bear electricity, and film surface chargedization is remarkably improved membrane flux and antifouling property or even can realize the permanent of film
Hydrophilic modifying；（3）Only when the networked pore structures that the generation spinodal phase separation of casting film liquid system can just be penetrated through, and revolve
The conditional regulatory difficulty of nodel line phase separation is big and temperature is usually very high（It is about 50 degree higher than polymer melting temperature）.In order to reduce heat
The temperature being mutually film-made is caused to improve fenestra connectivity, three kinds of methods of generally use simultaneously：（1）In the casting film that solid-liquid phase separation occurs
Inorganic nano-particle is added in liquid, such as（Xu Guoqiang, Li pioneer, Lv Xiaolong, calcium carbonate prepare Kynoar to Thermal inactive
The influence of porous membrane structure, polymer material science and engineering, 2007,23（5）：234-237）, by inorganic nano-particle after film forming
Son is got rid of.Though the method can improve the connectivity in hole to a certain extent, it is difficult to solve inorganic nano-particle in film
The problems such as homodisperse problem, fenestra uniformity are deteriorated, and the introducing of inorganic nano-particle makes film become fragile；（2）Composite thermotropic
Phase technology（Zhu Zhenxin etc., composite thermotropic phase separation film-making method, CN101396641A, 2008）, which has used by a variety of
Water-soluble polymer good solvent and undesirable additive composition dicyandiamide solution, make casting solution occur using Thermal inactive as
Phase separation main, supplemented by phase separation, by adjusting the ratio of good solvent and additive come regulate and control thermotropic phase and
Non-solvent causes the degree of phase.Although this method reduces film temperature to a certain extent, how to handle containing Multiple components
Solvent be problem, and according to the description of patent applicant, obtained film still falls within the microfiltration membranes of 0.1 microns
And film surface does not have charged, therefore, it is difficult to improve the antifouling property of film；（3）The thermotropic phase technology of low temperature（Lu will is put down, Lv Xiaolong,
Wu Chunrui, low temperature thermally induced phase separation prepare the research of polyvinylidene fluoride hollow fiber porous membrane, and 2012,32（1）：12-17, film
Science and technology）, i.e., the solvent of polymer is added in the diluent of polymer, according to its reported result, obtained film is still
So belong to the microfiltration membranes of 0.1 microns and film surface is not charged.Blending hydrophilic polymer is to improve film contamination resistance, contracting
Membranelle separating layer aperture simple effective method.Such as in polyether sulfone（PES）In be blended into it is poly-（Ethylene oxide-propylene oxide-oxygen
Change ethylene）（Trade name F127）, phase technology is caused to prepare PES/F127 blend films using non-solvent（Wen Juan Chen, Yan
Lei Su, Jin Ming Peng, et al., Engineering a robust, versatile amphiphilic
membrane surface through forced surface segregation for ultralow flux-
decline. Adv. Funct. Mater., 2011, 21(1): 191-198.）Although the antifouling property of film significantly carries
Height, but F127 is water-soluble substances, loses hydrophily as the use of film is dissolved in water.The most suitable structure of seperation film is thin
The separating layer structure of supporting layer, networked pore structures, the structure are that casting film liquid system is revolved in TIPS separation processes at present
Nodel line obtains in the case of being separated.Polymeric hydrophilic agent is usually amphipathic copolymer, and prepares Kynoar（PVDF）
Or polysulfones（PSF）The temperature of the spinodal phase separation of film is not less than 200 DEG C, and amphipathic copolymer is decomposed at this temperature.
Film surface chargedization not only can further improve the hydrophilic effect and antifouling property of film, but also hydrophilic effect is lasting.Film at present
Surface chargeization is all to be post-processed after film preparation comes out through surface（For example surface coating or plasma etc. are first in film surface
Functional group is introduced, then obtains bear electrode/porous film with alkali process again）.The product that equipment used is not only complicated, obtains
It can be unstable, it is difficult to industrialization, and the mechanics of the plasma treated pore structure and film for destroying film surface of film surface
Performance.
Invention content
The purpose of the present invention is：A kind of polymer bear electrolemma and preparation method thereof is provided, it can be less than casting film liquid system
Strong mechanical performance is obtained in the case where spinodal phase separation temperature occurs, supporting layer is networked pore structures, separating layer is thin and lotus
Negative electricity polymer porous film, and can effectively solve there is system during existing Thermal inactive technology prepares polymer porous film
Film temperature height, aperture can only be in micro-filtrations（0.08-0.2 microns）In the range of it is adjustable and ultrafiltration membrane cannot be obtained（Separating layer aperture exists
0.01-0.05 microns）And the problem of long-term hydrophilic modifying is difficult to realize, and functional modification has been carried out to prepared film
（Chargedization makes negative electrical charge on film surface band, belongs to film functional modification）, with overcome the deficiencies in the prior art.
The invention is realized in this way：Polymer bear electrolemma, is calculated according to the mass fraction, including polymer material 15-40
Part, water-insoluble polymer blend 1.5-10 parts, 0.1-1 parts of 49-83.4 parts of diluent and antioxidant.
The polymer material is Kynoar, the homopolymer or copolymer of polysulfones.
The water-insoluble polymer blend is poly-（Methyl methacrylate-g- sodium acrylate）It is or poly-（Styrene-g-
Sodium acrylate）.
The diluent is diamyl phthalate, tributyrin, diethylene glycol dibenzoate or glycerine
Tribenzoate；When water-insoluble polymer blend is poly-（Methyl methacrylate-g- sodium acrylate）When, select O-phthalic
Sour diamyl ester or tributyrin；When water-insoluble polymer blend is poly-（Styrene-g- sodium acrylate）When, select diethyl
Bisbenzoate or tribenzoin.
The antioxidant is β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester.
The preparation method of polymer bear electrolemma takes each component by above-mentioned mass fraction, and by polymer material, non-aqueous
Property polymer blend, diluent and the abundant mixing of antioxidant after, by blending extrusion, obtain compound particles；By the mixed of acquisition
Polymer beads at 120-170 DEG C after spinning or coating, rolling, then through air or water-bath cooling, are then gone through fully washing
Except diluent, you can obtain the polymer bear electrolemma.
The abundant washing is specifically, first pass through the washing of first time room temperature ethanol, then carry out second of room temperature ethanol and wash
It washs.
After spinning or coating, rolling, the doughnut of extrusion or the rolling of coating is allowed to pass through 0.5- in air
After 20cm, then batched after water-bath or air bath cooling.
The existing thermotropic phase separation film-making technology for obtaining polymer mesh pore structure is to use polymer and mixed diluting
The moderate diluent that interacts between agent so that casting film liquid system is directly entered unstable regin in temperature-fall period and revolves
Nodel line phase separation is realized.The condition that spinodal phase separation occurs is not only very harsh, but also temperature is molten higher than polymer material
Melt temperature so that polymer is easily degraded.In addition, polymer film prepared by previous Thermal inactive technology does not simply fail to realize
Film surface bear electricity hydrophilic modifying, and cannot get ultrafiltration membrane of the aperture in 0.01-0.05 micron ranges.
The present invention causes phase technology to prepare using Thermal inactive technology rather than previous non-solvent, hydrophilic chargedization be
It is realized rather than by being blended and extracting the means of diluent by being modified to realize to film progress surface in film-forming process.Separately
Outside, the bear electric polymer of blending can also influence film forming procedure, can obtain being suitable for the reticulated cell supporting layer of water process not to the utmost
Structure, and film is the micro-filtration either wider array of ultrafiltration membrane of purposes.
By adopting the above-described technical solution, compared with prior art, the present invention has the characteristics that following two：（1）Using
Different phase separation mode：Thermal inactive occurs for polymer material in temperature-fall period, and polymer blend was cooling down
Be not separated in journey, polymer blend only with ethyl alcohol will can just cure in diluent extraction process precipitation and be deposited on
The surface of Kynoar or polysulfones coats one layer of hydrophilic bear isoelectric substance, not only by extraction in surface of polymer material
The hydrophily of film is improved, and reduces the pore size of UF membrane layer, can obtain aperture in the super of 0.01-0.05 micron ranges
Filter membrane.（2）The acquisition of reticulated cell supporting layer and thin separating layer structure：Since polymer blend remains dissolved in temperature-fall period
In diluent, increase the viscosity of diluent, on the one hand not only slow down rate of heat transfer, so as to reduce the thickness of separating layer, Er Qieke
The curing aggregation procedure of polymer material is hindered, so as to advantageously form the networked pore structures for incomplete perforation of reuniting；In addition,
Since polymer material is good with polymer blend compatibility and is dissolved in diluent, diluent and polymer blend can be regarded as one
A entirety is equivalent to the interaction enhanced between polymer material and dilution so that casting film liquid system in temperature-fall period
Solid-liquid split-phase occurs at a lower temperature and forms the networked pore structures of perforation, due to not being by under previous hot conditions
Spinodal phase separation obtains networked pore structures, therefore avoids the decomposition of polymer blend.Simple and practicable, material of the invention
It derives from a wealth of sources, is of low cost, using effect is good.
Specific embodiment
The embodiment of the present invention 1：Polymer bear electrolemma, is calculated according to the mass fraction, non-aqueous including 15 parts of polymer material
0.1 part of 1.5 parts of dissolubility polymer blend, 83.4 parts of diluent and antioxidant；The polymer material is Kynoar (weight
Average molecular weight 33.7 is ten thousand)；The water-insoluble polymer blend is poly-（Methyl methacrylate-g- sodium acrylate）；It is described
Diluent be diamyl phthalate；The antioxidant is β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid 18
Ester.
The preparation method of polymer bear electrolemma takes each component by above-mentioned mass fraction, and by polymer material, non-aqueous
Property polymer blend, diluent and antioxidant in a mixer fully be blended after, squeezed out through double screw extruder, and in air
Cooling granulation obtains compound particles；By gained compound particles through double screw extruder spinning at 170 DEG C, by 0.5cm
Air cooling-down after, be cooled and shaped in room temperature water；Then with room temperature ethanol washing by soaking 1h, then with the secondary immersion of room temperature ethanol
After washing 1h, you can the hollow fiber porous film is made.
One group separately is taken, identical method is selected to prepare compound particles, gained compound particles are film-made through rolling
Extruder coats rolling at 170 DEG C, after the air cooling-down of 0.5cm, is cooled and shaped in room temperature water；Then room temperature second is used
Alcohol washing by soaking 1h, then with after the secondary washing by soaking 1h of room temperature ethanol, you can obtain the rolling perforated membrane.
After measured, film is three-dimensional perforation networked pore structures, and film surface bear is electric, 0.5 micron of aperture, 85 ° of pure water contact angle
（Contact angle numerical value is smaller, shows that hydrophily and contamination resistance are stronger）.
The embodiment of the present invention 2：Polymer bear electrolemma, is calculated according to the mass fraction, non-aqueous including 40 parts of polymer material
1 part of 10 parts of dissolubility polymer blend, 49 parts of diluent and antioxidant；The polymer material (is divided equally again for Kynoar
Son amount 33.7 is ten thousand)；The water-insoluble polymer blend is poly-（Methyl methacrylate-g- sodium acrylate）；Described is dilute
Agent is released as diamyl phthalate；The antioxidant is β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester.
The preparation method is the same as that of Example 1.
After measured, film is three-dimensional perforation networked pore structures, and film surface bear is electric, 0.05 micron of aperture, pure water contact angle
59°。
The embodiment of the present invention 3：Polymer bear electrolemma, is calculated according to the mass fraction, non-aqueous including 40 parts of polymer material
1 part of 10 parts of dissolubility polymer blend, 49 parts of diluent and antioxidant；The polymer material (is divided equally again for Kynoar
Son amount 70 is ten thousand)；The water-insoluble polymer blend is poly-（Styrene-g- sodium acrylate）；The diluent is three fourths
Acid glyceride；The antioxidant is β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester.
The preparation method is the same as that of Example 1.
After measured, film is three-dimensional perforation networked pore structures, and film surface bear is electric, 0.02 micron of aperture, pure water contact angle
65°。
The embodiment of the present invention 4：Polymer bear electrolemma, is calculated according to the mass fraction, non-aqueous including 15 parts of polymer material
0.1 part of 1.5 parts of dissolubility polymer blend, 83.4 parts of diluent and antioxidant；The polymer material is polysulfones (Weight-average molecular
Measure 7.9 ten thousand)；The water-insoluble polymer blend is poly-（Ethylene glycol terephthalate-g- sodium acrylate）；Described is dilute
Agent is released as diethylene glycol dibenzoate；The antioxidant is β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester.
The preparation method is the same as that of Example 1.
After measured, film is three-dimensional perforation networked pore structures, and film surface bear is electric, 0.05 micron of aperture, pure water contact angle
59°。
The embodiment of the present invention 5：Polymer bear electrolemma, is calculated according to the mass fraction, non-aqueous including 40 parts of polymer material
0.1 part of 10 parts of dissolubility polymer blend, 49.9 parts of diluent and antioxidant；The polymer material is polysulfones (Weight-average molecular
Measure 8.2 ten thousand)；The water-insoluble polymer blend is poly-（Ethylene glycol terephthalate-g- sodium acrylate）；Described is dilute
Agent is released as diethylene glycol dibenzoate；The antioxidant is β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester.
The preparation method is the same as that of Example 1.
After measured, film is three-dimensional perforation networked pore structures, and film surface bear is electric, 0.01 micron of aperture, pure water contact angle
57°。
The embodiment of the present invention 6：Polymer bear electrolemma, is calculated according to the mass fraction, non-aqueous including 40 parts of polymer material
0.1 part of 10 parts of dissolubility polymer blend, 49.9 parts of diluent and antioxidant；The polymer material is polysulfones (Weight-average molecular
Measure 8.2 ten thousand)；The water-insoluble polymer blend is poly-（Styrene-g- sodium acrylate）；The diluent is glycerine three
Benzoic ether；The antioxidant is β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester.
The preparation method is the same as that of Example 1.
After measured, film is three-dimensional perforation networked pore structures, and film surface bear is electric, 0.01 micron of aperture, pure water contact angle
52°。
The reasonable selection of water-insoluble polymer blend and diluent is prepare perforated membrane two of the invention in the present invention
Key technology.Its selection gist is：1. water-insoluble polymer blend is good with polymer material compatibility, itself bear electricity；2.
Diluent can in case of heating soluble polymeric object material, drop to room temperature and cannot dissolve polymer material, but can be at 0 DEG C
Polymer blend is dissolved, i.e. diluent is the solvent of polymer blend；3. the water-insoluble polymer blend additive amount of allotment, makes
Less than forming polymer solution under conditions of molten polymer material temperature.
In the present invention, it is intended to obtain the membrane product of identical mechanical property, the weight average molecular weight of polymer material is bigger, where
Ratio in mixture is lower, and porosity is also higher.Polymer material concentration reduces, and solution spinnability or coating become
Difference；And excessive concentration, since viscosity is excessive, mobility is deteriorated, solution spinnability or coating are also deteriorated solution.Experiment shows
Proportion is more suitable for 15-40% in the mixture for polymer material.
The additive amount of the polymer blend of the present invention has very big shadow to the connectivity, hydrophily and aperture of polymer fenestra
It rings.Additive amount is lower, and unobvious are got over to the raising effect of the hydrophilic modifying antipollution effect of film.And polymer was cured
The inhibition of journey is also weaker, and the separating layer not only formed is thicker, 0.01-0.05 microns of ultrafiltration membrane model is not achieved in aperture
It encloses, and polymer is formed by curing spherical agglomeration object and cannot penetrate through reticulated cell supporting layer structure；When ratio further increases,
It is easy to get to separating layer is thin, ultrafiltration membrane range of the aperture at 0.01-0.05 microns, the networked pore structures that supporting layer is perforation；When than
When example is excessively high, ambassador's system spinnability is crossed due to polymer solution viscosity and is deteriorated, polymer blend component in the formula
Ratio can not be less than 15/1.5 no more than 15/10.
The preparation method of perforated membrane of the present invention uses perforated membrane mass percent formula of the present invention, and is applicable in
In following techniques：After the perforated membrane each component mixing of the formula rate, through spinning or coating, rolling at 120-170 DEG C,
First through air or water-bath cooling, then after fully washing removes the diluent, you can respectively obtain the polymer material
Doughnut or rolling blend film.
The present invention is mixed using conventional mixed method, is included the use of mixing machine such as Henschel mixers, V-type and is mixed
Said components material is homogenously mixed together by conjunction machine, ribbon mixer etc..
The spinning of perforated membrane of the present invention or coating processes temperature parameter are 120-170 DEG C, by mixture spinning in hollow fibre
After dimension or rolling, its air cooling-down work in spinning nozzle (or coating scraper) between cooling bath Jing Guo a distance need to be allowed
Skill, then batched after water-bath or air bath cooling.Because doughnut squeezes out or the quenching of rolling applicator can shape in film surface
The thin layer relatively low into percent opening, and allow the doughnut of extrusion or the rolling of coating that can improve hole by a distance in air
Percent opening on porous film surface, so as to increase the conductivity of the water flux of film or battery.Doughnut squeezes out or rolling applies
After covering in air by distance it is related with its winding rate, the segment distance is designed as 0.5-20cm, if the distance is lacked
In 0.5cm, the water flux of gained film is substantially reduced.If it is described in air by distance be more than 20cm, film it is uniform
Property is seriously deteriorated, the preferred 0.5cm of the present embodiment.
In the method for the present invention, the perforated membrane of gained is needed by abundant washing process after melt spinning or coating cooling, with
Remove diluent.It is washed after melt spinning with ethyl alcohol of the purity not less than 99% as the important feature of the present invention.Described
Fully washing specifically includes ethyl alcohol washing and secondary ethanol wash process.Its technique sheet is as the prior art, by fully washing
Afterwards, you can obtain the polymeric hollow fibre for meeting requirement or rolling perforated membrane.
Polymeric hollow fibre of the present invention or the porous membrane product of rolling（Abbreviation perforated membrane）, film preparation temperature is less than
Polymer curing temperatures, there is film surface bear electricity, separating layer is thin, aperture in 0.01-0.05 micron ranges, supporting layer is uniform
Three-dimensional perforation networked pore structures.The uniformity of the uniform three-dimensional perforation networked pore structures for referring to perforated membrane, in SEM
Under do not observe the visibly different hole in aperture, and hole wall is perforation.Its reason is in temperature-fall period that polymer blend hinders
Hinder the reunion solidification process of polymer material.
Maximum feature of the invention is using the bear electric polymer good with polymer material compatibility as polymer blend, uses
The perforated membrane is made in melt spinning or solid-liquid split-phase of the preparation method through Thermal inactive technology of coating rolling, thus
By adjusting the additive amount of the polymer blend, formation relatively easily can be obtained or control with ultrafiltration pore diameter range, film table
The perforated membrane of face bear electricity, three-dimensional perforation networked pore structures；Since film preparation is under less than polymer material solidification temperature
It carries out, avoids the resolution problem of polymer blend under the conditions of previous spinodal phase separation film-making, while the system of the perforated membrane
Standby simple for process, adaptability is good, does not need to more new equipment, convenient for promoting, has good industrial prospect.
Proposed by the present invention have micro-filtration, ultrafiltration pore diameter range, film surface bear electricity and separating layer is thin, supporting layer is perforation
The preparation method and its product of reticulated cell polymer porous film, are described, related technical personnel are bright by embodiment
Show off one's talent or competence and do not departing from present disclosure, content as described herein be modified in spirit and scope or suitably change with combining
To realize the present invention.In particular, it should be pointed out that all similar replacements and change are aobvious for a person skilled in the art
And be clear to, they are considered as being included in the spirit, range and content of the present invention.
Claims (7)
1. a kind of polymer bear electrolemma, it is characterised in that：It calculates according to the mass fraction, it is non-aqueous including 15-40 parts of polymer material
0.1-1 parts of 1.5-10 parts of dissolubility polymer blend, 49-83.4 parts of diluent and antioxidant；The water-insoluble blending polymerization
Object is poly- (methyl methacrylate-g- sodium acrylate) or poly- (styrene-g- sodium acrylate)；Each group is taken by above-mentioned mass fraction
Point, and by after polymer material, water-insoluble polymer blend, diluent and the abundant mixing of antioxidant, by blending extrusion, obtain
Obtain compound particles；By the compound particles of acquisition at 120-170 DEG C after spinning or coating, rolling, then through air or water
Then bath cooling removes diluent, you can obtain the polymer bear electrolemma through fully washing.
2. polymer bear electrolemma according to claim 1, it is characterised in that：The polymer material for Kynoar,
The homopolymer or copolymer of polysulfones.
3. polymer bear electrolemma according to claim 1, it is characterised in that：The diluent is phthalic acid two
Pentyl ester, tributyrin, diethylene glycol dibenzoate or tribenzoin；When water-insoluble polymer blend is poly-
When (methyl methacrylate-g- sodium acrylate), diamyl phthalate or tributyrin are selected；When water-insoluble common
When mixed polymer is poly- (styrene-g- sodium acrylate), diethylene glycol dibenzoate or tribenzoin are selected.
4. polymer bear electrolemma according to claim 1, it is characterised in that：The antioxidant is β-(3,5- bis- uncles
Butyl -4- hydroxy phenyls) propionic acid octadecyl ester.
5. a kind of preparation method of polymer bear electrolemma as described in claim 1, it is characterised in that：By above-mentioned mass fraction
Each component is taken, and by after polymer material, water-insoluble polymer blend, diluent and the abundant mixing of antioxidant, by blending
It squeezes out, obtains compound particles；By the compound particles of acquisition at 120-170 DEG C after spinning or coating, rolling, then through sky
Then gas or water-bath cooling remove diluent, you can obtain the polymer bear electrolemma through fully washing.
6. preparation method according to claim 5, it is characterised in that：The abundant washing is specifically, first pass through first
Secondary room temperature ethanol washing, then carry out second of room temperature ethanol washing.
7. preparation method according to claim 5, it is characterised in that：After spinning or coating, rolling, extrusion allowed
Doughnut or the rolling of coating in air by 0.5-20cm after, then batched after water-bath or air bath cooling.
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| CN105727752B (en) | 2016-05-11 | 2018-08-14 | 贵州省材料产业技术研究院 | A kind of preparation method and product of high-intensity anti-pollution antibacterial hollow fiber nanofiltration membrane |
| CN108837709A (en) * | 2018-07-02 | 2018-11-20 | 上海城市水资源开发利用国家工程中心有限公司 | A kind of collaboration self assembly preparation PVDF bear Electricity Functional ultrafiltration film method |
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| CN102512970A (en) * | 2011-12-05 | 2012-06-27 | 天津工业大学 | Preparation method of polyvinylidene fluoride blending porous diaphragms and product thereof |
| WO2013023006A2 (en) * | 2011-08-08 | 2013-02-14 | California Institute Of Technology | Filtration membranes, and related nano and/or micro fibers, composites, methods and systems |
| CN104474921A (en) * | 2014-12-04 | 2015-04-01 | 贵州省材料产业技术研究院 | Polyolefin porous membrane with perforated honeycomb pore structure and preparation method thereof |
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| CN102416300A (en) * | 2010-09-28 | 2012-04-18 | 中国石油化工股份有限公司 | Preparation method of polypropylene flat separation membrane |
| WO2013023006A2 (en) * | 2011-08-08 | 2013-02-14 | California Institute Of Technology | Filtration membranes, and related nano and/or micro fibers, composites, methods and systems |
| CN102512970A (en) * | 2011-12-05 | 2012-06-27 | 天津工业大学 | Preparation method of polyvinylidene fluoride blending porous diaphragms and product thereof |
| CN104474921A (en) * | 2014-12-04 | 2015-04-01 | 贵州省材料产业技术研究院 | Polyolefin porous membrane with perforated honeycomb pore structure and preparation method thereof |
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