CN106731883A - A kind of poly-dopamine nano lignocellulose Kynoar composite hyperfiltration membrane and preparation method thereof - Google Patents
A kind of poly-dopamine nano lignocellulose Kynoar composite hyperfiltration membrane and preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
Abstract
The present invention relates to a kind of poly-dopamine nano lignocellulose Kynoar composite hyperfiltration membrane and preparation method thereof, this includes：1) sour water solution high pressure homogenization method prepares nano lignocellulose；2) nano lignocellulose polyvinylidene blending milipore filter is prepared with immersion precipitation phase inversion process；3) poly-dopamine nano lignocellulose Kynoar composite hyperfiltration membrane is prepared with immersed surface cladding process.Be combined for the nano-cellulose containing lignin and Kynoar first by the present invention, form the compound film strength of hydrogen bond enhancing, improve the hydrophily with Kynoar as matrix milipore filter, contamination resistance is strong, the introducing of lignin solves the problems, such as that nano-cellulose caused mechanical property bad with polyvinylidene fluoride compatability is low, improves the adhesive attraction of boundary.
Description
Technical field
The invention belongs to field of organic polymer compound, and in particular to a kind of poly-dopamine nano lignocellulose is poly- inclined
PVF composite hyperfiltration membrane and preparation method thereof.
Background technology
It is Piezoelectricity under Kynoar normality, fluorine, carbon, three kinds of elements of hydrogen is contained in its strand.Due to it
With excellent film forming, heat resistance, hydrolytic resistance, creep resistance, nontoxicity, physical and mechanical property, chemical stability, heat-resisting
The features such as property, it has also become widely used ultrafiltration membrane material, but due to a certain degree of hydrophobicity of its own, easily cause film
Pollution, limits its application field, therefore improve milipore filter hydrophily and then improve the resistance tocrocking of milipore filter to a certain extent
The key areas of membrane material research now can be turned into.
Nanometer ligno-ccllulose is the key component of true qualities pulpboard, is to pass through LCC (lignin carbon aquations by lignin and cellulose
Compound) relative molecular mass that is bound up material higher.Lignin have three basic structures, i.e. guaiacyl structure,
Lilac based structures and p-hydroxyphenyl structure.Contain various active functional group, such as hydroxyl, carbonyl, carboxyl, methyl and side chain simultaneously
Structure, is the most abundant organic matter of second in the world.Cellulose is mainly what is synthesized by photosynthesis by plant, is the earth
The most abundant natural reproducible organic high molecular polymer of upper content, with it is inexpensive, be easy to get, renewable, bio-compatible, prepare letter
Single many advantages, such as, paid close attention to by each area research person.
Because nanometer ligno-ccllulose has specific surface energy higher, good hydrophilicity, can be effectively increased compound
The hydrophily of membrane material, so as to improve the contamination resistance of composite film material；Nanometer ligno-ccllulose crystalline texture, shows very
Strong nano effect so that composite membrane obtains mechanical strength raising.Nano-cellulose has mechanical strength high, simple hydrophily
Interface compatibility between nano-cellulose and hydrophobic polymeric polymer is poor, and nanometer ligno-ccllulose can be by lignin
Improve Kynoar in the presence of part to be acted on the interface cohesion of nano-cellulose, improve composite property.The presence of lignin
Improve that Kynoar is compatible with the interface of nano-cellulose, but lignin can not with the interface cohesion effect of Kynoar
Bring greatly improving for composite property.Therefore, addition Kynoar can with the Interfacial compatibilization agent of nanometer ligno-ccllulose
Further to improve the combination property of nanometer ligno-ccllulose/polyvinylidene fluoride composite material.
To be further enhanced by the quantity that blending modification method improves film surface hydrophilic group, strengthen the anti-soil of milipore filter
Dye ability, dopamine D OPA molecules contain catechol and amido functional group, in an oxidizing environment, can be in substrate material surface certainly
It is poly- compound, the poly-dopamine layer with high-adhesiveness is formed, introduced in ultrafiltration membrane surface by the way that poly-dopamine is surface coating modified
More hydrophilic radicals, make composite film material be improved at aspects such as antifouling property, mechanical performances, with preferably application
Prospect and important theory value.
Nano lignocellulose is prepared using sour water solution-high-pressure homogeneous method and immersion precipitation phase inversion process is prepared and received
Rice lignocellulosic/polyvinylidene fluoride blending film material, then prepare poly-dopamine/nanometer by the way that poly-dopamine is surface coating modified
Lignocellulosic/Kynoar composite hyperfiltration membrane, the enhancing of nano-cellulose, lignin can be given full play to by the above method
Compatibilization effect, poly-dopamine improves film hydrophily, obtains good mechanical performance, and the poly-dopamine/nanometer of good hydrophilic property is wooden
Cellulose/Kynoar composite ultrafiltration membrane material.
The content of the invention
For the weak point that this area is present, the purpose of the present invention is to propose to a kind of poly-dopamine nano lignocellulose
Kynoar composite hyperfiltration membrane and preparation method thereof.
The technical scheme for realizing above-mentioned purpose of the present invention is：
A kind of poly-dopamine nano lignocellulose Kynoar composite hyperfiltration membrane, its by including Kynoar, receive
The raw material of rice lignocellulosic, dopamine and organic solvent is made；It is wherein described Kynoar, nano lignocellulose, many
The weight ratio of bar amine is (16-18):(0.06-0.4):(1.8-2.2)；In terms of g/mL, the Kynoar is organic with described
The ratio between bulking value of solvent is (16-18):(70-85)；The organic solvent is N, N dimethyl acetamide.
Preferably, the Kynoar, nano lignocellulose, the weight ratio of dopamine are 16:(0.1-0.4):
(1.8-2.2)。
Preferably, in terms of g/mL, the ratio between the Kynoar and bulking value of the organic solvent are 16:(83-
84)。
Further, the raw material of above-mentioned poly-dopamine nano lignocellulose Kynoar composite hyperfiltration membrane also includes going
Ionized water.
Further, the thickness of above-mentioned poly-dopamine nano lignocellulose Kynoar composite hyperfiltration membrane is 100-
200μm。
Lignocellulosic of the present invention can be prepared using prior art conventional method, such as with true qualities pulpboard or this pulpboard
It is raw material, is prepared (such as described acid is dilute sulfuric acid) by sour water solution-high pressure homogenization method.
The present invention also provides the preparation method of above-mentioned poly-dopamine nano lignocellulose Kynoar composite hyperfiltration membrane,
Comprise the following steps：
1) sour water solution-high pressure homogenization method prepares nano lignocellulose：By true qualities pulpboard with dilute sulfuric acid hydrolyze, at a high speed from
The heart, precipitation is washed with deionized water to neutrality, and gained solids is ligno-ccllulose；Gained solids is transferred to by proportioning
It is high-pressure homogeneous during organic solvent is DMA, nano lignocellulose solution is obtained；
2) nano lignocellulose polyvinylidene blending milipore filter is prepared with immersion precipitation phase inversion process：Step is taken by proportioning
Rapid 1) gained nano lignocellulose solution, Kynoar mixing, are obtained casting film stoste；The casting film stoste is carried out into vacuum
Deaeration is processed, and is then made film, as nano lignocellulose polyvinylidene blending milipore filter；
3) poly-dopamine nano lignocellulose Kynoar composite hyperfiltration membrane is prepared with immersed surface cladding process：Will step
It is rapid 2) obtained in blended ultrafiltration membrane be fixed in reactive tank, add concentration for 2g/L poly-dopamine solution, shake (or shake
It is dynamic), be coated under room temperature and aerobic conditions modified, the poly-dopamine for then being remained gained membrane surface with deionized water is molten
Liquid is washed down, and gained diaphragm is dipped in into (at least 20min) in absolute ethyl alcohol, the unstable poly-dopamine of removal adhesion, obtains final product institute
State poly-dopamine nano lignocellulose Kynoar composite hyperfiltration membrane.Can be stored in deionized water.
Preferably, the step 1) the dilute sulfuric acid concentration be 30-35wt%.
Preferably, step 1) first crushed with pulverizer before true qualities pulpboard sour water solution.Preferably, in terms of g/mL, true qualities
Pulpboard is 1 with the w/v of 30-35wt% dilution heat of sulfuric acid:18.
Preferably, step 1) hydrolysis temperature be 60-70 DEG C, hydrolysis time be 6-9 hours.
Preferably, step 1) the high speed centrifugation rotating speed be 3000r/min-4000r/min.
Preferably, step 1) the high-pressure homogeneous pressure be 80-100MPa, homogeneous 5-10 times.
Specifically, step 1) including true qualities pulpboard is placed in 30-35wt% dilution heat of sulfuric acid, water under the conditions of 60-70 DEG C
Solution 6-9 hours, high speed centrifugation cleans up to eluate is neutral precipitation with deionized water, and it is fine that gained solids is lignin
, then be transferred to solids in DMA, homogenous disperse 5-10 times under 80-100MPa pressure, i.e., by dimension element
Obtain the nano lignocellulose solution.Preferably, in terms of g/mL, the ligno-ccllulose or the nano lignocellulose with
The ratio between bulking value of DMAC N,N' dimethyl acetamide is (0.06-0.4):(70-85)；More preferably (0.1-0.4):(83-
84)。
Preferably, step 2) casting film stoste is prepared under the conditions of ultrasonic agitation.
Preferably, step 2) ultrasonic agitation temperature be 80-100 DEG C, mixing time is 4-6h；The ultrasonic power
It is 200w-300w.
Specifically, step 2) including Kynoar to be added to the N, N bis- of the nano lignocellulose after homogenous disperse
In methyl vinyl amine aqueous solution, ultrasonic agitation dissolves it, obtains casting film stoste.
Wherein, the step 2) in, vacuumized under ultrasonication, vacuum defoamation treatment is carried out to the casting film stoste,
Vacuum during deaeration is -0.05 to -0.09MPa.
Preferably, step 2) time of vacuum defoamation treatment is 1-2h.
Wherein, the step 2) in, include the step of be made film：Casting film stoste is placed in striking film forming on glass plate；
Glass plate is immersed in deionized water, immersion precipitation inversion of phases is carried out at normal temperatures, stand 1~2h, obtain blended ultrafiltration membrane
Material.The thickness of film can be 100-200 μm.
Preferably, step 3) film coating modification time is 2-6h.
Step 3) can be placed in reactive tank on shaking table and carry out by the shake (or vibrations).
Poly-dopamine solution of the present invention can be prepared using this area conventional method；Dopamine is for example weighed, under normal temperature
It is dissolved into appropriate amount of deionized water, ultrasonic agitation 3h (ultrasonic power 200W) obtains poly-dopamine solution.
The ratio between weight of the present invention and volume, or other unit well known to those skilled in the art, such as thousand
G/l.
It is compound present invention additionally comprises poly-dopamine nano lignocellulose Kynoar obtained in above-mentioned preparation method
Milipore filter.
The beneficial effects of the present invention are：
Be combined for the nano-cellulose containing lignin and Kynoar first by the present invention, using in nano lignocellulose
Hydroxyl and Kynoar form hydrogen bond, the compound film strength of enhancing, it is matrix milipore filter to improve with Kynoar
Hydrophily, gained composite hyperfiltration membrane contamination resistance is strong；Meanwhile, the introducing of lignin solves nano-cellulose and Kynoar
The low problem of mechanical property caused by matrix compatibility is bad, improves the adhesive attraction of boundary.To be further enhanced by altogether
Mixed modification method improves the quantity of film surface hydrophilic group, strengthens the contamination resistance of milipore filter, and dopamine D OPA molecules contain
Catechol and amido functional group, in alkaline solution and oxidation environment, can be compound in substrate material surface autohemagglutination, formation has
The poly-dopamine layer of high-adhesiveness, more hydrophilic radicals are introduced by the way that poly-dopamine is surface coating modified in ultrafiltration membrane surface,
Composite film material is set to be improved at aspects such as antifouling property, mechanical performances, with preferable application prospect and important reason
Value.
The key parameter for being determined by experiment control poly-vinylidene-fluoride composite film mechanical property and hydrophilicity is nano wood
The addition of matter cellulose, ultrafiltration membrane thickness, surface coating time.
Brief description of the drawings
Fig. 1：Vinylidene milipore filter multiplication factor prepared by comparative example is 400 times of surface scan electromicroscopic photograph.
Fig. 2：Embodiment 1 prepare poly-dopamine nano lignocellulose Kynoar composite hyperfiltration membrane multiplication factor be
400 times of surface scan electromicroscopic photograph.
Fig. 3：Embodiment 2 prepare poly-dopamine nano lignocellulose Kynoar composite hyperfiltration membrane multiplication factor be
400 times of surface scan electromicroscopic photograph.
Fig. 4：Embodiment 3 prepare poly-dopamine nano lignocellulose Kynoar composite hyperfiltration membrane multiplication factor be
400 times of surface scan electromicroscopic photograph.
Specific embodiment
Following examples are used to illustrate the present invention, but are not limited to the scope of the present invention.It is unreceipted specific in embodiment
Technology or condition person, according to technology or condition described by document in the art, or are carried out according to product description.It is used
Reagent or the unreceipted production firm person of instrument, are the conventional products that can be commercially available by regular distributor.
Employed in the embodiment of the present invention：True qualities pulpboard is purchased from Shandong spring woods papermaking；Sulfuric acid, DMAC N,N' dimethyl acetamide
Purchased from Beijing Chemical Plant；Dopamine, Kynoar (PVDF) are purchased from Shanghai Yi Sheng Co., Ltds.
Vacuum degasser used below using laboratory simple instrument constitute, mainly including vavuum pump, bottle,suction with
Ultrasonator, casting film stoste is poured into bottle,suction, and bottle,suction is placed in ultrasonator, bottle,suction connect vavuum pump from
And realize the vacuum outgas of casting film stoste.
Embodiment 1
1st, got the raw materials ready according to following proportioning：
Kynoar 16g, nano lignocellulose 0.1g, DMA 83.9mL, dopamine 4g, go from
Sub- water 4L.
By in the deionized water of 4g dopamines normal-temperature dissolution to 2L, ultrasonic agitation 3h (ultrasonic agitation power 200W) obtains dense
Spend the poly-dopamine solution for 2g/L.
Nano lignocellulose solution manufacturing method：It is molten that true qualities pulpboard (first being crushed with pulverizer) is placed in 30wt% dilute sulfuric acids
In liquid, solid-to-liquid ratio 1:18g/mL, hydrolyzes 8 hours under the conditions of 60 DEG C, is then precipitated by high speed centrifugation, cleans heavy with deionized water
Form sediment up to eluate is neutrality, then solids 0.1g is transferred to 83.9mL's by the solids for obtaining as ligno-ccllulose
In DMA, the homogeneous under the high pressure of 100MPa, homogeneous 10 times, nano lignocellulose is dispersed in altogether
In DMA, obtain final product.
2nd, casting film stoste is prepared
To step 1) gained nano lignocellulose solution in add Kynoar 16g, under conditions of 80 DEG C ultrasound
Stirring 5h (ultrasonic agitation power 200W), obtains nano lignocellulose Kynoar casting film stoste.
3rd, the degassing of casting solution
The casting film stoste of preparation is placed in vacuum degasser, open vavuum pump carries out ultrasound to casting film stoste at 90 DEG C
Decompression vacuum pumping deaerates (ultrasonic power 200W), and relative degree of vacuum is -0.09MPa, and degassing time is 4h.
4th, knifing shaping
1) it is 200 μm to take the casting solution after deaeration and be cast on clean glass plate, adjust automatic knifing machine to scrape film thickness；
2) glass plate is immersed in deionized water, immersion precipitation inversion of phases is carried out at normal temperatures, stand 1~2h, obtained
Blended ultrafiltration membrane material.The thickness of film is 200 μm.
5th, surface coating
Blended ultrafiltration membrane is fixed in reactive tank and dopamine solution is poured into reactive tank, then put clamping plate reactive tank
In on shaking table, 3h is coated in being the 2g/L aqueous solution in poly-dopamine concentration under room temperature and aerobic conditions, after the completion of coating is modified,
Under the dopamine solution of remained on surface is washed away with deionized water, and diaphragm is dipped in 20min in absolute ethyl alcohol, makes adhesion loosely
Solid polymerization dopamine removed, obtain final product the poly-dopamine nano lignocellulose Kynoar composite hyperfiltration membrane.Can
It is stored in deionized water.
Compare knowable to the weight of the front and rear film of poly-dopamine coating, the poly-dopamine of 2g is coated with above-mentioned composite hyperfiltration membrane.
Multiplication factor is that 400 times of surface scan electromicroscopic photograph is shown in Fig. 2.
Sample ultrafiltration performance is tested, film sample 100mm × 100mm × 0.2mm (length × width x thickness degree), testing time 10
Secondary, results averaged obtains the performance indications of composite membrane, the water flux 544L/m of membrane material2/ h, rejection 93.1%.
The extension test of sample be according to ASTM (ZB-WL300) testing standard, film sample 100mm × 15mm ×
0.15mm (length × width x thickness degree), rate of extension is 1mm/min, testing time 10 times, and results averaged obtains composite membrane
Performance indications, the tensile strength and elongation at break of membrane material are respectively 6.7MPa and 7.4%.
Embodiment 2
1st, got the raw materials ready according to following proportioning：
Kynoar 16g, nano lignocellulose 0.1g, DMA 83.9mL, dopamine 4g, go from
Sub- water 2L.
By in the deionized water of 4g dopamines normal-temperature dissolution to 2L, ultrasonic agitation 3h (ultrasonic agitation power 200W) obtains dense
Spend the poly-dopamine solution for 2g/L.
Nano lignocellulose solution manufacturing method is：True qualities pulpboard (first being crushed with pulverizer) is placed in 30wt% dilute sulfuric acids
In solution, solid-to-liquid ratio 1:18g/mL, hydrolyzes 8 hours under the conditions of 60 DEG C, is then precipitated by high speed centrifugation, is cleaned with deionized water
Precipitation is neutrality up to eluate, and then solids 0.1g is transferred to 83.9mL by the solids for obtaining as ligno-ccllulose
DMA in, the homogeneous under the high pressure of 100MPa, homogeneous 10 times, dispersed by nano lignocellulose altogether
In DMA, obtain final product.
2nd, casting film stoste is prepared
To step 1) gained nano lignocellulose solution in add Kynoar 16g, under conditions of 80 DEG C ultrasound
Stirring 5h (ultrasonic agitation power 200W), obtains nano lignocellulose Kynoar casting film stoste.
3rd, the degassing of casting solution
The casting film stoste of preparation is placed in vacuum degasser, open vavuum pump carries out ultrasound to casting film stoste at 90 DEG C
Decompression vacuum pumping deaerates (ultrasonic power 200W), and relative degree of vacuum is -0.09MPa, and degassing time is 4h.
4th, knifing shaping
1) it is 200 μm to take the casting solution after deaeration and be cast on clean glass plate, adjust automatic knifing machine to scrape film thickness；
2) glass plate is immersed in deionized water, immersion precipitation inversion of phases is carried out at normal temperatures, stand 1~2h, obtained
Blended ultrafiltration membrane material.The thickness of film is 200 μm.
5th, surface coating
Blended ultrafiltration membrane is fixed in reactive tank and dopamine solution is poured into reactive tank, then put clamping plate reactive tank
In on shaking table, 6h is coated in being the 2g/L aqueous solution in poly-dopamine concentration under room temperature and aerobic conditions, after the completion of coating is modified,
Under the dopamine solution of remained on surface is washed away with deionized water, and diaphragm is dipped in 20min in absolute ethyl alcohol, makes adhesion loosely
Solid polymerization dopamine removed, obtain final product the poly-dopamine nano lignocellulose Kynoar composite hyperfiltration membrane.Can
It is stored in deionized water.
Compare knowable to the weight of the front and rear film of poly-dopamine coating, the poly-dopamine of 2g is coated with above-mentioned composite hyperfiltration membrane.
Multiplication factor is that 400 times of surface scan electromicroscopic photograph is shown in Fig. 3.
Sample ultrafiltration performance is tested, film sample 100mm × 100mm × 0.2mm (length × width x thickness degree), testing time 10
Secondary, results averaged obtains the performance indications of composite membrane, the water flux 597L/m of membrane material2/ h, rejection 92.3%.
The extension test of sample be according to ASTM (ZB-WL300) testing standard, film sample 100mm × 15mm ×
0.15mm (length × width x thickness degree), rate of extension is 1mm/min, testing time 10 times, and results averaged obtains composite membrane
Performance indications, the tensile strength and elongation at break of membrane material are respectively 6.9MPa and 7.9%.
Embodiment 3
1st, got the raw materials ready according to following proportioning：
Kynoar 16g, nano lignocellulose 0.4g, DMA 83.5mL, dopamine 4g, go from
Sub- water 2L.
By in the deionized water of 4g dopamines normal-temperature dissolution to 2L, ultrasonic agitation 3h (ultrasonic agitation power 200W) obtains dense
Spend the poly-dopamine solution for 2g/L.
Nano lignocellulose solution manufacturing method is：True qualities pulpboard (first being crushed with pulverizer) is placed in 30wt% dilute sulfuric acids
In solution, solid-to-liquid ratio 1:18g/mL, hydrolyzes 8 hours under the conditions of 60 DEG C, is then precipitated by high speed centrifugation, is cleaned with deionized water
Precipitation is neutrality up to eluate, and then solids 0.4g is transferred to 83.5mL by the solids for obtaining as ligno-ccllulose
DMA in, the homogeneous under the high pressure of 100MPa, homogeneous 10 times, dispersed by nano lignocellulose altogether
In DMA, obtain final product.
2nd, casting film stoste is prepared
To step 1) gained nano lignocellulose solution in add Kynoar 16g, under conditions of 80 DEG C ultrasound
Stirring 5h (ultrasonic agitation power 200W), obtains nano lignocellulose-Kynoar casting film stoste.
3rd, the degassing of casting solution
The casting film stoste of preparation is placed in vacuum degasser, open vavuum pump carries out ultrasound to casting film stoste at 90 DEG C
Decompression vacuum pumping deaerates (ultrasonic power 200W), and relative degree of vacuum is -0.09MPa, and degassing time is 4h.
4th, knifing shaping
1) it is 200 μm to take the casting solution after deaeration and be cast on clean glass plate, adjust automatic knifing machine to scrape film thickness；
2) glass plate is immersed in deionized water, immersion precipitation inversion of phases is carried out at normal temperatures, stand 1~2h, obtained
Blended ultrafiltration membrane material.The thickness of film is 200 μm.
5th, surface coating
Blended ultrafiltration membrane is fixed in reactive tank and dopamine solution is poured into reactive tank, then put clamping plate reactive tank
In on shaking table, when 6h is coated in being the 2g/L aqueous solution in poly-dopamine concentration under room temperature and aerobic conditions, coating is modified to be completed
Afterwards, under the dopamine solution of remained on surface is washed away with deionized water, and diaphragm is dipped in 20min in absolute ethyl alcohol, makes adhesion
Unstable polymerization dopamine is removed, and obtains final product the poly-dopamine nano lignocellulose Kynoar Compound Ultrafiltration
Film.Can be stored in deionized water.
Compare knowable to the weight of the front and rear film of poly-dopamine coating, the poly-dopamine of 2g is coated with above-mentioned composite hyperfiltration membrane.
Multiplication factor is that 400 times of surface scan electromicroscopic photograph is shown in Fig. 4.
Sample ultrafiltration performance is tested, film sample 100mm × 100mm × 0.2mm (length × width x thickness degree), testing time 10
Secondary, results averaged obtains the performance indications of composite membrane, the water flux 658L/m of membrane material2/ h, rejection 90.7%.
The extension test of sample be according to ASTM (ZB-WL300) testing standard, film sample 100mm × 15mm ×
0.15mm (length × width x thickness degree), rate of extension is 1mm/min, testing time 10 times, and results averaged obtains composite membrane
Performance indications, the tensile strength and elongation at break of membrane material are respectively 8.1MPa and 8.3%.
Comparative example
1st, got the raw materials ready according to following proportioning：
Kynoar 16g, DMA 84mL.
2nd, casting film stoste is prepared
By Kynoar add DMA in, the ultrasonic agitation 5h (ultrasonic agitations under conditions of 80 DEG C
Power 200W), obtain pure Kynoar casting film stoste.
3rd, the degassing of casting solution
The casting film stoste of preparation is placed in vacuum degasser, open vavuum pump carries out ultrasound to casting film stoste at 90 DEG C
Decompression vacuum pumping deaerates (ultrasonic power 200W), and relative degree of vacuum is -0.09MPa, and degassing time is 3h.
4th, knifing shaping
1) it is 200 μm to take the casting solution after deaeration and be cast on clean glass plate, adjust automatic knifing machine to scrape film thickness；
2) glass plate is immersed in deionized water, immersion precipitation inversion of phases is carried out at normal temperatures, stand 1~2h, obtained
Composite ultrafiltration membrane material.The thickness of film can be 200 μm.Multiplication factor is that 400 times of surface scan electromicroscopic photograph is shown in Fig. 1.
Sample ultrafiltration performance is tested, film sample 100mm × 100mm × 0.2mm (length × width x thickness degree), testing time 10
Secondary, results averaged obtains the performance indications of composite membrane, the water flux 231L/m of membrane material2/ h, rejection 92.1%.
The extension test of sample be according to ASTM (ZB-WL300) testing standard, film sample 100mm × 15mm ×
0.15mm (length × width x thickness degree), rate of extension is 1mm/min, testing time 10 times, and results averaged obtains composite membrane
Performance indications, the tensile strength and elongation at break of membrane material are respectively 3.2MPa and 4.7%.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (9)
1. a kind of poly-dopamine nano lignocellulose Kynoar composite hyperfiltration membrane, it is characterised in that it is by including poly- inclined
The raw material of PVF, nano lignocellulose, dopamine and organic solvent is made；Wherein described Kynoar, nanometer are wooden
Cellulose, the weight ratio of dopamine are (16-18):(0.06-0.4):(1.8-2.2)；In terms of g/mL, the Kynoar with
The ratio between bulking value of the organic solvent is (16-18):(70-85)；The organic solvent is N, N dimethyl acetamide.
2. composite hyperfiltration membrane according to claim 1, it is characterised in that the Kynoar, nano lignocellulose,
The weight ratio of dopamine is 16:(0.1-0.4):(1.8-2.2)；Preferably, in terms of g/mL, the Kynoar has with described
The ratio between bulking value of machine solvent is 16:(83-84).
3. composite hyperfiltration membrane according to claim 1 and 2, it is characterised in that the thickness of the composite hyperfiltration membrane is 100-
200μm。
4. the preparation method of composite hyperfiltration membrane described in any one of claim 1-3, it is characterised in that comprise the following steps：
1) sour water solution-high pressure homogenization method prepares nano lignocellulose：True qualities pulpboard is hydrolyzed with dilute sulfuric acid, high speed centrifugation, will
Precipitation is washed with deionized water to neutrality；Gained solids is transferred in organic solvent by proportioning, it is high-pressure homogeneous, nano wood is obtained
Matter cellulose solution；
2) nano lignocellulose polyvinylidene blending milipore filter is prepared with immersion precipitation phase inversion process：Step 1 is taken by proportioning)
Gained nano lignocellulose solution, Kynoar mixing, are obtained casting film stoste；The casting film stoste is carried out into vacuum defoamation
Treatment, is then made film, as nano lignocellulose polyvinylidene blending milipore filter；
3) poly-dopamine nano lignocellulose Kynoar composite hyperfiltration membrane is prepared with immersed surface cladding process：By step 2)
Obtained blended ultrafiltration membrane is fixed in reactive tank, and it is the poly-dopamine solution of 2g/L to add concentration, in shake, room temperature and aerobic
Under the conditions of be coated modified, the dopamine solution that gained membrane surface is remained is washed down with deionized water then, and by gained
Diaphragm is dipped in absolute ethyl alcohol, the unstable polymerization dopamine of removal adhesion, obtains final product the poly-dopamine nano lignocellulose
Kynoar composite hyperfiltration membrane.
5. preparation method according to claim 4, it is characterised in that the step 1) the dilute sulfuric acid concentration is 30-
35wt%；In terms of g/mL, true qualities pulpboard is 1 with the w/v of 30-35wt% dilution heat of sulfuric acid:18.
6. the preparation method according to claim 4 or 5, it is characterised in that step 2) casting is prepared under the conditions of ultrasonic agitation
Film stoste；The temperature of the ultrasonic agitation is 80-100 DEG C, and mixing time is 4-6h；The ultrasonic power is 200w-300w.
7. the preparation method according to claim 4 or 5, it is characterised in that the vacuum when vacuum defoamation is processed
Spend is -0.05 to -0.09MPa；Preferably, the vacuum defoamation process time is 1-2h.
8. the preparation method according to claim 4 or 5, it is characterised in that the step 2) include the step of be made film：
Casting film stoste is placed in striking film forming on glass plate；Glass plate is immersed in deionized water, immersion precipitation is carried out at normal temperatures
Inversion of phases, stands 1~2h, obtains blended ultrafiltration membrane material.
9. the preparation method according to claim 4 or 5, it is characterised in that step 3) the film coating modification time is 2-
6h。
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