CN102258950A - Polysulfone-polypyrrole nanoparticle asymmetric composite ultrafiltration film and preparation method thereof - Google Patents
Polysulfone-polypyrrole nanoparticle asymmetric composite ultrafiltration film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a polysulfone-polypyrrole nanoparticle asymmetric composite ultrafiltration film. The polysulfone-polypyrrole nanoparticle asymmetric composite ultrafiltration film with different components is prepared by using polysulfone as a substrate film-forming material and a highly dispersive polypyrrole nano particle as a filler through solvent blending and phase transfer. The preparation method provided by the invention requires simple equipment and has convenience for operation, low production cost and no after-treatment. The obtained polypyrrole nanoparticle in the composite film is dispersed very uniformly in polysulfone, and the obtained film has no pollution. In the preparation process, a pore structure of the film, hydrophilicity and charge propery are controlled through regulating the content and the particle diameter of the polypyrrole nanoparticle and a casting film solution concentration so as to optimize the separation property of the film. The obtained composite ultrafiltration film is suitable for ultimate filtering of various western medicine injections, oral liquid, eye lotions and the like, protein separation and purification, human body hemodialysis and the like and has favorable selective separation functions for bovine serum proteins.
Description
Technical field
The invention belongs to the preparing technical field of modified ultrafiltration membrane, be specifically related to polysulfones-compound asymmetric milipore filter of polypyrrole nano particle of a kind of high-hydrophilic energy, highly charged response performance, high permeability and high protein rejection and preparation method thereof.
Background technology
In recent years, advantage such as asymmetric ultrafiltration membrane technique is simple with it, energy consumption is little and efficient shows the unique advantage of more traditional isolation technics in the bio-separation field.(Ghosh R. Protein separation using membrane chromatography:opportunities and challenges [J]. Journal of Chromatography A, 2002,952 (1-2): 13 –, 27. Feins M, Sirkar K K. Highly selective membranes in protein ultrafiltration [J]. Biotechnology and Bioengineering, 2004,86 (6): 603 –, 611. Feins M, Sirkar K K. Novel internally staged ultrafiltration for protein purification [J]. Journal of Membrane Science, 2005,248 (1-2): 137 – 148.) this mainly is embodied in, asymmetric ultrafiltration membrane technique can reduce cost greatly, accelerate the new drug development paces, be specially adapted to haemodialysis, terminal processes device in wastewater treatment and the ultra-pure water preparation.In addition, successfully utilize hyperfiltration technique to carry out the concentrated purification of Chinese herbal medicine in China.
The present conventional ultrafiltration of development both at home and abroad film generally adopts phase transfer method, promptly by steps such as casting solution preparation, knifing, exchange of solvent, makes the unsymmetric structure film of the finger-hole supporting layer that has fine and close epidermal area and loosen.During use for bearing the big needs of operating pressure, generally film is adhered to or directly striking on the nonwoven supporter.It is generally acknowledged that desirable asymmetric milipore filter satisfies four fundamentals: high osmosis energy, high selectivity energy, good antifouling property and suitable mechanical strength.(Gaborski T R, Snyder J L, Striemer C C, Fang D Z, Hoffman M, Fauchet P M, McGrath J L. High-performance separation of nanoparticles with ultrathin porous nanocrystalline silicon membranes [J]. ACS Nano, 2010,4 (11): 6973 – 6981.) moreover, in separation processes such as biological substance such as protein, milipore filter also must satisfy cheap, excellent two aspect key elements such as surperficial charged response performance.
Polysulfones (Polysulfone) has obtained extensive use because of its relative low price, high mechanical properties, superior film forming and good characteristics such as chemical stability in asymmetric hyperfiltration technique.But, there is not the functional group that can be directly used in immobilized large biological molecule on intrinsic hydrophobicity, charged bad response and the molecule of polysulfones, in the Separation of Proteins process, be easy to generate the scale inhibition effect, greatly reduce separative efficiency and film service life; Simultaneously, the milipore filter permeance property and the selectivity that are made by polysulfones can have both simultaneously, must carry out modification to it.
In addition on the one hand, polypyrrole (polypyrrole) is as a kind of special fragrant heterocycle conducting polymer, has good wettability, environmental stability, highly charged density, high conductivity and simple and easy plurality of advantages such as synthetic.(Chen S J, Wang D Y, Yuan C W, Wang X D, Zhang P Y, Gu X S. Template synthesis of the polypyrrole tube and its bridging in vivo sciatic nerve regeneration [J]. Journal of Materials Science Letters, 2000,19 (23): 2157 – 2159.) the big π key of polypyrrole uniqueness is given its unusual photo electromagnetic effect, electrochemical effect, electrochemical machinery actuating effect etc.; Simultaneously, the transmission of the free electron of polypyrrole strand is subjected to specific environment as the control of acidity, humidity, atmosphere and chemical bonding etc. and influence the size of its conductance.
But insoluble, the unmanageable characteristic of polypyrrole causes and can only prepare polysulfones-composite polypyrrole film by original position propagate polymerization method.(Bhattacharya A, Mukherjee D C, Gohil J M, Kumar Y, Kundu S. Preparation, characterization and performance of conducting polypyrrole composites based on polysulfone [J]. Desalination, 2008,225 (1-3): 366 –, 372. Muscalu C, David R, Garea S A, Nechifor A C, Vaireanu D I, Voicu S I, Nechifor G. Polysulfone-polypyrrole ionic conductive composite membranes synthesized by phase inversion with chemical reaction [C]. International Semiconductor Conference, CAS 2009, p557 – 560. Madaeni S S, Molaeipour S. Investigation of filtration capability of conductive composite membrane in separation of protein from water [J]. Ionics, 2010,16 (1): 75 – 80.) dispersion of composite membrane polypyrrole in polysulfones of still this original position propagate polymerization method preparation is inhomogeneous, and oxidant and monomer are residual easily, the pore structure of film is relatively poor, finally influences its use.
Therefore, be badly in need of seeking a kind of simple and can prepare the new method of pure polysulfones-polypyrrole composite hyperfiltration membrane, improve hydrophilicity, charging performance and the separating property etc. of polysulphone super-filter membrane conscientiously.
Summary of the invention
Purpose of the present invention is inhomogeneous in order to solve the dispersion of above-mentioned composite membrane polypyrrole in polysulfones, and technical problem such as oxidant and monomer be residual easily and a kind of polysulfones-polypyrrole nano particle asymmetric compound milipore filter and preparation method thereof is provided.
Prepared composite membrane has more amino, imido grpup active group, good water-wetted surface, biocompatibility, and highly charged performance, mechanical strength, characteristics such as pore passage structure ideal, the affinity ultrafiltration that can be widely used in multiple material separates.
Technical scheme of the present invention
A kind of polysulfones-polypyrrole nano particle asymmetric compound milipore filter is characterized in that its raw material polypyrrole receives
The amount of rice particle and polysulfones, calculating by mass percentage is the polypyrrole nano particle: polysulfones: be 0～20:
80～100；
Described polypyrrole nano particle, its particle diameter are 80～120 nm or 150～250 nm.
The preparation method of above-mentioned a kind of polysulfones-polypyrrole nano particle asymmetric compound milipore filter, promptly be that matrix filmogen, polymolecularity polypyrrole nano particle are filler with the polysulfones, prepared different composition polysulfones-compound asymmetric milipore filter of polypyrrole nano particle by solvent blend and phase transfer, specifically comprised the steps:
(1), preparation casting solution
Polysulfones is dissolved in makes the polysulfones matrix solution in first solvent, the polypyrrole nanoparticulate dispersed is made nanoparticulate dispersion in second solvent, the polysulfones matrix solution is added in the polypyrrole nanoparticulate dispersion again, the mechanical agitation blend forms casting solution;
Described first solvent is selected from
N-methyl pyrrolidone or dimethyl sulfoxide (DMSO) or dimethylacetylamide;
Described second solvent is selected from
N-methyl pyrrolidone or dimethyl sulfoxide (DMSO) or dimethylacetylamide; And first solvent and second solvent are compatible each other;
The mixing ratio of described polypyrrole nano particle and polysulfones, calculating by mass percentage is the polypyrrole nano particle: polysulfones: be 0～20:80～100; The total amount of polysulfones and polypyrrole nano particle is that the concentration of casting solution is 10～18wt%;
Described polypyrrole nano particle diameter is 80～250 nm.
(2), film
After the casting solution stirring deaeration for preparing, place on the supporter, to film, coating thickness all is controlled to be 152 μ m;
Described supporter is level and smooth polyester non-woven fabric, carbon fiber or glass plate etc.; When supporter is a flexible material,, utilize the water-resistance adhesive plaster to assist when filming polyester non-woven fabric is layered on the glass plate as polyester non-woven fabric or carbon fiber.
(3) film forming
The supporter that scribbles casting solution in the above-mentioned steps (2) is horizontal positioned puts into the 3rd solvent and carry out exchange of solvent, i.e. phase transfer promptly obtains polysulfones-polypyrrole nano particle asymmetric compound milipore filter after the phase transfer fully.
Wherein, described the 3rd solvent and step (1) described first kind and second kind of solvent dissolve each other, and are into the poor solvent of membrane matrix polysulfones.The third solvent is a deionized water in the preferred embodiments of the present invention.
Polysulfones-polypyrrole nano particle asymmetric compound milipore filter the product of gained of the present invention is placed in the deionized water and preserves, stand-by.
The prepared polysulfones of the present invention-polypyrrole nano particle asymmetric compound milipore filter is owing to have more amino, imido grpup active group, good water-wetted surface, biocompatibility, highly charged response performance, mechanical strength, characteristics such as pore passage structure ideal.Simultaneously, the unique effect of nano material will give film higher specific area, its specific area reaches 1.8～3.9%, and the specific area of the polysulfones-composite polypyrrole film of original position propagate polymerization method preparation is suitable with pure PS membrane, and the specific area of pure PS membrane only is 1.6%.
In addition, the adding of polypyrrole nano particle can improve the heat resistance of polysulphone super-filter membrane; Simultaneously, polysulfones and polypyrrole are non-toxic material.Therefore; this composite membrane is applicable to many applications such as medical science, food, health, chemical industry, electronics industry and environmental protection; end-filtration as various Chinese and Western medicine injections, oral liquid, eye liquid etc.; the separation purification of protein and blood of human body dialysis etc.; especially bovine serum albumin matter is had good Selective Separation function, also be applicable to the fields such as processing of industrial wastewater.
Useful technique effect of the present invention
The preparation method of a kind of polysulfones of the present invention-polypyrrole nano particle asymmetric compound milipore filter, because pure machinable polypyrrole nano particle and polysulfones are dispersed or dissolved in solvent respectively, formed uniform nano dispersion fluid, can form composite membrane very uniformly by the casting phase transfer method.
Simultaneously, owing in film forming procedure, do not add any additional substance, thus solved the unpurified problem of film of prior art for preparing.
Again since in the preparation process by regulating content, particle diameter and the casting solution concentration of polypyrrole nano particle, can be to pore structure, hydrophily and the charge of film controlling efficiently, and then optimize the separating property of film.
In addition, the preparation method of a kind of polysulfones of the present invention-polypyrrole nano particle asymmetric compound milipore filter, equipment needed thereby is simple, easy to operate, low production cost, need not post processing.
Description of drawings
The infrared absorpting light spectra of the milipore filter of Fig. 1 a, embodiment 1 gained;
The infrared absorpting light spectra of the milipore filter of Fig. 1 b, embodiment 2 gained;
The infrared absorpting light spectra of the milipore filter of Fig. 1 c, embodiment 3 gained;
The infrared absorpting light spectra of the milipore filter of Fig. 1 d, embodiment 4 gained;
The infrared absorpting light spectra of the milipore filter of Fig. 1 e, embodiment 5 gained;
The surface scan electron microscope picture of the milipore filter of Fig. 2 a, embodiment 1 gained;
The surface scan electron microscope picture of the milipore filter of Fig. 2 b, embodiment 2 gained;
The surface scan electron microscope picture of the milipore filter of Fig. 2 c, embodiment 3 gained;
The surface scan electron microscope picture of the milipore filter of Fig. 2 d, embodiment 4 gained;
The surface scan electron microscope picture of the milipore filter of Fig. 2 e, embodiment 5 gained;
The AFM histogram on the milipore filter surface of Fig. 3 a, embodiment 1 gained;
The AFM histogram on the milipore filter surface of Fig. 3 b, embodiment 2 gained;
The AFM histogram on the milipore filter surface of Fig. 3 c, embodiment 3 gained;
The AFM histogram on the milipore filter surface of Fig. 3 d, embodiment 4 gained;
The AFM histogram on the milipore filter surface of Fig. 3 e, embodiment 5 gained;
The scanning electron microscope diagram of the milipore filter section of Fig. 4 a, embodiment 1 gained;
The scanning electron microscope diagram of the milipore filter section of Fig. 4 b, embodiment 2 gained;
The scanning electron microscope diagram of the milipore filter section of Fig. 4 c, embodiment 3 gained;
The scanning electron microscope diagram of the milipore filter section of Fig. 4 d, embodiment 4 gained;
The scanning electron microscope diagram of the milipore filter section of Fig. 4 e, embodiment 5 gained;
The thermal analysis curue of the milipore filter of Fig. 5 a, embodiment 15 gained;
The thermal analysis curue of the milipore filter of Fig. 5 b, embodiment 5 gained;
The milipore filter of Fig. 6 a, embodiment 1～5 gained is the schematic diagram of the pure water flux (being permeability) measured under the 10psi at room temperature, pressure;
The milipore filter of Fig. 6 b, embodiment 1～5 gained is the schematic diagram of the bovine serum albumin matter rejection measured under the 10psi at room temperature, pressure;
The charged response curve in film surface that the milipore filter of Fig. 7, embodiment 1～5 gained is measured under different pH values;
The scanning electron microscope diagram on Fig. 8 a, embodiment 1 pure PS membrane milipore filter surface;
The scanning electron microscope diagram on the milipore filter surface of Fig. 8 b, embodiment 3 gained;
The scanning electron microscope diagram on the milipore filter surface of Fig. 8 c, embodiment 6 gained;
The scanning electron microscope diagram on the milipore filter surface of Fig. 8 d, embodiment 7 gained;
The scanning electron microscope diagram on the milipore filter surface of Fig. 8 e, embodiment 8 gained;
The scanning electron microscope diagram of the milipore filter section of Fig. 9 a, embodiment 1 gained;
The scanning electron microscope diagram of the milipore filter section of Fig. 9 b, embodiment 3 gained;
The scanning electron microscope diagram of the milipore filter section of Fig. 9 c, embodiment 6 gained;
The scanning electron microscope diagram of the milipore filter section of Fig. 9 d, embodiment 7 gained;
The scanning electron microscope diagram of the milipore filter section of Fig. 9 e, embodiment 8 gained;
The milipore filter of Figure 10 a, embodiment 3 and embodiment 6～8 gained is the schematic diagram of the pure water flux (being permeability) measured under the 10psi at room temperature, pressure.
The milipore filter of Figure 10 b, embodiment 3 and embodiment 6～8 gained is the schematic diagram of the bovine serum albumin matter rejection measured under the 10psi at room temperature, pressure.
The specific embodiment
Also in conjunction with the accompanying drawings the present invention is further set forth below by embodiment, but do not limit the present invention.
The present invention relates to structure, form and the performance characterization method of milipore filter
Infrared absorption spectroscopy characterizes
After film taken out from water-bath, under the room temperature behind dry 72 h, adopt ATR/FT-IR JASCO 6300 type Fourier transformation attenuate total reflection infrared absorption spectrometers (Japanese surface chemistry Co., Ltd.), directly the surface chemistry functional group to milipore filter characterizes, and sweep limits is 4000～400cm
-1, resolution ratio is 1cm
-1
SEM characterizes
The direct blade coating of casting solution casting solution is obtained self-supported membrane on glass plate.After film taken out, behind dry 72 h, adopt JEOL JSM 6700 type field emission scanning electron microscopes (Jeol Ltd.) under the room temperature from water-bath, the pattern of the upper surface of milipore filter is observed;
Dried film is positioned over brittle failure in the liquid nitrogen, adopts JEOL JSM 6700 type field emission scanning electron microscopes that the brittle failure of milipore filter is observed in the face of pattern; Before observing sample all being carried out metal spraying handles.
AFM characterizes
After film taken out, under the room temperature behind dry 72 h, adopt Synergy ESPM 3-D type AFM (Japanese basis nanometer instrument company) from water-bath, the surface roughness of milipore filter is tested, test specification is 1cm * 1cm.
Hot analysis and characterization
After film taken out from water-bath, 50
oBehind C vacuum drying 72 h, adopt Perkin Elmer TGA Pyris 1 type thermogravimetric analyzer (U.S. Perkinelmer Instruments LLC), in argon gas (Ar), pure PS membrane and polypyrrole-polysulfone composite membrane are carried out hot analytical test, the intensification scope is 25～1000 ℃, and heating rate is 10 ℃/min.
Hydrophilicity characterizes
Adopt the water contact angle of testing pure polysulfones and composite membrane surface to characterize the hydrophilicity of milipore filter.Adopt Kr ü ss DSA 10 Goniometer type water contact angle testers (Hamburg, Germany company), the surface hydrophilicity of milipore filter is tested by gas prisoner method; Every film is tested 5 times at least, averages then.
Water permeation performance characterizes
Use Osborne Arch Punch type punching instrument (U.S. Zack White Leather company) on above-mentioned composite membrane, to get the disk of diameter as 150mm, adopt AMI UHP-25 type continous way ultrafiltration apparatus (U.S. AMI company), at pressure is that the bio-separation performance of test compound film under the 10psi condition is promptly to water permeability (water flux) with to bovine serum albumin (Bovine serum albumin, repellency BSA) (selectivity).
Characterize the permeance property of milipore filter by measuring the flux of pure water by pure polysulfones and polysulfones-polypyrrole nano particle composite membrane, concrete steps are as follows:
Regulating vacuum valve makes the pressure of system be controlled at 10psi, after stablizing 10min, measure and write down the interior weight of 1 min by water, and the usefulness formula (Fan Zhifeng. polyaniline composite Nano milipore filter preparation research [D]. University Of Tianjin's doctorate paper, 2008, p57.):
Calculate permeability of the membrane, wherein J, V, m, ρ, S and t be respectively water under volume by water of the pure water flux, certain hour inner membrance of film, weight, the mensuration temperature density, measure the effective area and the testing time of diaphragm.The effective area of this research test diaphragm is 3.5cm
2, the testing time is fixed as 60s.
Rate and protein retention characterizes
By measuring pure PS membrane and polysulfones-polypyrrole nano particle composite membrane characterizes milipore filter to the rejection of bovine serum albumin matter (BSA) selection performance.The molecular weight of BSA is about 66kDa, and it is oval spherical that its molecular shape is, and size is 4 nm * 4nm * 14nm; If it is regarded as spheric granules, the about 6nm of its average diameter.Concrete steps are as follows:
Be that the mother liquor compound concentration is the BSA standard liquid of 1.0g/L at first with 0.05mol/L potassium chloride.Adopt ultraviolet specrophotometer to measure solution absorbency at the 278nm place.Then, under 10psi, make the BSA standard liquid see through film to be measured, collect 3mL filtrate; Measure the absorbance of filtrate at the 278nm place, according to formula (Guillen G R, FarrellT P, Kaner R B, Hoek E M V. Pore-structure, hydrophilicity, and particle filtration characteristics of polyaniline – polysulfone ultrafiltration membranes [J]. Journal of Materials Chemistry, 2010,20 (22): 4621-4628.):
The rejection that calculates BSA is a selectivity, wherein
R,
C p With
C f Be respectively the ultraviolet absorptivity of rate and protein retention, standard liquid and the ultraviolet absorptivity of filtrate.
Charged response performance characterizes
The charged response of film is that the Zeta potential by the test membrane surface comes intermediate description.And film surface Zeta potential can adopt streaming potential method, electro-osmosis method, film potential method and electric viscosity method etc. to measure usually, and wherein the streaming potential method is one of method that is acknowledged as the most convenient practicality.The Zeta potential of film in different pH scopes adopts Anton Paar Surpass type potentiometric analyzer (Austrian Anton Paar company) to test, and flowing is the 0.001mol/L Klorvess Liquid mutually; Regulate the pH value that flows mutually by the 0.1mol/L hydrochloric acid solution with the 0.1mol/L sodium hydroxide solution.
?
The preparation of pure PS membrane
(1) preparation of casting solution
Take by weighing the 1.5g polysulfones and join 6.83g
NIn-the methyl pyrrolidone, 50 ℃ of lower magnetic forces stirred two days, formed concentration and were the light yellow homogeneous phase polysulfones solution of 18wt%, and are stand-by;
(2) film
Utilize the water-resistance adhesive plaster auxiliary, polyester non-woven fabric is layered on the glass plate very reposefully, adopt the adjustable coating device of Doctor Blade to film, coating thickness is controlled to be 152 μ m; Polysulfones solution after the deaeration is coated on the straight line level on the polyester non-woven fabric equably, adopts Doctor Blade type coating device to film then;
(3) film forming
The glass plate that scribbles casting solution in the above-mentioned steps (2) is horizontal positioned immerses in the deionization water-bath, by the diffusion in the deionized water of poor solvent, contained in the polymer
N-methyl pyrrolidone is separated from polymer solution; Simultaneously, the deionized water as poor solvent enters in the polymer solution.At room temperature carry out phase transfer, treat exchange of solvent 12h after, can be frozen into pure polysulphone super-filter membrane, the pure polysulphone super-filter membrane of gained be white.
The pure polysulphone super-filter membrane that makes is with a large amount of deionized water rinsings, immersion 4h, and is residual to remove in the striping
N-methyl pyrrolidone, and in deionized water, preserve, stand-by.
After measured, the water contact angle of prepared pure PS membrane is 64.7 ± 3.8
oThe pure water flux that records under 10 psi pressure (being permeability) is 9.2gfd/psi, and the rejection of bovine serum albumin matter is 90.2 ± 5.8%.
In this embodiment, if solvent adopts dimethyl sulfoxide (DMSO) or dimethylacetylamide to substitute
N-methyl pyrrolidone can prepare film like the performance classes.
The polypyrrole nano-particle content is the preparation method of polysulfones-compound asymmetric milipore filter of polypyrrole nano particle of 2.0%, comprises the steps:
(1), the preparation of casting solution
Take by weighing polypyrrole nano particle 0.03g doped hydrochloride attitude, diameter 80～100nm and add 6.83g respectively
N-methyl pyrrolidone after 50 ℃ of following ultrasonic waves disperse 6h, stirs 24h at same temperature lower magnetic force again, and the polypyrrole nano particle is dispersed in
NIn-the methyl pyrrolidone; Then the 1.47g polysulfones is joined respectively in above-mentioned each dispersion liquid, 50 ℃ of lower magnetic forces stir 24h, and ultrasonic again 2h forms polypyrrole content and is 2.0% polysulfones-polypyrrole nano particle blend solution, and is stand-by;
(2), film
Changing pure polysulfones solution into step (1) described polypyrrole content is 2.0% polysulfones-polypyrrole nano particle blend solution, and other are with the step among the embodiment 1 (2);
(3), film forming
The glass plate that scribbles casting solution in the above-mentioned steps (2) is horizontal positioned immerses in the deionization water-bath, by the diffusion in the deionized water of poor solvent, contained in the polymer
N-methyl pyrrolidone is separated from polymer solution; The contained adulterant example hydrochloric acid of polypyrrole nanosphere, ferric trichloride spread in water-bath; Simultaneously, the deionized water as poor solvent enters in the polymer solution.At room temperature carry out phase transfer, treat exchange of solvent 12h after, can be frozen into polysulfones of the present invention-polypyrrole nano particle composite hyperfiltration membrane, the polysulfones of gained-polypyrrole nano particle composite hyperfiltration membrane is brown.
The film that makes is with a large amount of deionized water rinsings, immersion 4h, and is residual to remove in the striping
N-methyl pyrrolidone and adulterant are preserved in deionized water, and be stand-by.
Embodiment 3
The polypyrrole nano-particle content is the preparation method of polysulfones-compound asymmetric milipore filter of polypyrrole nano particle of 4.0%, comprises the steps:
(1), the preparation of casting solution:
Take by weighing polypyrrole nano particle 0.06g doped hydrochloride attitude, diameter 80～100nm and add 6.83g respectively
N-methyl pyrrolidone after 50 ℃ of following ultrasonic waves disperse 6h, stirs 24h at same temperature lower magnetic force again, and the polypyrrole nano particle is dispersed in
NIn-the methyl pyrrolidone; Then the 1.44g polysulfones is joined respectively in above-mentioned each dispersion liquid, 50 ℃ of lower magnetic forces stir 24h, ultrasonic again 2h, and formation polypyrrole content is polysulfones-polypyrrole nano particle blend solution of 4.0%, and is stand-by;
(2), film
Changing pure polysulfones solution into step (1) described polypyrrole content is polysulfones-polypyrrole nano particle blend solution of 4.0%, and other are with embodiment 1;
(3), film forming
With the step (3) of embodiment 2, finally obtain polypyrrole content and be 4.0% the compound asymmetric milipore filter of polysulfones-polypyrrole nano particle, the compound asymmetric milipore filter of the polysulfones of gained-polypyrrole nano particle is a brownish black.
The polypyrrole nano-particle content is the preparation method of polysulfones-compound asymmetric milipore filter of polypyrrole nano particle of 10%, comprises the steps:
(1), the preparation of casting solution:
Take by weighing polypyrrole nano particle 0.15g doped hydrochloride attitude, diameter 80～100nm and add 6.83g respectively
N-methyl pyrrolidone after 50 ℃ of following ultrasonic waves disperse 6h, stirs 24h at same temperature lower magnetic force again, and the polypyrrole nano particle is dispersed in
NIn-the methyl pyrrolidone; Then the 1.35g polysulfones is joined respectively in above-mentioned each dispersion liquid, 50 ℃ of lower magnetic forces stir 24h, and ultrasonic again 2h forms polypyrrole content and is 10% polysulfones-polypyrrole nano particle blend solution, and is stand-by;
(2), film
Changing pure polysulfones solution into step (1) described polypyrrole content is 10% polysulfones-polypyrrole nano particle blend solution, and other are with the step among the embodiment 1 (2);
(3), film forming
With the step among the embodiment 2 (3), finally obtain polypyrrole content and be 10% the compound asymmetric milipore filter of polysulfones-polypyrrole nano particle, the compound asymmetric milipore filter of the polysulfones of gained-polypyrrole nano particle is black-and-blue.
The polypyrrole nano-particle content is the preparation method of polysulfones-compound asymmetric milipore filter of polypyrrole nano particle of 20%, comprises the steps:
(1), the preparation of casting solution:
Take by weighing polypyrrole nano particle 0.30g doped hydrochloride attitude, diameter 80～100nm and add 6.83g respectively
N-methyl pyrrolidone after 50 ℃ of following ultrasonic waves disperse 6h, stirs 24h at same temperature lower magnetic force again, and the polypyrrole nano particle is dispersed in
NIn-the methyl pyrrolidone; Then the 1.20g polysulfones is joined respectively in above-mentioned each dispersion liquid, 50 ℃ of lower magnetic forces stir 24h, and ultrasonic again 2h forms polypyrrole content and is 20% polysulfones-polypyrrole nano particle blend solution, and is stand-by;
(2), film
Changing pure polysulfones solution into step (1) described polypyrrole content is 20% polysulfones-polypyrrole nano particle blend solution, and other are with the step among the embodiment 1 (2);
(3), film forming
With the step among the embodiment 2 (3), finally obtain the polypyrrole nano-particle content and be 20% the compound asymmetric milipore filter of polysulfones-polypyrrole nano particle, the compound asymmetric milipore filter of the polysulfones of gained-polypyrrole nano particle is a black.
In embodiment 2～5, if solvent adopts dimethyl sulfoxide (DMSO) or dimethylacetylamide to substitute
N-methyl pyrrolidone can prepare composite hyperfiltration membrane like the performance classes.
Naturally the polysulfones after drying-polypyrrole nano particle composite membrane surface is very smooth, and irradiation presents the pattern of metalloid gloss under light.Thereby show that polypyrrole and polysulfones blend are respond well, the physical imperfection that exists in the composite membrane is less.
Infrared spectrum analysis by to pure PS membrane and polysulfones-polypyrrole nano particle composite membrane the results are shown in Figure 1a, Fig. 1 b, Fig. 1 c, Fig. 1 d and Fig. 1 e, can find that from Fig. 1 a pure PS membrane is 835,1324 and 1170cm
-1The stretching vibration of contraposition phenyl ring, the symmetry and the nonsymmetrical vibration absworption peak of sulfuryl appear respectively in the place; Find out from Fig. 1 b, Fig. 1 c, Fig. 1 d and Fig. 1 e, after adding the polypyrrole nano particle, because the INFRARED ABSORPTION of the contained methyl of polysulfones is obvious especially at fingerprint, relative polypyrrole, its INFRARED ABSORPTION is covered by the absorption of polysulfones substantially, and all composite membranes and pure polysulfones show very approaching characteristic infrared absorption; Along with the variation of polypyrrole nano-particle content, chemical shift does not take place in the infrared absorption peak of composite membrane, does not have new chemical bond to generate yet, and shows that the filling of polypyrrole nano particle does not change the chemical constitution of polysulfones, and both are pure physical blending.
Utilize SEM that embodiment 1～5 pure PS membrane and the polysulfones-surface of the compound asymmetric milipore filter of polypyrrole nano particle and the microscopic appearance of section are observed.
Can find out that from the electron scanning micrograph on Fig. 2 a, Fig. 2 b, Fig. 2 c, Fig. 2 d and Fig. 2 e film surface the adding of polypyrrole nano particle causes the aperture porosity on polysulphone super-filter membrane surface obviously to improve.Along with the increase of polypyrrole nanosphere content, micropore size progressively increases.
Utilize NIH ImageJ software that electron scanning micrograph original among Fig. 2 a, Fig. 2 b, Fig. 2 c, Fig. 2 d and Fig. 2 e is handled, measured compound asymmetric milipore filter porosity.In embodiment 1～5, increase to 2.0,4.0 and 10% with the polypyrrole nano-particle content from 0.0% priority, the porosity of film increases to 3.6,5.2 and 5.6% from 1.6% respectively; Continue to increase polypyrrole nano-particle content to 20%, the porosity of film then no longer continues to increase, and maintains about 5.5%.The aperture of compound asymmetric milipore filter surface micropore and porosity increase be because polypyrrole/
N-methyl pyrrolidone disperses liquid phase to differ with the polysulfones/exchange rate of N-methyl pyrrolidone solution in water, and the solvent difference has caused the polypyrrole nano particle to play a part " pore-forming agent " of similar CNT in film forming procedure.
AFM is to utilize the interaction force between probe and the material to scan.The rugged pattern on film surface can cause the generation of probe and sample to be about 10
-11～10
-6Newton's active force makes probe that extremely several microns the distortion of 0.1 dust takes place simultaneously, and laser light reflected Shu Jinhang sensing is passed through in this distortion, thereby obtains the shape appearance figure on film surface.Utilize AFM can obtain the high-precision shape appearance figure in film surface, thereby become one of important means of research milipore filter microstructure.
Utilize among the AFM observation embodiment 1～5, after the adding of different content polypyrrole nano particle to the histogrammic influence of microscopic appearance of the compound asymmetric milipore filter of gained, thereby can know surface average roughness, r.m.s. roughness, maximal roughness and the specific area of composite hyperfiltration membrane.The histogram analysis of the polysulfone composite membrane milipore filter of different polypyrrole nano-particle content is seen Fig. 3 a, Fig. 3 b, Fig. 3 c, Fig. 3 d and Fig. 3 e, and its result is summarised in the table 1.
Table 1, polypyrrole nano-particle content are to the mean roughness (R of polysulfone composite membrane
a), r.m.s. roughness (RMS), maximal roughness (R
Max), the influence of specific area (SAR), water contact angle and surface free energy
As can be seen from Table 1, the surface average roughness of pure polysulfone composite membrane, r.m.s. roughness, maximal roughness and specific area are respectively 2.6nm, 3.3nm, 24.5nm and 1.8%.
As 2.0%, the mean roughness of composite membrane, r.m.s. roughness, maximal roughness and specific area did not change little when the addition of polypyrrole nano particle was high.
Along with the continuous adding of polypyrrole nano particle, the mean roughness of film, r.m.s. roughness and maximal roughness increase afterwards earlier and reduce, and reach maximum when the polypyrrole nano-particle content is 10%.And the specific area of composite membrane is with the improve of polypyrrole nano-particle content, and specific area constantly increases generally.
The compound asymmetric milipore filter section microscopic pattern of different polypyrrole nano-particle content gained is seen Fig. 4 a, Fig. 4 b, Fig. 4 c, Fig. 4 d and Fig. 4 e among the embodiment 1～5.As can be seen, the cortex that a layer thickness is 1～2 μ m is all contained on the section top layer of all films from Fig. 4 a, Fig. 4 b, Fig. 4 c, Fig. 4 d and Fig. 4 e.The section overall picture of all films all presents the big cavity of a large amount of asymmetric finger-like, down increases in the finger-hole aperture from top layer, and bottom is a spongelike structure.And along with nano-filled agent content successively increases to 2.0,4.0,10 and at 20% o'clock from 0 %, film thickness is reduced to 130,120,105 and 85 μ m from 140 μ m respectively; Simultaneously, the perforate enhancing of the macroporous cavity of finger-like, the connectivity between the Kong Yukong improves.The minimizing of film thickness may be relevant with the doping situation of polypyrrole, in film forming procedure because adulterant as acid, oxidant etc. easily by the water filtering, the gross weight of polymer is lower than the gross weight of actual pure PS membrane in the composite membrane.Along with the increase of doping attitude polypyrrole content, the amount that contains adulterant is many more, and the gross weight of polymer is low more in the composite membrane that obtains at last, causes the thickness of film just more little.
Utilize thermogravimetric analysis that the pure PS membrane of gained and the compound asymmetric milipore filter that polypyrrole content is 20% o'clock gained in embodiment 1 and the enforcement 5 have been carried out thermal stability analysis, see Fig. 5 a and Fig. 5 b respectively.
The temperature of the residual burnt amount of the maximum temperature correspondence on the weight-loss curve, the highest weight-loss ratio and the highest weight-loss ratio correspondence often is to weigh the important parameter of material heat endurance.As can be seen, pure PS membrane is the highest by 1000 from Fig. 5 a and Fig. 5 b
oResidual burnt amount during C is for only being 30%, and adopts residual burnt the measuring of compound asymmetric milipore filter to reach 47%; The highest weight-loss ratio of polysulfones and compound asymmetric milipore filter is respectively 17.1%/min and 11.2%/min; The temperature of the highest weight-loss ratio correspondence is 515
oAbout C, show that compound asymmetric milipore filter has the heat endurance higher than PS membrane.
Measure through Kr ü ss DSA 10 Goniometer type water contact angle testers (Hamburg, Germany company), prepared pure polysulfones and polypyrrole content are that the water contact angle of 2.0,4.0,10 and 20% compound asymmetric milipore filter is respectively 64.7 ± 3.8,54.0 ± 5.8,42.1 ± 0.7,45.6 ± 4.1 and 42.9 ± 2.0 among the embodiment 1,2,3,4 and 5
o, see Table 1;
The pure water flux that under 10psi pressure, records (being permeability).Prepared pure polysulfones and polypyrrole content are that the permeability of 2.0,4.0,10 and 20% compound asymmetric milipore filter is respectively 9.2 ± 0.7,41.3 ± 0.7,41.7 ± 3.3,71.8 ± 6.2 and 97.6 ± 6.9 gfd/psi among the embodiment 1,2,3,4 and 5, see Fig. 6 a; The rejection of bovine serum albumin matter is 90.2 ± 5.8,96.3 ± 2.5,94.4 ± 2.8,92.4 ± 3.1 and 85.7 ± 5.3%, sees Fig. 6 b.Compare with pure PS membrane, the hydrophilicity of compound asymmetric milipore filter improves many, and the pure water flux maximum has improved more than 9 times (9.2
Vs.97.6 gfd/psi); Simultaneously, the rejection to bovine serum albumin matter has kept peer-level about 90%.
In addition, can improve the charged response performance in PS membrane surface greatly by in PS membrane, adding the polypyrrole nano particle among the embodiment 1～5, see Fig. 7.
As can be seen from Figure 7 with the increase of nano-filled agent content, the isoelectric point of compound asymmetric milipore filter is toward high pH displacement, being strengthened by protonated ability of compound asymmetric milipore filter; Reduce with the pH value, compound asymmetric milipore filter positive surface charge density increases, and the positive potential response of flowing becomes big; With the rising of pH value, the negative electricity density on compound asymmetric milipore filter surface increases, and the negative potential response of flowing becomes big, and composite hyperfiltration membrane is the charged response milipore filter of a quasi-representative.
The hydrophily that generally believes PS membrane in the prior art is relatively poor, is the major reason that causes its contamination resistance difference and water flux difference.The present invention is by adding hydrophilic, the charged response performance that the polypyrrole nano particle has improved pure PS membrane greatly in polysulfones; this improves the water permeability of compound asymmetric milipore filter and the automatically cleaning ability of film etc. and has very positive effect reducing the absorption of separate substance on the film surface.
Particle diameter is the preparation method of polysulfones-compound asymmetric milipore filter composite membrane of polypyrrole nano particle of forming of the polypyrrole nano particle of 100～120nm, comprises the steps:
(1), the preparation of casting solution
Taking by weighing the 0.06g particle diameter respectively is the polypyrrole nano particle of 100～120nm, is added to 6.83 g
N-methyl pyrrolidone after 50 ℃ of following ultrasonic waves disperse 6h, stirs 24h at same temperature lower magnetic force again, and the polypyrrole nano particle is dispersed in
NIn-the methyl pyrrolidone; The polysulfones that with quality is 1.44g then joins respectively in above-mentioned each dispersion liquid, and 50 ℃ of lower magnetic forces stir 24h, and ultrasonic again 2h forms polypyrrole content and be 4.0%, total concentration is polysulfones-polypyrrole nano particle blend solution of 18wt%, and is stand-by;
(2), film
Polysulfones solution changed into the described formation polypyrrole of step (1) content is 4.0%, total concentration is polysulfones-polypyrrole nano particle blend solution of 18wt%, other are with the step among the embodiment 1 (2);
(3), film forming
With the step among the embodiment 2 (3), finally obtaining particle diameter is the compound asymmetric milipore filter composite membrane of polysulfones-polypyrrole nano particle of the polypyrrole nano particle formation of 100～120nm.
Embodiment 7
Particle diameter is the preparation method of polysulfones-compound asymmetric milipore filter of polypyrrole nano particle of forming of the polypyrrole nano particle of 150～220nm, comprises the steps:
(1), the preparation of casting solution
Taking by weighing the 0.06g particle diameter respectively is the polypyrrole nano particle of 150～220nm, is added to 6.83g
N-methyl pyrrolidone after 50 ℃ of following ultrasonic waves disperse 6h, stirs 24h at same temperature lower magnetic force again, and the polypyrrole nano particle is dispersed in
NIn-the methyl pyrrolidone; The polysulfones that with quality is 1.44g then joins respectively in above-mentioned each dispersion liquid, and 50 ℃ of lower magnetic forces stir 24h, and ultrasonic again 2h forms polypyrrole content and be 4.0%, total concentration is polysulfones-polypyrrole nano particle blend solution of 18wt%, and is stand-by;
(2), film
Polysulfones solution changed into the described polypyrrole content of step (1) is 4.0%, total concentration is polysulfones-polypyrrole nano particle blend solution of 18 wt%, other are with embodiment 1 step (2);
(3), film forming
With the step among the embodiment 2 (3), the polypyrrole that finally obtains particle diameter and be 150～220nm is received
The compound asymmetric milipore filter of rice granuloplastic polysulfones-polypyrrole nano particle.
Particle diameter is the preparation method of polysulfones-compound asymmetric milipore filter of polypyrrole nano particle of forming of the polypyrrole nano particle of 220～250nm, comprises the steps:
(1), the preparation of casting solution:
Taking by weighing the 0.06g particle diameter respectively is the polypyrrole nano particle of 220～250nm, is added to 6.83g
N-methyl pyrrolidone after 50 ℃ of following ultrasonic waves disperse 6h, stirs 24h at same temperature lower magnetic force again, and the polypyrrole nano particle is dispersed in
NIn-the methyl pyrrolidone; The polysulfones that with quality is 1.44g then joins respectively in above-mentioned each dispersion liquid, and 50 ℃ of lower magnetic forces stir 24h, and ultrasonic again 2h forms polypyrrole content and be 4.0%, total concentration is polysulfones-polypyrrole nano particle blend solution of 18wt%, and is stand-by;
(2), film
Polysulfones solution changed into the described polypyrrole content of step (1) is 4.0%, total concentration is polysulfones-polypyrrole nano particle blend solution of 18wt%, other are with embodiment 1 step (2);
(3), film forming
With the step among the embodiment 2 (3), finally obtaining particle diameter is the compound asymmetric milipore filter of polysulfones-polypyrrole nano particle of the polypyrrole nano particle formation of 220～250nm.
In embodiment 6～8, if solvent adopts dimethyl sulfoxide (DMSO) or dimethylacetylamide to substitute
N-methyl pyrrolidone, available is compound asymmetric milipore filter similarly.
Prepared different-grain diameter polypyrrole nano particle composite hyperfiltration membrane surface microscopic topographic is seen Fig. 8 a, Fig. 8 b, Fig. 8 c, Fig. 8 d and Fig. 8 e among embodiment 1, embodiment 3 and the embodiment 6～8.From Fig. 8 a, Fig. 8 b, Fig. 8 c, Fig. 8 d and Fig. 8 e as can be seen, (i.e. 80～100,100～120,150～220 and 220～250nm) polypyrrole nano particle, grain diameter is very unobvious to the influence of composite hyperfiltration membrane configuration of surface to add 4.0% different-grain diameter in polysulfones.The polypyrrole nano particle diameter is also different to prepared film thickness, but with the increase of particle diameter or reduce not find that rule changes.
The compound non-cross-section morphology figure that piles milipore filter of prepared different-grain diameter polypyrrole nano particle sees Fig. 9 a, Fig. 9 b, Fig. 9 c, Fig. 9 d and Fig. 9 e among embodiment 1, embodiment 3 and the embodiment 6～8.
After measured, among the embodiment 3 and 6～8 with particle diameter be 80～100,100～120,150～220 and the compound non-milipore filter water contact angle that piles of 220～250nm polypyrrole preparation of nanoparticles be respectively 42.1 ± 0.7,38.5 ± 3.1,33.8 ± 2.5 and 33.8 ± 2.2
o, compare the water contact angle (64.7 ± 3.8 of the pure PS membrane of embodiment 1 gained
o) reduce many;
The pure water flux that records under 10 psi pressure (being permeability) is respectively 41.7 ± 3.3,39.1 ± 2.8,48.0 ± 3.2 and 47.1 ± 4.0gfd/psi, sees Figure 10 a;
The rejection of bovine serum albumin matter is 94.4 ± 2.8,97.5 ± 3.2,91.4 ± 2.9 and 89.7 ± 3.6%, sees Figure 10 b.
Compare with pure PS membrane, the hydrophilicity of compound asymmetric milipore filter improves many, and the pure water flux maximum has improved more than 4 times (9.2
Vs.48.0 gfd/psi); Simultaneously, kept peer-level about 90% to the rejection of bovine serum albumin matter, even high (90.2
Vs.97.5%).The influence of analyzing different-grain diameter polypyrrole nano particle shows, increases with particle mean size, and the pure water flux of corresponding membrane increases, and the rejection of bovine serum albumin matter slightly reduces.
Above-mentioned specific embodiment just is used for the present invention that explains, rather than limits the invention, and in spirit of the present invention and claim protection domain, any modification and change to the present invention makes all fall into protection scope of the present invention.
Claims (9)
1. the preparation method of polysulfones-polypyrrole nano particle asymmetric compound milipore filter is characterized in that comprising the steps:
(1), preparation casting solution
Polysulfones is dissolved in makes the polysulfones matrix solution in first solvent, the polypyrrole nanoparticulate dispersed is made nano dispersion fluid in second solvent, the polysulfones matrix solution is added in the polypyrrole nano dispersion fluid again, the mechanical agitation blend forms casting solution;
Described first solvent and second solvent mix each other;
(2), film
After the casting solution stirring deaeration for preparing, place on the supporter, to film, coating thickness all is controlled to be 152 μ m;
(3) film forming
The supporter that scribbles casting solution in the above-mentioned steps (2) is horizontal positioned puts into the 3rd solvent and carry out exchange of solvent, i.e. phase transfer promptly obtains polysulfones-polypyrrole nano particle asymmetric compound milipore filter after the phase transfer fully;
Wherein, described the 3rd solvent is a deionized water.
2. the preparation method of a kind of polysulfones as claimed in claim 1-polypyrrole nano particle asymmetric compound milipore filter, the mixing ratio that it is characterized in that described polypyrrole nano particle of step (1) and polysulfones, calculating by mass percentage is the polypyrrole nano particle: polysulfones is 0～20:80～100; And the total amount of polysulfones and polypyrrole nano particle is that the concentration of casting solution is 10～18 wt%.
3. the preparation method of a kind of polysulfones as claimed in claim 2-polypyrrole nano particle asymmetric compound milipore filter is characterized in that the particle diameter of the described polypyrrole nano particle of step (1) is 80～250 nm.
4. the preparation method of a kind of polysulfones as claimed in claim 3-polypyrrole nano particle asymmetric compound milipore filter, the particle diameter that it is characterized in that the described polypyrrole nano particle of step (1) is 80～120 nm or 150～250 nm.
5. the preparation method of a kind of polysulfones as claimed in claim 4-polypyrrole nano particle asymmetric compound milipore filter, the total amount that it is characterized in that described polysulfones of step (1) and polypyrrole nano particle are that the concentration of casting solution is 18 wt%.
6. as the preparation method of the arbitrary described a kind of polysulfones of claim 1～5-polypyrrole nano particle asymmetric compound milipore filter, it is characterized in that:
Described first solvent of step (1) is
N-methyl pyrrolidone or dimethyl sulfoxide (DMSO) or dimethylacetylamide;
Described second solvent is
N-methyl pyrrolidone or dimethyl sulfoxide (DMSO) or dimethylacetylamide;
Described the 3rd solvent of step (3) is a deionized water, and three kinds of solvents mix each other.
7. the preparation method of a kind of polysulfones as claimed in claim 6-polypyrrole nano particle asymmetric compound milipore filter is characterized in that the described supporter of step (2) is level and smooth polyester non-woven fabric, carbon fiber glass or glass plate;
When supporter is polyester non-woven fabric or carbon fiber, utilize the water-resistance adhesive plaster to assist when filming polyester non-woven fabric is layered on glass plate.
8. a kind of polysulfones-polypyrrole nano particle asymmetric compound milipore filter as preparation method's gained of the arbitrary described a kind of polysulfones of claim 1～5-polypyrrole nano particle asymmetric compound milipore filter is used for:
The end-filtration of Chinese and Western medicine injection, oral liquid or eye liquid;
Or the separation purification of protein or blood of human body dialysis;
Or the processing of industrial wastewater.
9. being used for bovine serum albumin matter as the arbitrary described a kind of polysulfones of claim 1～5-polypyrrole nano particle asymmetric compound milipore filter separates.
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