CN106823860B - A kind of preparation method of ethylene-vinyl alcohol copolymer highly-hydrophilic ultrafiltration membrane - Google Patents
A kind of preparation method of ethylene-vinyl alcohol copolymer highly-hydrophilic ultrafiltration membrane Download PDFInfo
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- CN106823860B CN106823860B CN201710122653.0A CN201710122653A CN106823860B CN 106823860 B CN106823860 B CN 106823860B CN 201710122653 A CN201710122653 A CN 201710122653A CN 106823860 B CN106823860 B CN 106823860B
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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
- B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
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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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/24—Use of template or surface directing agents [SDA]
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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Abstract
The present invention is a kind of preparation method of ethylene-vinyl alcohol copolymer highly-hydrophilic ultrafiltration membrane.This method is micro- rolling collaboration submergence gel method, using the non-woven fabrics of transmission as basement membrane, striking casting solution thereon, by method one (the complete gelation of semigel-rolling -) or method two (gelation II completely of complete I-erosion of gelation-rolling -), it is prepared for highly-hydrophilic ultrafiltration membrane.In the operation of rolling unit, the micron scale construction of micro-structure roller template is reproduced in film surface, operates in conjunction with subsequent complete gelation Unit II, and micro-nano dual structure feature is presented in ultrafiltration membrane surface, significantly improves the hydrophily of film surface.The contact of casting solution and micro-structure roller template, without always, need to only be in contact through film-forming process in limited rolling link, realize that film-forming process is become operating continuously from intermittently operated, and the method more meets industrial demand, and preparation process is quickly and efficiently.
Description
Technical field
The invention belongs to membrane material preparation technical field, in particular to a kind of ethylene-vinyl alcohol copolymer (EVAL/EVOH,
Indicated below with EVAL) highly-hydrophilic ultrafiltration membrane and its film-forming process.
Background technique
Ultrafiltration is a kind of using pressure difference as the membrane separation technique of motive force, compared with the traditional separation technology, has separation
It is high-efficient, low energy consumption and it is easy to operate the advantages that, be used widely in fields such as the concentrations, separation, purification of aqueous solution.When super
When filter membrane handles aqueous solution, its main feature is that the major part of macromolecule, oil droplet, colloid, microorganism in solution etc. is trapped, water and
Other small molecules penetrate film.In ultrafiltration operational process, mitigation fouling membrane is very crucial, relies heavily on film surface
Hydrophilicrty (Journal of Chemical Industry and Engineering, 2013,64 (1): 173-181).Therefore, seek good hydrophilic film material and improve film surface parent
Water degree is to mitigate the important channel of fouling membrane.
EVAL is the copolymer containing hydrophilic radical vinyl alcohol segment, has good hydrophilic property, high mechanical strength, chemical stabilization
Property and it is heat-resist the advantages that, be a kind of good membrane material (Materials Chemistry and Physics, 2002,73
(1): 1-5).
Riyasudheen etc. (Desalination, 2012,294:17-24) is prepared for EVAL using submergence gel method and surpasses
Filter membrane, static contact angle are 75 °, and after polyvinylpyrrolidone blending is added, contact angle drops to 55 °.
It is more that Hao Changqing etc. (Tianjin Polytechnic University's journal, 2016,35 (1): 1-5) uses thermally induced phase separation to be prepared for EVAL
Pore membrane, static contact angle are 49.8 ° ± 2.6 °, and after being blended into nano silica in casting solution, contact angle drops to 44.8 °.
Although the above method all improves the hydrophily of film, the requirement of highly-hydrophilic is still not achieved in film surface, there are also into
One step improves its hydrophilic necessity.
Dong Chunhua etc. (Journal of Chemical Industry and Engineering, 2007,58 (6): 1501-1506) by polysulfone ultrafiltration membrane be placed in acrylic acid, phosphoric acid and
Graft modification is carried out in the mixed solution of tin tetrachloride, obtained hydrophilic modifying film contact angle is 10 °, and anti-protein capability is not better than
Modified Membrane.Although this method improves the hydrophily and antifouling property of film, but acid solution will cause film surface damage, film meeting portion
Divide dissolution.
Application publication number CN105797432 discloses " a kind of preparation method of super hydrophilic water-oil separationg film ", and this method is:
Using electro-deposition techniques, by super hydrophilic Ni grained deposits on supporting network, obtaining super hydrophilic water-oil separationg film, the contact of the film
Angle has good Superhydrophilic less than 4 °.But this method can not achieve prepare with scale.
Gong etc. (Separation and Purification Technology, 2014,122:32-40) is with polypropylene
Nitrile is basement membrane, has prepared the super hydrophilic TiO for infiltration evaporation by the method for LBL self-assembly2Nano hybrid film, it is ultraviolet
After irradiation, film surface contact angle is reduced to 3 ° by 62 °, forms ultra-hydrophilic surface.The characteristics of the method is that the Superhydrophilic of film is
As caused by photocatalytic activity, ultraviolet irradiation equipment is needed, expensive, modifying process is complicated, and ultraviolet irradiation also will affect film
Performance.
Above method is to carry out hydrophilic reinforcing to film, effectively increases the hydrophily of film, but there is also respective defects.
Parent/hydrophobicity of material surface can be codetermined by the surface of material with the surface topography of material.For high surface
The more coarse energy material, surface the more hydrophilic；For low-surface-energy material, the more coarse surface the more hydrophobic.
Based on above-mentioned thought, Wang Zhiying, Yang Zhensheng etc. (application publication number CN101632903) propose a kind of using coarse
The method that substrate prepares PVDF microporous barrier, by casting solution striking in the substrate with micro-structure, using phase separation
High hydrophobicity is presented in the lower surface of method film, film, and permeation flux is big, more conventional use smooth substrate film, the machinery of film
Performance does not reduce.
Yang Zhensheng, Wang Zhiying etc. propose a kind of preparation method (application publication number of very hydrophobic microporous barrier
CN103272484), this method assists thermally induced phase separation using solid template, casting solution is evenly applied to micro-structure is presented
The solid template surface of feature prepares microporous barrier by thermally induced phase separation, by template and the synergistic effect mutually separated, improves
The hydrophobicity and other film properties, water contact angle of film bottom surface (face that microporous barrier is in contact with rectangle micro-structure template) reach as high as
165 °, through performance is high and mechanical performance is outstanding.
The above method needs liquid film to immerse in gelling agent together with micro-structure template, i.e. the contact of film and micro-structure template
Through entire film-forming process.The deficiency of this method is embodied in: (1) using solid template as substrate be film-made, micropore membrane area by
The restriction of template size；(2) intermittent operation cannot achieve serialization preparation；(3) in gelation step, with micro-structure template
The film liquid of contact cannot occur instantaneous phase and separate, and after film-forming, the film lower surface with double micro-nano structure is open structure,
It is not compact texture, i.e., can not prepares the ultrafiltration membrane that double micro-nano structure surface is presented.
Summary of the invention
It is an object of the present invention to for deficiency existing for art methods, provide a kind of EVAL highly-hydrophilic ultrafiltration membrane
Preparation method.This method is micro- rolling collaboration submergence gel method, using the non-woven fabrics being continuously driven as basement membrane, striking casting film thereon
Liquid passes through the gelation (method one) completely of semigel-rolling-or complete gelation-erosion-rolling-gelation (method completely
Two) highly-hydrophilic ultrafiltration membrane is prepared, to realize simple and direct efficient, large area, serialization, prepare with scale.
Technical method of the invention are as follows:
Method one: the following steps are included:
(1) with scraper by casting solution striking on non-woven fabrics, formed on non-woven fabrics with a thickness of 50 μm~500 μm of film
Liquid；
The casting solution is ethylene-vinyl alcohol copolymer solution, and solid content is 10wt%~25wt%, and solvent is mixing
Solvent；Mixed solvent includes component A and component B, and component A is 60wt%~95wt% in the content of in the mixed solvent；
(2) in the semigel agent of 15 DEG C~60 DEG C of the non-woven fabrics immersion for the coating film liquid for obtaining upper step, the residence time is
15s~60s obtains semigel film；
The semigel agent is the aqueous solution of component A, and the content of component A is 5wt%~40wt%；
(3) under room temperature environment, the semigel film that upper step obtains is purged, purge gas is air, airflow rate
For 0.1m/s~1m/s, purge time is 10s~30s；
(4) upper step is rolled by the film of purging by pressure roller, the transmission linear velocity of roller is identical with cloth speed；
(5) in the water of 15 DEG C~60 DEG C of the film immersion by upper step by rolling, the residence time is 3min~10min, is obtained
Primary membrane；Post-treated step again obtains highly-hydrophilic ultrafiltration membrane；
Described step (1)-(5) are continuously and smoothly's transmission process, and non-woven fabrics cloth speed is 1.0m/min~4.0m/min；
Alternatively, method two, comprising the following steps:
(1) with scraper by casting solution striking on non-woven fabrics, formed on non-woven fabrics with a thickness of 50 μm~500 μm of film
Liquid；
(2) non-woven fabrics for the coating film liquid for obtaining upper step immerses in 15 DEG C~60 DEG C of water, the residence time be 5min~
10min obtains complete gelating film；Then using attack step, the attack step is one of following two method:
Method 1) spraying erosion: complete gelating film is sprayed with 25 DEG C~45 DEG C of aggressive agent, spray time is
15s~30s, sprinkle density are 0.05L/ (m2S)~0.45L/ (m2·s)；
Alternatively, method 2) submergence erosion: in complete 25 DEG C~45 DEG C of gelating film immersion of aggressive agent, the residence time is
10s~25s；
The aggressive agent is the aqueous solution of component A, and the content of component A is 75wt%~98wt%；Or component A and component
The mixed solution of B, the content of component A are 40wt%~80wt%；
(3) film by upper step Jing Guo attack step purges, and purge gas is air, airflow rate be 0.1m/s~
1m/s, purge time are 10s~30s；
(4) upper step is rolled by the film of purging by pressure roller, the transmission linear velocity of roller is identical with cloth speed；
(5) in the water of 15 DEG C~60 DEG C of the film immersion by upper step by rolling, the residence time is 2min~5min, is obtained just
Filming；Post-treated step again obtains highly-hydrophilic ultrafiltration membrane；
Described step (1)-(5) are continuously and smoothly's transmission process, and non-woven fabrics cloth speed is 1.0m/min~4.0m/min.
In the scheme one or scheme two, component A is dimethyl sulfoxide, n,N-Dimethylformamide, N, N- dimethyl
Acetamide or N-Methyl pyrrolidone, sulfolane；Component B is n-hexyl alcohol, n-heptanol, n-octyl alcohol, ethylene glycol, polyethylene glycol or poly-
Vinylpyrrolidone.
In the method one or method two, the pressure roller in step (4) is made of upper and lower two rollers, between two rollers
Spacing lower than 10 μm -30 μm of film thickness before rolling.The roller of lower part is the smooth cylinder in surface；Top roller is surface tool
There is the cylinder of micro-structure, the order of magnitude of the scale of the micro-structure is 101μm~102μm；The halfwidth section of micro-structure, it is recessed
Point rate that the projected area in hole accounts for all surfaces projected area is 0.3~0.7.
The micro-structure of the roller with micro-structure is melted by injection processing, electrical discharge machining, Ultrasonic machining, laser
It covers, laser engraving or 3D printing obtain.
In the method one or method two, the preferred 15wt%~18wt% of solid content, the content of in the mixed solvent component A
It is preferred that 80wt%~92wt%.
In the method one, the preferred 10wt%~20wt% of the content of component A in semigel agent.
In the method two, aggressive agent is preferably the aqueous solution of DMSo, and the content of component A is 85wt%~90wt%；
Or the mixed solution of DMSo and EH, the content of component A are 60wt%~70wt%.
Substantive distinguishing features of the invention are as follows:
(1) preparation of the film before rolling is realized using the semigel of liquid film or complete gelation-erosion pattern.Half
Gelation mode can control the semigel journey of film by change semigel agent composition, residence time of the film in semigel agent
Degree, to regulate and control the effect of rolling of micro-structure roller template.Complete gelation-erosion pattern can by change aggressive agent composition and
Erosion time weathers degree to control film surface, to regulate and control the effect of rolling of micro-structure roller template.
(2) it is operated by rolling, the micron scale construction of micro-structure roller template is reproduced in film surface；By subsequent solidifying
Gelatinization step makes film surface form dense layer surface, finally obtains the highly-hydrophilic ultrafiltration membrane that micro-nano dual structure is presented in surface.
(3) contact of casting solution and micro-structure roller template, without always, need to only have through entire film-forming process
The rolling link of limit is in contact, and film-forming process is become operating continuously from intermittently operated.
Compared with prior art, the invention has the benefit that
(1) the contact angle CA of the EVAL highly-hydrophilic ultrafiltration membrane and water that prepare according to the present invention within the scope of 9 °~17 °,
Pure water flux >=200L/ (m under 0.1MPa membrane pressure2.h), to rejection >=90% of bovine serum albumin, fouling membrane refers to
Number≤0.529, bovine serum albumin static adsorbance≤21 μ g.cm-2。
(2) in film-forming process, used micro-structure template is roller form, solves membrane area and is limited by template size
The problem of, film large area can be made to prepare.
(3) preparation process of the present invention carries out under room temperature close, the preparation of used micro-structure template-pressure roller
Method is simple, and rolling process is simple and direct efficiently, therefore is easily achieved scale, preparation of industrialization.Prepared highly-hydrophilic ultrafiltration membrane
Performance is stablized, and collimation is good.
Detailed description of the invention
Fig. 1 is the process flow diagram of method one.
Fig. 2 is the spraying eroding process flow diagram in method two.
Fig. 3 is the submergence eroding process flow diagram in method two.
Fig. 4 is the operation principle schematic diagram of rolling component.
Fig. 5 is the scanning electron microscope for the EVAL film that the reference examples-of 1~embodiment of embodiment 6 are handled without rolling
(SEM) photo, wherein Fig. 5 a is surface, and Fig. 5 b is section.
Fig. 6 is the SEM photograph of EVAL film prepared by embodiment 1, and wherein Fig. 6 a is surface, and Fig. 6 b is section.
Fig. 7 is the SEM photograph of EVAL film prepared by embodiment 3, and wherein Fig. 7 a is surface, and Fig. 7 b is section.
Fig. 8 is the SEM photograph of EVAL film prepared by embodiment 5, and wherein Fig. 8 a is surface, and Fig. 8 b is section.
Fig. 9 is the water drop contact horn shape for the EVAL film surface that the reference examples-of 1~embodiment of embodiment 6 are handled without rolling
State figure.
Figure 10 is the water droplet contact angle state diagram of EVAL film surface prepared by embodiment 1.
Figure 11 is the water droplet contact angle state diagram of EVAL film surface prepared by embodiment 3.
Figure 12 is the water droplet contact angle state diagram of EVAL film surface prepared by embodiment 5.
Specific embodiment
The present invention is using micro- rolling collaboration submergence gel method, and the ultrafiltration membrane of micro-nano dual structure is presented in preparation surface, to mention
Hydrophily, resistance tocrocking and the other film properties of high film.
The present invention prepares highly-hydrophilic ultrafiltration membrane using continuation mode, the preparation of preparation, film including casting solution and rear place
Manage three links.
In the present invention, casting solution prepare link refer to weigh polymer by a certain percentage, mixed solvent is placed in dissolution kettle,
It is complete to polymer dissolution that 3h~8h is stirred at 50 DEG C~80 DEG C, later sending casting solution to temperature through filter device is 25 DEG C
In~45 DEG C of fluid reservoirs, standing and defoaming 3h~6h.
In the present invention, casting solution transmission process is conveyed using nitrogen supercharging mode, i.e., increases dissolution kettle, liquid storage using nitrogen
Casting solution is delivered to next operating unit by the pressure above jar liquid surface.
The preparation link of film can be realized by two methods, including method one-successively undergoes and 1. puts cloth, 2. coating, 3. half
Gelation, 4. purging, 5. rolling, 6. complete gelation, 7. the operation of winding each unit and method two-successively undergo and 1. put cloth, 2.
Coating, 3. complete gelation I- erosion, 4. purging, 5. rolling, 6. complete gelation II, the 7. operation of winding each unit.
Film-forming process in method one by load cloth unit, striking unit, semigel unit, purge unit, rolling unit,
Complete gelation unit, rolling unit sequentially form, which is stated in detail by Fig. 1.Each unit is by nonwoven fabric roll around phase
Even, wherein carrying cloth unit and rolling unit offer power, make entire film-forming apparatus transmission operating.Film-forming process in method two,
It is identical as method one to carry cloth unit, striking unit, purge unit, rolling unit, complete gelation unit, rolling unit, it will be partly
Gelation unit replaces with complete gelation I- spray unit or complete gelation I- submergence unit, detailed by Fig. 2, Fig. 3 respectively
Statement.The apparatus described above unit is known device, only rolling assembly of elements designed, designed, is with artificial micro-structure
Roller template.
In the present invention, last handling process includes extracting and cleaning two steps.Extraction, which refers to, extracts the film extractant after winding
For 24 hours~48h is taken, to go the residual organic solvents in membrane removal, extraction temperature is room temperature；6h~12h is washed with water after extraction, is cleaned
Temperature is room temperature, and last naturally dry obtains highly-hydrophilic ultrafiltration membrane.
In the present invention, polymer EVAL, model H171B, content be 10wt%~25wt%, preferably 15wt%~
18wt%.
In the present invention, the component A of in the mixed solvent selects dimethyl sulfoxide (DMSo is indicated with DMSo below), mixes molten
Agent component B selects n-octyl alcohol (EH is indicated with EH below), and the content of DMSo is 60wt%~95wt%, and preferably 80wt%~
92wt%.
In the present invention, semigel agent is the aqueous solution of DMSo, and the content of DMSo is 5wt%~40wt%, preferably
10wt%~20wt%
In the present invention, aggressive agent is the aqueous solution of DMSo, and the content of component A is 75wt%~98wt%, preferably 85wt%
~90wt%；Or the mixed solution of DMSo and EH, the content of component A are 40wt%~80wt%, preferably 60wt%~70wt%.
In the present invention, extractant is one of ethyl alcohol (ET is indicated with ET below), isopropanol, methyl ethyl ketone or each self-contained
Amount >=80wt% aqueous solution.
In the present invention, supporter selects the non-woven fabrics of good mechanical performance, produces for Shanghai Tian Lve new material Co., Ltd
TA3633 polyester non-woven fabric (with a thickness of 120 μm).
In the present invention, lower than 20 μm of film thickness before rolling, (roller spacing of embodiment is roller spacing in the present invention
Less than non-woven fabrics and 20 μm of film overall thickness.).The roller of lower part is the smooth cylinder in surface；Top roller is surface with micro-
The cylinder of structure is handled to obtain by injection processing.The order of magnitude of the macro structural scale is 101μm~102μm；Micro-structure
Halfwidth section, point rate that the projected area of pit accounts for all surfaces projected area is 0.3~0.7.In the present invention, the roller
The stainless steel that cylinder material is trade mark 316L, specification are 100 × 5mm of φ.Top roller is the preparation method comprises the following steps: be 0.6MPa using gauge pressure
Compressed air carry under one's arms 320 mesh Brown Alundum quartz sands, 30 ° of nozzle inclination, slow uniform injection stainless steel tube outer surface 30s.Through
It is cleaned after compressed air purging with clear water, is obtained after natural drying.This top roller is applied to following all examples.
In the present invention, film surface, section are observed with model NanoSEM-450 scanning electron microscope；Water contact angle is adopted
/ static contact angle instrument measurement is moved with DSA20 type optics, five test points is taken on each sample film, calculates its average value；Film it is saturating
Cross performance and separating property uses pure water flux and film to characterize the rejection of bovine serum albumin respectively, and test device uses laboratory
Homemade cross-flow filtration device, operating pressure 0.1MPa；The antifouling property of film is using film to the static state of bovine serum protein
The gross contamination index of adsorbance and film characterization.
In the present invention, the order of magnitude of micro-structure roller template surface structure dimension is 101μm~102μm, submerge gel method shape
At phase separation structure the order of magnitude be 10-2μm~10-1μm.Based on this, microstructure appearance and scale are selected, changes film item
Part, so that rolling macro structural scale is equivalent to 10~1000 times of the phase separation structure that submergence gel method obtains (preferably
10~100 times) when, micro-nano dual structure pattern will be presented in film surface.
It elaborates with reference to the accompanying drawing to the embodiment of the present invention；The present embodiment is premised on the technology of the present invention method
Implemented, give detailed embodiment and specific operating process, but protection scope of the present invention be not limited to it is following
Embodiment.
In the step, the step of special statement relevant operating temperatures carry out at room temperature.
In the present invention, the reference examples of each embodiment are the EVAL ultrafiltration membrane for removing rolling related link and obtaining, i.e., only
By 1. putting cloth, 2. coating, 6. complete gelation, the film that 7. winding device unit is prepared.In correlation step, reference examples behaviour
It is consistent with operating condition in embodiment to make condition.
Embodiment 1
The present embodiment is prepared using method one.
The preparation of casting solution: casting solution gross weight 1000g, wherein the EVAL of model H171B is that 160.0g (it is total to account for casting solution
The 16wt% of weight), mixed solvent group is divided into DMSo and EH, total 840g (DMSo content is 88wt%).Dissolution kettle temperature is 80 DEG C,
6h is stirred, fluid reservoir temperature is 35 DEG C, standing and defoaming 4h.
The preparation of film: adjusting non-woven fabrics cloth speed is 1.5m/min, and non-woven fabrics is the TA3631 type of Shanghai Tian Lve company production
Polyester non-woven fabric (with a thickness of 120 μm, following steps and embodiment are same)；Striking liquid film at room temperature, thickness of liquid film are
200μm；It is coated in the semigel agent of 29 DEG C of non-woven fabrics immersion of film liquid, the residence time is that (residence time refers to nonwoven to 35s
Cloth passes through the time of solution, can realize by the geometric dimension of adjusting relevant device, non-woven fabrics cloth speed, around mode for cloth.Below
Step and other embodiments are same), the aqueous solution (DMSo content is 10wt%) that semigel agent is DMSo, obtained film thickness is
302μm；Film through semigel purges at room temperature, airflow rate 0.5m/s, purge time 20s；It is passed through after purging
Rolling unit rolls at room temperature, and two roller spacings are 282 μm, and it is identical as cloth speed that roller is driven linear velocity；After rolling
Film immerses in 29 DEG C of water, residence time 5min, to realize complete gelation；Rolling unit winding, rolling speed and cloth
Speed is identical, obtains primary membrane.
Post-processing: at room temperature for 24 hours to obtained nascent membrane extraction, extractant ET is immersed in the water cleaning 12h after extraction,
Last naturally dry obtains EVAL highly-hydrophilic ultrafiltration membrane.
The EVAL highly-hydrophilic ultrafiltration film properties of embodiment are as follows: 260 μm of (wherein TA3631 polyester non-woven fabric thickness of film thickness
It is 120 μm, following embodiment and reference examples are same), the pure water flux under 0.1MPa membrane pressure is 251L/ (m2.h), to ox blood
Albuminised rejection is 98%, and bovine serum albumin static adsorbance is 17 μ gcm-2, index of membrane fouling 0.529.By Fig. 6
The film surface of this method preparation has coarse structure known to electron microscope, show in this way, film surface effectively replicate it is micro-
The artificial micro-structure of structure roller template forms micro-nano dual structure, to improve the hydrophily of film surface, water droplet contact angle
For 12 ° (Figure 10).
The EVAL ultrafiltration film properties of reference examples are as follows: 275 μm of film thickness, the pure water flux under 0.1MPa membrane pressure is
174L/(m2It .h), is 92% to the rejection of bovine serum albumin, bovine serum albumin static adsorbance is 79 μ gcm-2, fouling membrane
Index is 0.705.Film surface by this method preparation known to Fig. 5 electron microscope is only nano-scale structures, and not formed micro-nano two
Weight structure, water droplet contact angle are 41 ° (such as Fig. 9).
Compared with reference examples, the pure water flux that contact angle reduces under 71%, 0.1MPa membrane pressure improves 44%, right
The rejection of bovine serum albumin improves 7%, and the static adsorbance of bovine serum albumin reduces 78%, and index of membrane fouling reduces
25%.
Embodiment 2
The present embodiment is prepared using method one.
The preparation of casting solution: with embodiment 1.
The preparation of film: cloth, coating, purging, rolling, complete gelation, rolling unit operation are put with embodiment 1.It is different single
Atom operation is semigel unit: the aqueous solution (DMSo content is 20wt%) that semigel agent is DMSo, and temperature is 29 DEG C, is stopped
Time is 30s, and the film thickness of formation is 304 μm.
Post-processing: with embodiment 1.
The EVAL highly-hydrophilic ultrafiltration film properties of embodiment are as follows: 256 μm of film thickness, water droplet contact angle is 9 °, 0.1MPa mistake
Pure water flux under membrane pressure difference is 263L/ (m2It .h), is 95% to the rejection of bovine serum albumin, bovine serum albumin Static Adsorption
Amount is 13 μ gcm-2, index of membrane fouling 0.479.
The EVAL ultrafiltration film properties of reference examples are as follows: 275 μm of film thickness, water droplet contact angle is 41 °, under 0.1MPa membrane pressure
Pure water flux be 174L/ (m2It .h), is 92% to the rejection of bovine serum albumin, bovine serum albumin static adsorbance is 79 μ
g·cm-2, index of membrane fouling 0.705.
Compared with reference examples, the pure water flux that contact angle reduces under 78%, 0.1MPa membrane pressure improves 51%, right
The rejection of bovine serum albumin improves 3%, and the static adsorbance of bovine serum albumin reduces 84%, and index of membrane fouling reduces
32%.
Embodiment 3
The present embodiment is prepared using the spraying corrosion method of method two.
The preparation of casting solution: casting solution gross weight 1000g, wherein the EVAL of model H171B is that 160.0g (it is total to account for casting solution
The 16wt% of weight), mixed solvent group is divided into DMSo and EH, total 840g (DMSo content is 88wt%).Dissolution kettle temperature is 80 DEG C,
6h is stirred, fluid reservoir temperature is 35 DEG C, standing and defoaming 4h.
The preparation of film: adjusting non-woven fabrics cloth speed is 1.5m/min, and non-woven fabrics is the TA3631 type of Shanghai Tian Lve company production
Polyester non-woven fabric.Striking liquid film at room temperature, thickness of liquid film are 200 μm；The non-woven fabrics for being coated with film liquid immerses 29 DEG C
In water, residence time 5min, to realize complete gelation；Complete gelating film is sprayed with 35 DEG C of aggressive agents, when spray
Between be 20s, sprinkle density be 0.1L/ (m2.s), the aqueous solution (DMSo content is 90wt%) that aggressive agent is DMSo, obtained film
With a thickness of 290 μm；Film through corroding purges at room temperature, airflow rate 0.5m/s, purge time 20s；After purging
It is rolled at room temperature through rolling unit, two roller spacings are 270 μm, and it is identical as cloth speed that roller is driven linear velocity；After rolling
Film immerse in 29 DEG C of water, residence time 5min, to realize complete gelation；The winding of rolling unit, rolling speed with
Cloth speed is identical, obtains primary membrane.
Post-processing: at room temperature for 24 hours to obtained nascent membrane extraction, extractant ET is immersed in the water cleaning 12h after extraction,
Last naturally dry obtains EVAL highly-hydrophilic ultrafiltration membrane.
The EVAL highly-hydrophilic ultrafiltration film properties of embodiment are as follows: 249 μm of film thickness, the pure water under 0.1MPa membrane pressure is logical
Amount is 247L/ (m2It .h), is 94% to the rejection of bovine serum albumin, bovine serum albumin static adsorbance is 19 μ gcm-2, film
Pollution index is 0.493.There is coarse structure by the film surface of this method preparation known to Fig. 7 electron microscope, show in this way,
Film surface effectively replicates the artificial micro-structure of micro-structure roller template, micro-nano dual structure is formed, to improve film table
The hydrophily in face, water droplet contact angle are 15 ° (Figure 11).
The EVAL ultrafiltration film properties of reference examples are as follows: 275 μm of film thickness, the pure water flux under 0.1MPa membrane pressure is
174L/(m2It .h), is 92% to the rejection of bovine serum albumin, bovine serum albumin static adsorbance is 79 μ gcm-2, fouling membrane
Index is 0.705.Film surface by this method preparation known to Fig. 5 electron microscope is only nano-scale structures, and not formed micro-nano two
Weight structure, water droplet contact angle are 41 ° (such as Fig. 9).
Compared with reference examples, the pure water flux that contact angle reduces under 63%, 0.1MPa membrane pressure improves 42%, right
The rejection of bovine serum albumin improves 2%, and the static adsorbance of bovine serum albumin reduces 76%, and index of membrane fouling reduces
30%.
Embodiment 4
The present embodiment is prepared using the spraying corrosion method of method two.
The preparation of casting solution: with embodiment 3.
The preparation of film: cloth, coating, purging, rolling, complete gelation, rolling unit operation are put with embodiment 3.It is different single
Atom operation is complete gelation I- erosion unit: the mixed solution (DMSo content is 70wt%) that aggressive agent is DMSo and EH, temperature
Degree is 35 DEG C, spray time 25s, and sprinkle density is 0.1L/ (m2.s), the film thickness obtained is 287 μm.
Post-processing: with embodiment 3.
The EVAL highly-hydrophilic ultrafiltration film properties of embodiment are as follows: 245 μm of film thickness, 17 ° of water contact angle, 0.1MPa crosses membrane pressure
Pure water flux under difference is 206L/ (m2It .h), is 96% to the rejection of bovine serum albumin, bovine serum albumin static adsorbance is
21μg·cm-2, index of membrane fouling 0.519.
The EVAL ultrafiltration film properties of reference examples are as follows: 275 μm of film thickness, 41 ° of water contact angle, pure under 0.1MPa membrane pressure
Water flux is 174L/ (m2It .h), is 92% to the rejection of bovine serum albumin, bovine serum albumin static adsorbance is 79 μ gcm-2, index of membrane fouling 0.705.
Compared with reference examples, the pure water flux that contact angle reduces under 59%, 0.1MPa membrane pressure improves 18%, right
The rejection of bovine serum albumin improves 14%, and the static adsorbance of bovine serum albumin reduces 73%, and index of membrane fouling reduces
26%.
Embodiment 5
The present embodiment is prepared using the submergence corrosion method of method two.
The preparation of casting solution: casting solution gross weight 1000g, wherein the EVAL of model H171B is that 160.0g (it is total to account for casting solution
The 16wt% of weight), mixed solvent group is divided into DMSo and EH, total 840g (DMSo accounts for 88wt%).Dissolution kettle temperature is 80 DEG C, stirring
6h, fluid reservoir temperature are 35 DEG C, standing and defoaming 4h.
The preparation of film: adjusting non-woven fabrics cloth speed is 1.5m/min, and non-woven fabrics is the TA3631 type of Shanghai Tian Lve company production
Polyester non-woven fabric.Striking liquid film at room temperature, thickness of liquid film are 200 μm；The non-woven fabrics for being coated with film liquid immerses 29 DEG C
In water, residence time 5min realizes complete gelation；Film through complete gelation immerses in 35 DEG C of aggressive agent, when stop
Between be 20s, the aqueous solution (DMSo content is 86wt%) that aggressive agent be DMSo, obtained film thickness be 283 μm；Film through corroding
It purges at room temperature, airflow rate 0.5m/s, purge time 20s；After purging at room temperature through rolling unit
Rolling, the spacing of two rollers are 263 μm, and it is identical as cloth speed that roller is driven linear velocity；Film after rolling immerses in 29 DEG C of water, stops
Staying the time is 5min, to realize complete gelation；Rolling unit winding, rolling speed is identical as cloth speed, obtains primary membrane.
Post-processing: at room temperature for 24 hours to obtained nascent membrane extraction, extractant ET is immersed in the water cleaning 12h after extraction,
Last naturally dry obtains EVAL highly-hydrophilic ultrafiltration membrane.
The EVAL highly-hydrophilic ultrafiltration film properties of embodiment are as follows: 241 μm of film thickness, the pure water under 0.1MPa membrane pressure is logical
Amount is 280L/ (m2It .h), is 95% to the rejection of bovine serum albumin, bovine serum albumin static adsorbance is 16 μ gcm-2, film
Pollution index is 0.494.There is coarse structure by the film surface of this method preparation known to Fig. 8 electron microscope, show in this way,
Film surface effectively replicates the artificial micro-structure of micro-structure roller template, micro-nano dual structure is formed, to improve film table
The hydrophily in face, water droplet contact angle are 10 ° (Figure 12).
The EVAL ultrafiltration film properties of reference examples are as follows: 275 μm of film thickness, the pure water flux under 0.1MPa membrane pressure is
174L/(m2It .h), is 92% to the rejection of bovine serum albumin, bovine serum albumin static adsorbance is 79 μ gcm-2, fouling membrane
Index is 0.705.Film surface by this method preparation known to Fig. 5 electron microscope is only nano-scale structures, and not formed micro-nano two
Weight structure, water droplet contact angle are 41 ° (such as Fig. 9).
Compared with reference examples, the pure water flux that contact angle reduces under 76%, 0.1MPa membrane pressure improves 38%, right
The rejection of bovine serum albumin improves 3%, and the static adsorbance of bovine serum albumin reduces 80%, and index of membrane fouling reduces
30%.
Embodiment 6
The present embodiment is prepared using the submergence corrosion method of method two.
The preparation of casting solution: with embodiment 5.
The preparation of film: cloth, coating, purging, rolling, complete gelation, rolling unit operation are put with embodiment 5, different lists
Atom operation is complete gelation I- erosion: the mixed solution (DMSo content is 65wt%) that aggressive agent is DMSo and EH, temperature is
35 DEG C, residence time 25s, obtain with a thickness of 281 μm of film.
Post-processing: with embodiment 5.
The EVAL highly-hydrophilic ultrafiltration film properties of embodiment are as follows: 237 μm of film thickness, 13 ° of water contact angle, 0.1MPa crosses membrane pressure
Pure water flux under difference is 258L/ (m2It .h), is 97% to the rejection of bovine serum albumin, bovine serum albumin static adsorbance is
21μg·cm-2, index of membrane fouling 0.504.
The EVAL ultrafiltration film properties of reference examples are as follows: 275 μm of film thickness, 41 ° of water contact angle, pure under 0.1MPa membrane pressure
Water flux is 174L/ (m2It .h), is 92% to the rejection of bovine serum albumin, bovine serum albumin static adsorbance is 79 μ gcm-2, index of membrane fouling 0.705.
Compared with reference examples, the pure water flux that contact angle reduces under 68%, 0.1MPa membrane pressure improves 48%, right
The rejection of bovine serum albumin improves 5%, and the static adsorbance of bovine serum albumin reduces 73%, and index of membrane fouling reduces
29%.
EVAL highly-hydrophilic ultrafiltration membrane and its film-forming process proposed by the present invention, are described by embodiment, phase
Can obviously the contents of the present invention not departed from, content as described herein is being modified or fitted in spirit and scope by closing technical staff
When changes and combinations realize the present invention.In particular, it should be pointed out that all similar replacements and change are to art technology
It is it will be apparent that they are considered as including in spirit of the invention, range and content for personnel.
Unaccomplished matter of the present invention is well-known technique.
Claims (5)
1. a kind of preparation method of ethylene-vinyl alcohol copolymer highly-hydrophilic ultrafiltration membrane, it is characterized in that this method is following two
One of method,
Method one: the following steps are included:
(1) with scraper by casting solution striking on non-woven fabrics, formed on non-woven fabrics with a thickness of 50 μm ~ 500 μm of film liquid；
The casting solution is ethylene-vinyl alcohol copolymer solution, and solid content is 10wt% ~ 25wt%, and solvent is mixed solvent；It is mixed
Bonding solvent includes component A and component B, and component A is 60wt% ~ 95wt% in the content of in the mixed solvent；
(2) non-woven fabrics for the coating film liquid for obtaining upper step immerses in 15 DEG C ~ 60 DEG C of semigel agent, the residence time be 15s ~
60s obtains semigel film；
The semigel agent is the aqueous solution of component A, and the content of component A is 5wt% ~ 40wt%；
(3) under room temperature environment, the semigel film that upper step obtains is purged, purge gas is air, and airflow rate is
0.1m/s ~ 1m/s, purge time are 10s ~ 30s；
(4) upper step is rolled by the film of purging by pressure roller, the transmission linear velocity of roller is identical with cloth speed；
(5) in the water of 15 DEG C ~ 60 DEG C of the film immersion by upper step by rolling, the residence time is 3min ~ 10min, obtains primary membrane；
Post-treated step again obtains highly-hydrophilic ultrafiltration membrane；
Described step (1)-(5) are continuously and smoothly's transmission process, and non-woven fabrics cloth speed is 1.0m/min ~ 4.0m/min；
Alternatively, method two, comprising the following steps:
(1) with scraper by casting solution striking on non-woven fabrics, formed on non-woven fabrics with a thickness of 50 μm ~ 500 μm of film liquid；
The casting solution is ethylene-vinyl alcohol copolymer solution, and solid content is 10wt% ~ 25wt%, and solvent is mixed solvent；It is mixed
Bonding solvent includes component A and component B, and component A is 60wt% ~ 95wt% in the content of in the mixed solvent；
(2) in the water of 15 DEG C ~ 60 DEG C of the non-woven fabrics immersion for the coating film liquid for obtaining upper step, the residence time is 5min ~ 10min,
Obtain complete gelating film；Then using attack step, the attack step is one of following two method:
Method 1) spraying corrode: complete gelating film is sprayed with 25 DEG C ~ 45 DEG C of aggressive agent, spray time for 15s ~
30s, sprinkle density are 0.05 L/(m2S) ~ 0.45 L/(m2S)；
Alternatively, method 2) submergence corrodes: complete gelating film immerses in 25 DEG C ~ 45 DEG C of aggressive agent, the residence time be 10s ~
25s；
The aggressive agent is the aqueous solution of component A, and the content of component A is 75wt% ~ 98wt%；Or the mixing of component A and component B
Solution, the content of component A are 40wt% ~ 80wt%；
(3) film by upper step Jing Guo attack step purges, and purge gas is air, and airflow rate is 0.1m/s ~ 1m/s, blows
Flyback time is 10s ~ 30s；
(4) upper step is rolled by the film of purging by pressure roller, the transmission linear velocity of roller is identical with cloth speed；
(5) in the water of 15 DEG C ~ 60 DEG C of the film immersion by upper step by rolling, the residence time is 2min ~ 5min, obtains primary membrane；
Post-treated step again obtains highly-hydrophilic ultrafiltration membrane；
Described step (1)-(5) are continuously and smoothly's transmission process, and non-woven fabrics cloth speed is 1.0m/min ~ 4.0m/min；
In the method one or method two, component A is dimethyl sulfoxide, n,N-Dimethylformamide, N, N- dimethylacetamide
Amine, N-Methyl pyrrolidone or sulfolane；Component B is n-hexyl alcohol, n-heptanol, n-octyl alcohol, ethylene glycol, polyethylene glycol or polyethylene
Pyrrolidones；
In the method one or method two, the pressure roller in step (4) is made of upper and lower two rollers, between two rollers between
Away from lower than 10 μm -30 μm of film thickness before rolling；The roller of lower part is the smooth cylinder in surface；Top roller is surface with micro-
The cylinder of structure, the order of magnitude of the scale of the micro-structure are 101μm~102μm；The halfwidth section of micro-structure, pit
Point rate that projected area accounts for all surfaces projected area is 0.3 ~ 0.7.
2. the preparation method of ethylene-vinyl alcohol copolymer highly-hydrophilic ultrafiltration membrane as described in claim 1, it is characterized in that institute
In the method one or method two stated, the preferred 15wt% ~ 18wt% of solid content in casting solution, in the mixed solvent component A in casting solution
Preferred 80wt% ~ the 92wt% of content.
3. the preparation method of ethylene-vinyl alcohol copolymer highly-hydrophilic ultrafiltration membrane as described in claim 1, it is characterized in that institute
In the method one stated, the preferred 10wt% ~ 20wt% of the content of component A in semigel agent.
4. the preparation method of ethylene-vinyl alcohol copolymer highly-hydrophilic ultrafiltration membrane as described in claim 1, it is characterized in that institute
In the method two stated, aggressive agent is preferably the aqueous solution of DMSO, and the content of component A is 85wt% ~ 90wt%；Or DMSO and n-octyl alcohol
Mixed solution, the content of component A is 60wt% ~ 70wt%.
5. the preparation method of ethylene-vinyl alcohol copolymer highly-hydrophilic ultrafiltration membrane as described in claim 1, it is characterized in that institute
The micro-structure for the roller with micro-structure stated is by injection processing, electrical discharge machining, Ultrasonic machining, laser melting coating, laser engraving
Or 3D printing obtains.
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| JPS63178803A (en) * | 1987-01-19 | 1988-07-22 | Nitto Electric Ind Co Ltd | Sheet compound film |
| CN101254424A (en) * | 2008-04-08 | 2008-09-03 | 中南大学 | Hydrophilic PVB blended hollow fiber film and method of preparing the same |
| CN101632903A (en) * | 2009-07-07 | 2010-01-27 | 河北工业大学 | Polyvinylidene fluoride microporous film and preparation method |
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