CN108246110B - A kind of attapulgite modified PVDF ultrafiltration membrane, preparation method and its application in protein solution filtration - Google Patents

A kind of attapulgite modified PVDF ultrafiltration membrane, preparation method and its application in protein solution filtration Download PDF

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CN108246110B
CN108246110B CN201810015083.XA CN201810015083A CN108246110B CN 108246110 B CN108246110 B CN 108246110B CN 201810015083 A CN201810015083 A CN 201810015083A CN 108246110 B CN108246110 B CN 108246110B
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pvdf
attapulgite
film
membrane
ultrafiltration membrane
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CN108246110A (en
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薛爱莲
周守勇
赵宜江
李梅生
王蓉
邢卫红
许家兴
胡磊
杨大伟
张艳
张莉莉
黄进
张玉洁
吴飞跃
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Huaiyin Normal University
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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
    • 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
    • B01D61/18—Apparatus therefor
    • 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
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • 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
    • 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
    • B01D71/02—Inorganic material
    • B01D71/024—Oxides
    • B01D71/027—Silicium oxide
    • 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
    • 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
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention discloses a kind of modified PVDF ultrafiltration membrane of attapulgite, preparation method and its applications in the pollution of anti-protein adsorption.Using triethyl phosphate as solvent, by a certain amount of polymethylacrylic acid N, the attapulgite ultrasonic disperse that N- dimethylaminoethyl PDMAEMA was modified is wherein, Kynoar powder is added and vigorous mechanical agitation extremely dissolves, it adds pore-foaming agent polyethylene glycol to stir evenly, last standing and defoaming obtains casting solution；Using water as coagulating bath, ultrafiltration membrane is made using immersion precipitation phase inversion process.The present invention is by by polymethylacrylic acid N, the attapulgite that N- dimethylaminoethyl was modified is introduced into polyvinylidene fluoride (PVDF) ultrafiltration membrane, both the unique nanofibrous structures of attapulgite can use and polyvinylidene fluoride material forms tridimensional network, to be effectively improved the structure and intensity of pure polyvinylidene fluoride (PVDF) ultrafiltration membrane；Permeability of the membrane and hydrophily are improved using the high-hydrophilic of attapulgite again, realizes resistance tocrocking and easy cleaning.

Description

A kind of attapulgite modified PVDF ultrafiltration membrane, preparation method and its in protein solution Application in filtering
Technical field
The present invention relates to a kind of attapulgite modified PVDF ultrafiltration membrane, preparation method and its in protein solution filtration Using belonging to separation membrane technical field.
Background technique
Kynoar is a kind of material of preparing of function admirable, has good chemical stability, high temperature resistant, oxytolerant The advantages that change, corrosion-resistant, good toughness, high intensity, is widely used in the fields such as food, medicine and sewage treatment.However, gathering inclined fluorine The low-surface-energy of ethylene makes film surface hydrophobicity stronger, adsorbed in oil-water separation or protein solution containing system it is seriously polluted, Flux decline speed is fast, and organic matter is liable to stick to film surface, causes Pore Blocking, forms fouling membrane, and the performance of film is difficult to fill Distribution is waved.Developing pollution-resistant membrane is current popular research direction.The hydrophily raising of film can reduce solute retention, special It is not the contact and non-directional combination between protein, the especially absorption of biological pollution substance.Therefore, the hydrophilic of film is improved Property, fouling membrane is reduced, making it have higher and stable permeation flux is the direction that current scholar studies always.
Mainly there is surface modified and blending and modifying two major classes the method for Kynoar membrane modifying at present.The modified master in surface There are surface coating and surface grafting.The modification that the former easy to operate but modifying agent is easy to run off in film use process, and falls off Substance can also pollute film；The latter need to post-process and be modified not enough uniformly, or even can block die hole, damage film properties.
Blending and modifying, which refers to, carries out physical blending, filming technology letter for hydroaropic substance and Kynoar matrix material It is single, complicated pre-treatment and post-processing are not needed, it is easy to operate high-efficient, it is most common polymeric membrane method of modifying.It is blended The compatibility of material and Kynoar matrix directly affects the formation of film, and common intermingling material includes having containing hydrophilic segment Machine copolymer and inorganic nano-particle etc..
Currently, being used for the inorganic nano-particle TiO of intermingling material2、SiO2、Al2O3Etc. being graininess, these nanoscales Inorganic particulate be easy to fall off in inversion of phases film forming procedure, influence the performance of film.In contrast, the 1-dimention nanos such as carbon nanotube Material mechanical property with super strength, high length-width ratio and high-ratio surface, and the 1-dimention nano material being dispersed in polymeric membrane Material, can effectively improve its stability in membrane material by the spiral winding of macromolecular chain.However, carbon nanotube etc. is artificial Synthesizing one-dimensional nano material preparation cost is high, under purity and low output, it is difficult to disperse, which greatly limits it in film blending and modifying In scale application.
Attapulgite is the main composition of non-metal clay mineral attapulgite clay, is a kind of typical layer chain structure Aqueous rich magnesium aluminium silicate mineral.Attapulgite is in rhabdolith combination, and single stick crystalline substance diameter is 20~70 nm, length About 0.5 ~ 5 μm.Due to the special 1-dimention nano fibrous structure of attapulgite, and surface can be into rich in great amount of hydroxy group The progress of one step is macromolecule modified, therefore attapulgite can be used as a kind of excellent pvdf membrane material blending additive.
Summary of the invention
The object of the present invention is to provide a kind of pollution-resistant polyvinylidene fluoride (PVDF) ultrafiltration membranes, utilize the unique nanometer of attapulgite The tridimensional network that fibre structure and Kynoar are formed is to be effectively improved the structure and by force of polyvinylidene fluoride (PVDF) ultrafiltration membrane Degree improves permeability of the membrane and hydrophily using attapulgite high-hydrophilic, realizes resistance tocrocking and easy cleaning.
The first aspect of the invention provides:
The surface of a kind of modified attapulgite, the modified attapulgite has structure as shown in the formula (I):
(I)；
Wherein, n is the arbitrary integer between 1~10000.
The second aspect of the invention provides:
A kind of modified PVDF ultrafiltration membrane of attapulgite, is also mixed with above-mentioned modified attapulgite in PVDF ultrafiltration membrane.
In one embodiment, the weight ratio between the modified attapulgite and PVDF is 1~10:20.
The second aspect of the invention provides:
A kind of preparation method of the modified PVDF ultrafiltration membrane of attapulgite, includes the following steps:
The coupling agent of the key containing C=C is grafted on the surface of attapulgite by step 1；
Step 2, by methacrylic acid N, the attapulgite of the coupling agent grafting that N- dimethylaminoethyl and step 1 obtain into Row polymerization reaction；
Step 3, the modified attapulgite that step 2 is obtained are added into PVDF casting solution, are prepared by phase conversion method Obtain ultrafiltration membrane.
In one embodiment, in the step 1, the coupling agent of the key containing C=C is silane coupling agent MPS；Concave convex rod The w/v of the coupling agent of Shi Yuhan C=C key is 12g:5~15mL, and graft reaction carries out under the conditions of organic solvent, institute The organic solvent stated is toluene, and 55~70 DEG C of reaction temperature, 2~6h of reaction time, product needs washed, dry after reaction Processing.
In one embodiment, in the step 2, methacrylic acid N, N- dimethylaminoethyl and coupling agent grafting The weight ratio of attapulgite be 0.5~6:2；Polymeric reaction temperature is 75~85 DEG C, and the reaction time is 1~5h, and reaction terminates Product needs washed, drying process afterwards.
In one embodiment, in the step 3, PVDF, organic solvent, pore-foaming agent are contained in PVDF casting solution, The mass ratio of modified attapulgite and PVDF, organic solvent, pore-foaming agent is: 0.05~0.42:10~14:1~5:30~60；Institute The organic solvent stated is triethyl phosphate；The pore-foaming agent is PEG.
In one embodiment, in the step 3, phase conversion method is by scratching PVDF casting solution in plate It is upper to be formed a film by immersion precipitation phase inversion process.
The third aspect of the invention provides:
Application of the modified PVDF ultrafiltration membrane of above-mentioned attapulgite in liquid filtering.
In one embodiment, contain protein in the liquid.
The fourth aspect of the invention provides:
Application of the modified attapulgite in polymer film preparation.
In the described application, modified attapulgite for reducing polymer film to the absorption of protein, reduce in polymer Big hole defect, reduce pore-size distribution width, improve porosity, improve thermal stability, improve tensile strength, improve break elongation Rate improves hydrophily, improves water flux, improves to dirty containing flux, the reduction filter process film during protein solution filtration Irreversible membrane pollution in flux recovery rate or reduction filter process after staining index MFI, raising Membrane cleaning.
Beneficial effect
1. the pollution-resistant polyvinylidene fluoride (PVDF) ultrafiltration membrane both utilized attapulgite typical nanofibrous structures and its with it is poly- The tridimensional network that vinylidene is formed effectively improves the structure and intensity of polyvinylidene fluoride (PVDF) ultrafiltration membrane, and utilizes concave convex rod The high-hydrophilic of stone effectively improves the permeability and hydrophily of polyvinylidene fluoride film, realizes its antipollution easy cleaning.2. with Traditional inorganic nano-particle is compared, and attapulgite is a kind of typical monodimension nanometer material, internal multichannel, high-specific surface area, And it is big in China's reserves, low in cost, to environment without negative effect, it is fine that cost performance is substantially better than artificial synthesized 1-dimention nano Tie up material.3. attapulgite surface is rich in hydroxyl, this provides convenience for the further functional modification in surface, and with it is unmodified Attapulgite compare, by improving inorganic nano-particle in its surface grafting polymethylacrylic acid N, N- dimethylaminoethyl Son and macromolecule between compatibility, improve the dispersibility of attapulgite, but can be improved by the winding of macromolecular chain its Stability in film.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of modified attapulgite；
Fig. 2 is the XRD spectrum of modified attapulgite；
Fig. 3 is material SEM figure；Wherein, the region a is PGS；The region b is PGS-MPS；The region c is PGS-g-PDMAEMA；
Fig. 4 is the EDX elemental analysis result of modified attapulgite；
Fig. 5 is the Adsorption experimental results comparison diagram of albumen；
Fig. 6 is the upper surface infrared spectrum of film；
Cortex, bottom surface and the cross-section diagram of the pure pvdf membrane of Fig. 7 and hybrid films；
The graph of pore diameter distribution of Fig. 8 difference film；
Fig. 9 is the hot weight curve of pure PVDF ultrafiltration membrane and hybrid films；
Figure 10 is the contact angle comparison diagram of the PGS-g-PDMAEMA film of different content；
The starting of the film of Figure 11 difference modifier content and the contact angle comparison diagram after 200 s；
Figure 12 is the dynamic contact angle comparison diagram of the PGS-g-PDMAEMA film of different content；
Figure 13 is the pure water flux comparison diagram of the PGS-g-PDMAEMA film of different content；
Figure 14 is adsorbance comparison diagram of the film to BSA；
Figure 15 film filtering BSA permeation flux changes over time curve graph；
The rejection of Figure 16 film and steady seepage flux vs figure；
Dynamic adsorbance comparison diagram of Figure 17 film to BSA；
Figure 18 index of membrane fouling comparison diagram；
The flux recovery rate comparison diagram of PVDF/P0 and PVDF/P4 under Figure 19 difference cleaning way；
The steady seepage flux and flux recovery rate comparison diagram of Figure 20 film；
The pollution resistance analysis comparison diagram of Figure 21 film.
Specific embodiment
Attapulgite (Attapulgite, ATP) is the main composition of non-metal clay mineral attapulgite clay.1980 Recommend its English entitled Palygorskite(PGS year Bailey).Attapulgite belongs to sepiolite group, is a kind of typical layer chain The aqueous rich magnesium aluminium silicate mineral of shape structure, common structural formula are Mg5(Si4O10)2(OH)2(OH2)4·4H2O.Concave convex rod Stone is in rhabdolith combination, and single stick crystalline substance diameter is 20 ~ 70 nm, and length is about 0.5 ~ 5 μm.In each 2:1 type chain stratiform In structure sheaf, 180 ° are overturn along y-axis tetrahedron top every some cycles, that is, may make up the link layer for being parallel to x-axis.This spy Different structure feature makes attapulgite meet the feature of monodimension nanometer material, is capable of forming the one-dimensional of the nm of 0.38 nm × 0.63 Duct.The special diameter and duct that attapulgite has, interior Extra specific surface area is big, and possesses special surface charge distribution and more Remaining positive and negative charge, the high-specific surface area that attapulgite has, distribution of charges are uneven；Due to attapulgite surface be rich in it is big Negative electrical charge and silicone hydroxyl are measured, organic modification can be carried out to it with coupling agent and polymer etc..
Attapulgite surface polymethylacrylic acid N, N- dimethylaminoethyl (PDMAEMA) grafting and modifying are divided into two steps, stream Journey is as follows, is first modified with silane coupling agent MPS to attapulgite, makes its surface rich in carbon-carbon double bond, is then drawing Using free yl graft polymerization method in modified attapulgite surface grafting PDMAEMA under the action of hair agent potassium peroxydisulfate (KPS).
The preparation of 1 modified attapulgite of embodiment
The preparation of PGS-MPS
In the four-neck flask of 500 mL, dry 12 g attapulgites and 200 mL toluene are sequentially added, are protected in nitrogen It protects mechanical stirring under 60 DEG C of oil baths to mix them thoroughly, 10 mL silane coupling agent MPS is added dropwise after 30 min dropwise, are added dropwise The reaction was continued afterwards 4 h.After the reaction was completed, product is centrifugated, is washed three times with dehydrated alcohol, except unreacted in dereaction Silane coupling agent and solvent, the product finally obtained is dried in vacuo at 60 DEG C, is ground after 5 h, the first step can be obtained Modified product PGS-MPS.
The preparation of PGS-g-PDMAEMA
250 mL four-neck flasks, sequentially add 2 g PGS-MPS and 80 mL deionized waters, after 2 h of ultrasonic disperse, 80 Mechanical stirring under DEG C oil bath is added dropwise 0.06 g KPS solution with dropping funel after 30 min, removing polymerization inhibitor is slowly added dropwise after 1 h DMAEMA afterwards, respectively 0.5 g, 2 g, 4 g, 6 g, the reaction was continued under nitrogen protection 3 h.Product after the reaction was completed from It is washed with deionized three times after heart separation, monomer and initiator extra in solution is removed, after being finally freeze-dried 24 h Grinding obtains final product PGS-g-PDMAEMA.
The characterization of modified attapulgite
(1) infrared spectrum measurement (FTIR): the solid powder obtained after reaction is mixed with potassium bromide (KBr) solid and is ground Mill, is developed into transparent thin slice, using infrared spectrometer AVATAR 360FT-IR to attapulgite and modified attapulgite (PGS, PGS-MPS, PGS-g-PGS) carries out infrared spectrum analysis, and scanning accuracy is to set 4, and scanning times are set as 32 times, scan model It encloses and is set as 4000 cm-1~500 cm-1.As shown in Figure 1, by curve (a) (b) it is found that (b) in 1305 cm-1Nearby occur new Peak, corresponding C-O stretching vibration peak, in 1708 cm of wavelength-1There is the stretching vibration peak of C=O-O ester bond in place, in 2970 cm-1 Nearby there is-CH2The characteristic peak of methylene, after this illustrates that the first step is modified, silane coupling agent is successfully grafted on concave convex rod Shi Shang.(b) (c) curve is observed, (c) curve is in 1727 cm of wavelength-1There is obvious characteristic peak in place, and C=O carbonyl is special in corresponding ester group Levy absorption peak, 2722 cm of wavelength-1, 2822 cm-1Neighbouring appearance-N (CH3)2The stretching vibration of c h bond absorbs in tertiary amino group Peak, and 2970 cm-1Locate corresponding methylene absorption peak strength to be remarkably reinforced.It is recessed that this illustrates that monomer DMAEMA is successfully grafted on On convex stick stone.
(2) Crystalline form analysis, pipe electricity X-ray diffraction spectra analysis (XRD): are carried out to attapulgite using X-ray diffractometer Stream is set as 40 mA, and tube voltage is set as 45 kV, and scanning model is 5 ° < 2 θ < 80 °.Attapulgite is analyzed using X difraction spectrum Whether crystal form generates variation after before modification.As shown in Fig. 2, attapulgite PGS and modified attapulgite PGS-MPS, PGS-g- There is strong characteristic peak when 2 θ are 8.3 °, 13.8 °, 16.4 °, 19.8 °, 27.5 ° and 35.4 ° in PDMAEMA, Respectively correspond 110 crystal faces, 200 crystal faces, 130 crystal faces, 040 crystal face, 400 crystal faces and 161 crystal faces of attapulgite.It is wherein most strong Corresponding 110 crystal face of characteristic peak be attapulgite hydroxyl diffraction maximum, observe the discovery of modified attapulgite XRD curve not There are other characteristic peaks, this illustrates that attapulgite crystal structure of in modifying process itself is not destroyed, monomer DMAEMA is grafted on attapulgite surface.
(3) thermogravimetric analysis (TG): in a nitrogen atmosphere, thermogravimetric analysis is carried out using thermogravimetric analyzer, heating rate is set as 10 DEG C/min, Range of measuring temp is 20 DEG C ~ 800 DEG C.Grafting rate is calculated using following formula.
GR indicates grafting rate (%)；ΔW 1 It is warming up to for the modified attapulgite of the first step (PGS-MPS) from 300 DEG C Weightlessness (%) at 700 DEG C；ΔW 2 Attapulgite (PGS-g-PDMAEMA) after indicating modified grafting is warming up to from 300 DEG C Weightlessness during 700 DEG C；W p For PGS-g-PDMAEMA when temperature is 700 DEG C remaining weight (%).
(4) scanning electron microscope and energy spectrum analysis (SEM, EDX): attapulgite is observed using cold field emission scanning electron microscope Topographical property, after analyzing it before modification pattern variation.Attapulgite is placed under infrared lamp dry 10min, is vacuumized Voltage under high vacuum mode, is set as 10kV by metal spraying 90s after 1min.Using cold field emission scanning electron microscopic observation PGS, PGS-MPS With the pattern of PGS-g-PDMAEMA, energy spectrum analysis sample surfaces element composition and content are utilized.As shown in figure 3, compared with PGS, The surface PGS-MPS, PGS-g-PDMAEMA becomes uneven and more loose, especially the modified product of final step The surface of PGS-g-PDMAEMA is the most coarse, this is primarily due to attapulgite surface grafting organic matter.It can be with from Fig. 4 It was found that PGS-g-PDMAEMA has compared more than PGS-MPS N element, content 4.98%；The content of C is risen to by 13.19% 32.59%, the content of other elements O, Mg, Si etc. have different degrees of reduction, absolutely prove that monomer PDMAEMA is successfully grafted Attapulgite surface is arrived.
(5) adsorption experiment of the attapulgite to albumen
The drafting of BSA solution standard curve: the BSA solution of accurate configuration different quality concentration uses visible spectrophotometer The absorbance of various concentration is measured at 278 nm of maximum absorption wavelength.
Adsorption experiment: the attapulgite for weighing 30 mg pours into the conical flask of 250 mL, molten with the phosphoric acid buffer of pH=7.4 Liquid configures the BSA solution of 0.1 g/L, and pipettes the configured solution of 30 mL with pipette and be transferred in conical flask, after sealing Conical flask be put into the shaking table of 25 DEG C of water-baths, taken out after 300 min, the mixture in conical flask poured into centrifuge tube.Turning Speed be 4500 r/min under be centrifugated 5 min, take supernatant liquor, with visible light photometer absorbing wavelength be 278 nm place survey Determine absorbance, corresponding mass concentration is calculated using standard working curve, calculates adsorbance using following formula.
qFor the adsorbance (mg/g) of sample after 300 min；VFor the volume (L) of BSA solution；mFor the quality (g) of sample；C 0 For the initial concentration (g/L) of BSA solution；C f For the concentration (g/L) of BSA solution after absorption.
Tri- kinds of samples of PGS, PGS-MPS and PGS-g-PDMAEMA are at 25 DEG C, it is to bovine serum albumin after adsorbing 300 min (BSA) adsorbance is as shown in Figure 5.As can be seen from the figure PGS is to the adsorbance very little of BSA, about 23.89 mg/g；PGS- The adsorbance of MPS is maximum, reaches 65.12 mg/g；And the adsorbance of PGS-g-PDMAEMA is minimum, only 5.03 mg/g.Explanation PGS-g-PDMAEMA not will increase the absorption to albumen as the blending additive of polyvinylidene fluoride (PVDF) ultrafiltration membrane, not will cause straight Connect pollution.
The preparation of 2 ultrafiltration membrane of embodiment
Casting solution preparation: 48 g triethyl phosphates (TEP) are added in screw thread reagent bottle as solvent, add certain matter 12 g Kynoar (PVDF) powders are added after 2 h of ultrasonic disperse in the modified attapulgite of amount, mechanical under 80 DEG C of oil baths 24 h are stirred, the PEG-400 of 3 g is added as pore-foaming agent, then proceedes to 24 h of stirring, mixture is made to form uniform casting film Liquid.
Casting solution deaeration: configured casting solution is put into vacuum oven, 3 h deaerations are vacuumized at 80 DEG C.
Knifing film forming: using 4340 type knifing machine of Elcometer, and set temperature is 80 DEG C, and adjusting scraper registration is 200 μm, it by casting solution curtain coating on clean glass plate, is formed a film using immersion precipitation phase inversion process, the air evaporation time is 5 s, is coagulated Gu bath temperature is 20 DEG C.
The preparation of dry film: wet film is immersed in dehydrated alcohol, and transfer is placed in hexane solution after 6 h, is taken out after 4 h Naturally dry.
The casting solution composition of different PGS-g-PDMAEMA additive amounts is as shown in the table:
The characterization of ultrafiltration membrane
(1) film surface FTIR-ATR is analyzed: being analyzed using infrared spectrometer film surface chemical composition, scanning accuracy 4 are set as, scanning times are set as 32 times, and scanning range is set as 4000 cm-1~500 cm-1.Infrared analysis is carried out to film surface, such as Shown in Fig. 6, with the increase of modifying agent additive amount, PVDF hybrid films are in 1650 cm-1The peak intensity at place gradually increases, corresponding ester C=O carbonyl characteristic absorption peak in base[88].This illustrates that modifying agent PGS-g-PDMAEMA is successfully mixed into film.
(2) it the electron microscope of film, aperture analysis of porosity: scanning electron microscope analysis (SEM): is scanned using cold field emission Electron microscope analyzes the pattern of film surface and section, sample need to be quenched in liquid nitrogen when shooting section Electronic Speculum disconnected, with Clap to obtain complete clearly cross-section diagram.Fig. 7 is cortex, bottom surface and the cross-section diagram of pure pvdf membrane and hybrid films, can be with from cortex figure Find out, PVDF/P0 film surface contains a large amount of defective holes, and there are many quantity of macropore；The defective hole of PVDF/P1 film significantly reduces, hole Size than more uniform,；The big hole number on the surface PVDF/P4 and PVDF/P7 gradually increases, and is added to modifier particles Hybrid films, defect hole number are respectively less than pure film.From graph of pore diameter distribution as can be seen that PVDF/P0 size distribution compared with Extensively, average pore size proportion only has 35 %, and the hybrid films average pore size proportion after modifying agent has been added to be substantially improved, PVDF/P1 mean pore size percentage is about 76%.This can illustrate that modifier particles can be with PVDF matrix mixed phase well Hold, the macromolecular chain on PGS-g-PDMAEMA particle can be intertwine with each other with PVDF strand, therefore mix what ultrafiltration membrane was formed Big hole count is less than pure film.Can be seen that the increase with PGS-g-PDMAEMA particle weight from film ground plan, the nucleus of film by Decrescence few, quantity gradually increases, and the gap between nucleus also gradually increases.This is because the increase of modifier particles makes precipitating speed Degree is accelerated, and then accelerates the process of PVDF crystallization.As can be seen that the section of film is in unsymmetric structure from cross-section diagram, by Cortex, finger-like pore, spongy hole composition.Its finger-like hole length of the hybrid films of modifying agent is added to less than pure film, skin thickness is small In pure film.This is because the addition of modifying agent makes the viscosity of casting solution become larger, during inversion of phases, between solvent and non-solvent Kinetic exchange process obviously slow down, therefore postpone mutually separate the phenomenon that it is more obvious, be unfavorable for the generation of finger-like pore.Separately Outside, the quickening for crystallizing process will lead to the split-phase speed quickening of film surface, and the film skin thickness of generation reduces.In gel process In, casting solution film-forming, organic phase contraction causes to generate interfacial stress between organic and inorganic phase, it can increase the porosity of film, Pore structure appropriate is formed, therefore the increase of PGS-g-PDMAEMA particle also functions to the effect of pore to a certain extent, makes film Porosity is improved.
(3) opening size test: taking liquid-liquid displacement method to analyze the aperture of film and its distribution using membrane aperture analyzer, Experiment uses isobutyl alcohol-water system, to be saturated water phase as mobile phase.The diaphragm for needing to cut certain diameter before test, is being saturated It is tested again after being impregnated one day in alcohol phase solution, every kind of film at least tests 5 samples, is averaged.
(4) porosity test: membrane porosity is analyzed using wet-dry change.A certain size wet film of clip, uses filter paper The water for quickly wiping film surface attachment away obtains wet film quality after weighing, wet film is placed at least two days in air, until wet film is complete It is complete to spontaneously dry, dry film quality is obtained after weighing.To reduce error, every kind of film at least tests 9 samples, and calculating is averaged.Benefit Porosity calculating is carried out with following formula.
εRefer to the porosity (%) of film,m 1 Withm 2 The quality of wet film and dry film is respectively referred to,ρ w For pure water density (20 DEG C, 1 g/cm3)；ρ m For film density (depending on PVDF and PGS specific gravity and respective density, whereinρ PVDF = 1.79 g/cm3；ρ PGS = 2.05 g/cm3).
Corresponding totality film thickness, skin thickness, average pore size, porosity data are as shown in the table:
Fig. 8 is different the pore-size distribution of film.
(5) thermal stability of film: by thermogravimetric analysis (TG), carrying out thermal stability analysis to film using thermogravimetric analyzer, Use nitrogen as protective atmosphere, heating rate is 10 DEG C/min, and temperature range is 25 DEG C ~ 1000 DEG C.
Fig. 9 is the hot weight curve of pure PVDF ultrafiltration membrane and hybrid films.It can be seen from the figure that the residue of PVDF/P0 contains Amount percentage is minimum, and the remaining percentage composition of PVDF/P1 is maximum, and the remaining percentage composition of PVDF/P4 is slightly less than PVDF/ P1.This may be because split-phase speed is accelerated, more PVDF- in casting solution phase process with the increase for being modified dosage G-PDMAEMA particle is carried over membrane pore structure with the outflow of solvent, forms large hole.Residual mass is mainly derived from PVDF material, so residual mass difference and modified additive PVDF-g-PDMAEMA between PVDF/P0 and other composite membranes The content of particle is related.
(6) film mechanical strength test: mechanical strength test includes elongation and tensile strength test, and dry film is cut into centainly Film both ends are respectively fixed on puller system by the rectangle of size, are at nature straight condition.Sample actual test size For the mm of 10 mm × 50, puller system tensile speed is set as 10 mm/min.Elongation and tensile strength meter are carried out using following formula It calculates.Every kind of film at least prepares 5 samples and is tested, and as a result takes its average value.
WhereinσtFor tensile strength (MPa)；FFor peak load (N)；bFor membrane sample width (mm)；dIt is thick for membrane sample sample It spends (mm) (being obtained by section Electronic Speculum measurement)；ΔcIt is broken length (mm) of moment when being stretched during stretching for sample；L 0 For the initial length (mm) of sample.
Following table is the mechanical strength test data of pure pvdf membrane and hybrid films.
From table it can be found that with the increase for being modified dosage, the tensile strength and elongation of film increase, The tensile strength of PVDF/P7 hybrid films is maximum, reaches 1.898 MPa, and the elongation of PVDF/P4 is maximum, is 52.4 %.This may Be because be added to inorganic particulate, and the PDMAEMA strand of attapulgite surface grafting in film forming process with PVDF Strand is intertwine with each other, therefore the toughness of hybrid films is stronger than pure film, and the tensile strength of film becomes larger, and the addition of inorganic particulate is simultaneously Film can be made to become fragile, so the elongation of hybrid films can decrease down to a certain degree.
(7) contact angle of film: contact angle is the important measurement for measuring wetness degree, and contact angle is whether measurement substance is hydrophilic Major criterion.From General Principle, water will form a θ angle, as contact angle in film surface.It is carried out using sessile drop method The test of film surface static contact angle, carries out dynamic contact angle test with DropMeter A-100p, and drop size is 2 μ L, moves The state contact angle test time is 200 s, and to reduce error, every kind of film at least takes 5 different locations to be tested.To pure PVDF and Hybrid films carry out contact angle test, and as shown in Figure 10, the contact angle of PVDF/P0 is 91.46 °, are added PGS-g-PDMAEMA After son, the contact angle of hybrid films is declined, and the hydrophily of film is improved.Wherein the contact angle of PVDF/P1 film is minimum, is 75.81 ° hydrophily is best.Dynamic test further is carried out to film, studies its permeance property, Figure 11 is measurement dynamic contact angle Corresponding contact angular data can be obtained by software analysis in screenshot in the process.In figure 12 it can be seen that being doped with PGS-g- The contact angle decrease speed of the mixing ultrafiltration membrane of PDMAEMA particle is faster than pure film, illustrates that permeability of the membrane can be improved.200 After s, the contact angle ratio PVDF/P0 of PVDF/P1 film is 20 ° about low, illustrates that modified film hydrophily obtains biggish mention again It is high.This is because during inversion of phases, due to the inductive effect of water, the phenomenon that the oriented film surface isolation of hydrophilic chain and enrichment, The dimethylamino hydrophilic radical that PGS-g-PDMAEMA possesses partially is enriched in film surface during inversion of phases, to make film Hydrophily is enhanced.
(8) pure water flux is tested: being used dead-end filtration mode, is carried out with the cup type ultrafiltration cup of 8400 type of Millipore pure Water flux test.At 25 DEG C, with 0.2 MPa pressure then 30 min of film precompressed is carried out under 0.1 MPa pressure first Test, measures penetrating fluid volume per minute and calculates its pure water flux.Pure water flux calculation formula is as follows:
WhereinJIndicate pure water flux (Lm-2·h-1)；VIt indicates penetrating fluid volume (L)；AIndicate effective membrane area (m2)；t It indicates filtration time (h).
Figure 13 is the pure water flux of hybrid films under pure pvdf membrane and Different adding amount, it can be seen from the figure that PVDF/P0 film Pure water flux it is minimum about 123.28 L/ (m2H), with the addition of modifying agent PGS-g-PDMAEMA particle, pure water flux by Gradually rise, the pure water flux of PVDF/P7 film is maximum, about 271.23 L/ (m2H), it is twice of PVDF/P0 film.In conjunction with Electronic Speculum Map analysis, it is smaller that PVDF/P0 film surface contains a large amount of defective hole fenestra quantity, and is doped with the film of PGS-g-PDMAEMA particle Aperture ratio is more uniform, and fenestra quantity increases.After PGS-g-PDMAEMA particle is added, the viscosity of casting solution increases, inversion of phases film forming Mass transfer velocity slows down between solvent and non-solvent in the process, between PVDF and PGS-g-PDMAEMA particle since contraction is different It will cause the increase of fenestra and porosity, to improve permeability of the membrane energy.Also, due to the parent of PGS-g-PDMAEMA particle Aqueous, during inversion of phases, the dimethylamino hydrophilic radical part that PGS-g-PDMAEMA possesses is enriched in film surface, to make The hydrophily and permeability of film are enhanced.
(9) it BSA Static Adsorption: is carried out with the BSA solution that the phosphate buffer solution of pH=7.4 configures 1 g/L mass concentration quiet State adsorption experiment.Wet film is cut into the rectangle of the mm size of 15 mm × 60, is immersed in phosphate buffer solution and balances film surface Charge takes out after half an hour and is transferred in the plastic test tube equipped with 20 mL BSA solution.By 25 DEG C of merging of plastic test tube sealing Shaking bath in wavelength is solution absorbance in testing tube at 278 nm after absorption 5 hours.Film under the conditions of every kind is at least tested Four samples.Adsorbance is calculated using following formula.
Wherein,q s Indicate static adsorbance (the μ gcm of sample to be tested-2)；C 0 WithC’Respectively indicate BSA under original state The concentration (g/L) of solution after the concentration and Static Adsorption of solution；AIndicate the area (m of wet film sample2)。
Figure 14 is the Static Adsorption of pure pvdf membrane and hybrid films.As can be seen from the figure the PVDF for being added to modifying agent is compound The adsorbance of ultrafiltration membrane is respectively less than pure pvdf membrane, this shows that the addition of modifying agent enhances the antifouling property of film.This is mainly Because modified attapulgite PGS-g-PDMAEMA is gradually migrated to film surface during inversion of phases during Static Adsorption, Hydrophilic layer is formed on film surface layer, therefore hydrophobic BSA solute destroys such water layer and needs certain energy, film surface absorption BSA amount is reduced.Wherein the adsorbance of PVDF/P1 is minimum, about 256.06 mgcm-2；The static adsorbance of PVDF/P7 film omits Less than PVDF/P4, this may be since during inversion of phases, PGS-g-PDMAEMA particle is lost with the outflow of solvent, The modifying agent PGS-g-PDMAEMA for moving to film surface is reduced, this is consistent with the thermogravimetric result of film.
(10) film filtering BSA experiment: experiment uses the cup type ultrafilter of 8400 type of Model of U.S. Millipore company. After wet film is fitted into ultrafilter, with heartily pure water, precompressed half an hour, adjusting pressure to 0.1 MPa are incited somebody to action at 0.2 MPa The BSA solution that feeding liquid changes 100 mL into carries out Ultrafiltration experiment, and (mass concentration is 1 g/L, and solvent is the phosphoric acid buffer of pH=7.4 Solution), penetrating fluid volume is collected in different time, terminates protein filtering after 60 min, penetrating fluid and residue BSA is taken respectively Sample measures absorbance value, determines protein concentration.
Rate and protein retention is calculate by the following formula:
WhereinRIt indicates rejection (%)；C p Penetrating fluid concentration (g/L) after indicating filtering one hour；C 0 It is initial for material liquid Concentration (g/L)
Defining dynamic adsorbance is the amount that unit membrane area penetrates the adsorbed BSA of every milliliter of penetrating fluid, it can reflect Filtering film in protein solution, also can side reflection cake layer and hole plug situation to the absorption situation of albumen.It is calculated using following formula dynamic State adsorbance.
Whereinq d Indicate dynamic adsorbance (μ gcm-2·mL-1)；C 0 、C p WithC 2 Respectively indicate material liquid initial concentration, The concentration and residue BSA solution concentration (g/L) of penetrating fluid；V、V 1 WithV 2 Respectively indicate initial volume, the penetrating fluid volume of material liquid With surplus solution volume in ultrafiltration cup；AIndicate the area (m of membrane sample2)。
Using amendment pollution index MFI come further analyzing film pollution situation, it can reflect that film is got dirty during the separation process The trend of dye, value is bigger, and the contaminated trend of explanation is bigger.First made according to formula following formulat/V - VCurve, then Calculate MFI.
AFor membrane area；VFor penetrating fluid volume；ΔpFor transmembrane pressure；R m For the resistance of film itself；R c For film surface pollution object Drag overall；μFor viscosity of sludge；tFor filtration time.
Film is filtered using BSA as pollutant, permeation flux in experimentation is investigated and changes with time.Such as Figure 15 Shown, all in all, the permeation flux of film is decayed with time change, is finally intended to stablize, and filters preceding 5 min, flux Decline most fast, when to 20 min, slowly, last 30 min is the flux stabilized phase for permeation flux decaying.Having in figure can be seen that The permeation flux rate of decay of hybrid films is less than pure PVDF ultrafiltration membrane, and with the increase of modifying agent additive amount, steady seepage Flux gradually increases, and flux decline speed is slow.This is because with the variation of time, film surface meeting absorbed portion BSA, And it blocks fenestra and gradually forms cake layer, and the addition of modified attapulgite PGS-g-PDMAEMA can be improved and improve film Hydrophily enhances the antifouling property of film.With the increase of PGS-g-PDMAEMA additive amount, the aperture of film and porosity also phase The increase answered.Figure 16 is the steady seepage flux that film filters BSA, the PVDF composite hyperfiltration membrane under PVDF/P0 and Different adding amount Rejection be 100 %, twice of the stabilized flux of PVDF/P7 film nearly PVDF/P0 film, guaranteeing the constant feelings of rejection Water flux is increased under condition.In the above filtering, each pvdf membrane is all 100% to the rejection of BSA.
Figure 17 is the BSA dynamic adsorbance of film surface during filtering BSA.It can be seen from the figure that pure pvdf membrane Dynamic adsorbance is apparently higher than the mixed-matrix ultrafiltration membrane after addition modified attapulgite, this explanation is in filtering BSA solution processes In, pure pvdf membrane hole and film surface are easier BSA adsorption molecule, and Pore Blocking is accumulated more serious with film surface.This is inhaled with static state Attached trend is similar.
Pollution index analysis is carried out to film using amendment pollution index MFI, is cross with permeation flux V as shown in figure 18 Coordinate pair t/V maps, and the slope in linear region is to correct pollution index, indicates that film is contaminated during separating pollutant Trend size.From the graph, it is apparent that the maximum slope of pure PVDF ultrafiltration membrane, MFI index is maximum, and contaminated trend is most Greatly.With the increase of modified attapulgite additive amount, MFI index is gradually reduced, contaminated trend during separating and filtering BSA Be gradually reduced, this further illustrates the addition of modified attapulgite can reduce ultrafiltration membrane during separating pollutant by Pollution level.
(11) comparative experiments of the performance easy to clean of film: the cleaning way of film: the difference for investigating polluted membrane after BSA is filtered is clear Influence of the clean mode to flux recovery, experiment use 8400 filter of ultrafiltration cup Millipore, respectively to the film after pollution into The solution of row pure water, pH=10.35 and pH=4.03 respectively cleans three times, is cleaned with different pH solution and is aided with ultrasonic cleaning.Every time with 20 Three times, each 10 min, filter revolving speed is set as 600 r/min to mL liquid rinse, and ultrasonic time is 3 min, and intensity is 40 %. Flux recovery rate after cleaning is calculated using following formula.
FRR It indicates flux recovery rate (%);J w1WithJ w2Respectively indicate the preceding pure water flux (Lm with cleaning caudacoria of filtering-2·h-1)。
The easy cleaning performance for investigating film, is cleaned with pure water respectively, is cleaned with the alkali of pH=10.35, clear with the acid of pH=4.03 It washes, adjust different pH value and is aided with the mode of ultrasound, be 4% modified attapulgite mixed base to pure PVDF ultrafiltration membrane and additive amount Matter ultrafiltration membrane PVDF/P4 is cleaned.As shown in figure 19, flux recovery rate of the PVDF/P4 film after Membrane cleaning under different modes Be all larger than pure pvdf membrane, and adjust different pH and be aided with ultrasound the obtained effect of cleaning way it is best.The result shows that pure film exists It adjusts different pH and cleans and be aided with flux recovery rate highest under the mode of ultrasound, reach 24 %, and PVDF/P4 mixed-matrix ultrafiltration Membrane flux can be restored to 43.19 %, close to twice of pure film.Using the highest cleaning way of flux recovery rate, to pure pvdf membrane It is cleaned with the mixed-matrix ultrafiltration membrane under different modifying agent additive amounts, tests its flux recovery rate, as a result as shown in figure 20. It can be seen from the figure that the flux recovery rate of mixing ultrafiltration membrane is all larger than PVDF/P0, the flux recovery rate of PVDF/P1 is maximum, reaches To 54.17 %, this is because the contact angle of PVDF/P1 is minimum, hydrophily is best, and the roughness of film surface is smaller, therefore Antifouling property is best, this is consistent with the trend of film Dynamic Adsorption.
(12) membrane pollution resistance is analyzed: introducing protein solution permeation fluxJp, it is logical with the pure water of cleaning caudacoria before filtering AmountJ w1WithJ w2, gross contamination resistanceR t , reversible membrane fouling resistanceR r With irreversible membrane fouling resistanceR ir , carry out membrane pollution resistance analysis.? Filtration protein solution carries out Membrane cleaning later, and the pollution that can be removed in cleaning process is known as reversible membrane fouling, this partial contamination Object is mainly deposited on the organic macromolecule and protein of film surface, and it is remaining be referred to as irreversible membrane fouling, mainly due to Strong hydrophobic effect and be adsorbed on the denatured protein of film surface and be blocked in the protein of fenestra.
Gross contamination resistanceR t
Reversible membrane fouling resistanceR r
Irreversible membrane fouling resistanceR ir
It can be seen from figure 21 that the composite membrane gross contamination resistance difference under pure film and Different adding amount is little, and it is pure The irreversible membrane fouling index of pvdf membrane occupies ratio maximum, accounts for about 73.81 %, this explanation pure film during filtering BSA is main It is influenced by irreversible membrane fouling, flux recovery rate is minimum.It is added to the mixed-matrix ultrafiltration membrane of modifying agent PGS-g-PDMAEMA, Its irreversible membrane fouling index proportion is respectively less than PVDF/P0, is conducive to flux recovery.The wherein irreversible membrane fouling index of PVDF/P1 It is minimum, about 44.17 %, flux recovery rate maximum.

Claims (5)

1. a kind of application of modified attapulgite in PVDF ultrafiltration membrane preparation, which is characterized in that the modified attapulgite It is polluted for reducing irreversible membrane in PVDF ultrafiltration membrane filter process；The filter process, which refers to, carries out 1 g/LBSA solution Ultrafiltration；Further include following steps in the application: polluted membrane uses the different pH value of adjusting and is aided with after BSA solution carries out ultrafiltration The mode of ultrasound is cleaned；
Modified attapulgite is mixed in PVDF ultrafiltration membrane；Weight ratio between the modified attapulgite and PVDF is 1 ~10:20；The surface of the modified attapulgite has structure as shown in the formula (I):
(I)；Wherein, n is the arbitrary integer between 1~10000.
2. application described in claim 1, which comprises the steps of:
The coupling agent of the key containing C=C is grafted on the surface of attapulgite by step 1；
Step 2, by methacrylic acid N, the attapulgite for the coupling agent grafting that N- dimethylaminoethyl is obtained with step 1 is gathered Close reaction；
Step 3, the modified attapulgite that step 2 is obtained are added into PVDF casting solution, are prepared by phase conversion method Ultrafiltration membrane.
3. application according to claim 2, which is characterized in that in the step 1, the coupling agent of the key containing C=C is silane Coupling agent MPS；The w/v of the coupling agent of attapulgite and the key containing C=C is 12g:5~15mL, and graft reaction is organic molten It is carried out under the conditions of agent, the organic solvent is toluene, and 55~70 DEG C of reaction temperature, 2~6h of reaction time is produced after reaction Object needs washed, drying process.
4. application according to claim 2, which is characterized in that in the step 2, methacrylic acid N, N- dimethylamino The weight ratio of ethyl ester and the attapulgite of coupling agent grafting is 0.5~6:2；Polymeric reaction temperature is 75~85 DEG C, the reaction time It is 1~5h, product needs washed, drying process after reaction.
5. application according to claim 2, which is characterized in that in the step 3, in PVDF casting solution containing PVDF, The mass ratio of organic solvent, pore-foaming agent, modified attapulgite and PVDF, organic solvent, pore-foaming agent is: 0.05~0.42:10~ 14:1~5:30~60；The organic solvent is triethyl phosphate；The pore-foaming agent is PEG；In the step 3, phase Method for transformation be by by PVDF casting solution blade coating on plate pass through immersion precipitation phase inversion process film forming.
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