CN105195028A - Preparation method of composite nanofiber ultra-filtration membrane - Google Patents
Preparation method of composite nanofiber ultra-filtration membrane Download PDFInfo
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Abstract
The invention relates to a preparation method of a composite nanofiber ultra-filtration membrane. The preparation method comprises the following steps: dissolving a high-molecular polymer in a solvent, and then stirring uniformly to obtain a spinning solution, and performing electrostatic spinning to obtain a nanofiber membrane; compounding the nanofiber membrane with nonwoven fabric to obtain nonwoven fabric/nano-membrane/nonwoven fabric composite membrane; performing bonding treatment on the nonwoven fabric/nano-membrane/nonwoven fabric composite membrane to obtain the composite nanofiber ultra-filtration membrane. The preparation method of the composite nanofiber ultra-filtration membrane, provided by the invention, is convenient and fast, the obtained composite membrane has the advantages that the strength variation range is within 50 N-60 N, the elongation at break is 50-75%, which is 60-70 times that of a pure nano membrane, the emulsified oil reject rate reaches up to 98.56%, which is higher than a PVDF commodity ultra-filtration membrane's 97%, the pure water flux is 4004L/(m<2>*h), and the obtained composite membrane is further suitable for fields like medicine, food, environmental protection, bioengineering and the like.
Description
Technical field
The invention belongs to the preparation field of filter membrane material, particularly a kind of preparation method of nanofiber composite hyperfiltration membrane.
Background technology
Oil-polluted water source is very extensive, and as industries such as petrochemical industry, exploitation, machining, leather, weaving, food, and discharge capacity is large, if directly enter water body, very harmful to balance of nature.Have Physical, chemical method, physical-chemical process and microbial method to the traditional treatment method of oil-polluted water, but traditional sewage water treatment method efficiency is low, cost is high and there is secondary pollution.Along with the development of modern science and technology, macromolecule member material is applied to sewage disposal more and more, and nano fibrous membrane is the one wherein had superiority most.
Electrostatic spinning nano fiber diameter is between sub-micron and nanometer, there is the advantages such as specific area is large, porosity is high, preparation process is simple, spin certain thickness even film and cause rapidly the concern of people because having the features such as high filter is imitated, porosity is high, frivolous and be applied to very soon in fields such as bio-medical, filtering material, composite, electronics, nano-sensors.But the poor mechanical property of nano fibrous membrane is the biggest factor of extensive use of holding it back now.
Existing a lot of scholar launches large quantity research for the powerful weak problem of nano fibrous membrane, and method is as follows: blended particle method, as added TiO
2, SiO
2deng, ShuaiW. [Wang, S., etal.AppliedSurfaceScience, 2013.279:p.150-158] etc. research show to add nano fibrous membrane prepared by Fe3O4SiO2POTS nano particle in electrostatic spinning process there is super-hydrophobicity, superparamagnetism, mechanical stability and acid resistance.When Fe3O4SiO2POTS/PVDF mass ratio is 0.10:12, the stress of nanometer film for being 3.53MPa, more than 4 times of to be Fe3O4SiO2POTSPVDF mass ratio be 0.30:12; Post processing, comprise heating, hot gas spring, pre-tension, raising crimpiness, calcining etc., Y.H.D. [Ding, Y., etal.Ionics, p.731-734] etc. 2009.15 (6): research shows that P (VDF-HFP) electrostatic spinning nano fiber film rises to 75 DEG C from 25 DEG C along with temperature, and the fracture strength of nanometer film, in downward trend gradually, drops to about 2MPa from 7MPa; Prepare oriented nanofibers film, B.H. [He, B., etal.TextileResearchJournal, p.1390-1395] etc. 2012.82 (13): research shows that MWNTs/PMIA nano fibrous membrane fracture strength increased along with adding of MWNT, when MWNTs mass ratio is 0.6%, the fracture strength of nanometer film improves 86%; Multiple material blending; Regulate spinning parameter, comprise the selection etc. of humiture, spinning concentration, spinning organic solvent, J.P. [Pelipenko, J., etal.InternationalJournalofPharmaceutics, p.125-134] etc. 2013.456 (1): research shows to control the change of spinning process humidity, can regulate the diameter of nanofiber, and then affect nanometer film mechanical property; Prepare coaxial or multiaxis composite nano-fiber membrane etc., Tijing [Tijing, L.D., etal.CurrentAppliedPhysics, 2013.13 (7): p.1247-1255] etc. research shows high by 25% than single shaft of twin shaft pure PU nano fibrous membrane fracture strength.
These methods solve to a certain extent nanometer film powerful low while, also there is certain weak point.Blendedly to spin, post processing while slightly improving nanometer film intensity, also can reduce the elasticity of nanometer film, and adding due to blended particle, the mixing uniformity of particle will cause harmful effect to the character of nanometer film and spinning condition; Although orientation nano film can improve along fiber direction nanometer film mechanical property to a certain extent, the mechanical property of the direction nanometer film such as Vertical dimension and 45 ° is still very weak; Although blending, regulate the modes such as spinning parameter, coaxial or multiaxis composite nano-fiber membrane can improve the mechanical property of nanometer film to a certain extent, but raising degree is not enough to overcome the defect of nanometer film in application, the such as aspect such as water filtration, water-oil separating, nanometer film is powerful at about 1N, greatly can weaken its service life, reduce its application.By hot rolling for composite filtering material [Sun Xi. a kind of acupuncture/water thorn and Static Spinning composite filtering material manufacture method [P]. Chinese patent: 201310036655.X, 2013-01-31], high-strength composite filtrate can be prepared.But have high-tenacity, the nanometer film preparation technology having high rejection and pure water flux concurrently but rarely has report.
Common have three kinds of methods improving nanometer film brute force and water treatmenting performance, and one is organic and inorganic blending method, and two is surface modification, grafting etc., and three is add material, enhancing process etc.Wei [Wei, Y., etal.Desalination, 2011.272 (1-3): p.90-97] etc. people have studied and prepares PVDF/TiO2 nanometer network composite hyperfiltration membrane with phase inversion, research finds, along with adding of TiO2 nano particle, the heat endurance of composite membrane improves, the hydrophily of dynamic contact angle test result display composite membrane improves, and the brute force of film and resistance tocrocking etc. have good improvement.Document [Wang, X., etal.JournalofMembraneScience, 2010.356 (1-2): p.110-116] adopt electro-spinning for PVA/PAN nano-fiber composite film, this composite membrane is the PVA layer that Static Spinning one deck is very thin in the substrate of Static Spinning PAN film, in pentanediol/acetone soln, steam and chemical crosslinking process are carried out to top layer PVA afterwards, form the barrier layer of PVA.Then carry out the strainability test of oil/water emulsion, result shows, and when operating pressure is 0.3MPa, the water flux of PVA/PAN nano-fiber composite film is up to 2101L/ (m
2h), rejection reaches 99.5%.By PVA crosslinked prepare nanofiber composite hyperfiltration membrane [Li Congju etc. a kind of preparation method [P] of the nanofiber composite hyperfiltration membrane based on electrostatic spinning technique. Chinese patent: 201210140415.X, 2012-05-08], this composite hyperfiltration membrane surface is containing a large amount of hydrophilic radicals and active group, there is good mechanical property and anti-fouling performance, but this milipore filter flux is only at 200L/ (m
2h) left and right.Document [Cao, X., etal.Desalination, 2013.316:p.120-126] have studied double-deck PAN Static Spinning film, enhancing process is carried out to its bringing Selection In property oxidation tossa element nano whisker, the excellent in mechanical performance of this film, has good filter efficiency to the particle of 7 ~ 40nm, can be widely used in drinking water and Industrial Wastewater Treatment.But these methods improve limited to nanometer film brute force, and the pure water flux of the nanometer film obtained is on the low side.
But, improve nanometer film brute force about preparing non-weaving cloth/electrostatic spinning nano fiber film/nonwoven cloth composite membrane by ultrasonic wave or hot rolling or compression molding heat bonding, and make the nanometer film be prepared into have high rejection, the method for high purity water flux then rarely has report.By modification of chitosan through electrospun nanofibers film and with non-woven fabrics, ultra-thin parting absciss layer compound prepare milipore filter [Zhao Zhiguo etc. composite hyperfiltration membrane of modification of chitosan composite electrostatic spinning nanofiber and preparation method thereof [P]. Chinese patent: 201110309966.X, 2011-10-13], the characteristics such as this filter membrane has high water flux, height retains efficiency, low stain, acid and alkali-resistance, but this filter membrane flux is at 100L/ (m
2h) left and right, protein retention efficiency is only 82.2%.By add at spinning solution various component prepare high-strength nano modified ultrafiltration membrane [Wang Beifu. high-strength nano modified ultrafiltration membrane and preparation method thereof [P]. Chinese patent: 201310251741.2,2013-06-21], there is higher porosity, but this patent nanometer film pure water flux is also at 200L/ (m
2h) left and right, rejection is less than 70%, and ultimate strength is greater than 11.56N, still on the low side.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of nanofiber composite hyperfiltration membrane, and the inventive method adhesion technique used is simple, quick, without the need to complicated processing, can prepare high-tenacity nano fibrous membrane convenient, fast, at an easy rate; Preparation method of the present invention is convenient, fast, the nano fibrous membrane obtained has powerful high, good springiness, oil-polluted water rejection is high and pure water flux is high advantage, this will break nanometer film powerful low defect in the application, promote the commercialization of nano material, promote the further expansion of nano material in field application such as bio-medical, filtering material, composite, electronics, nano-sensors.
The preparation method of a kind of nanofiber composite hyperfiltration membrane of the present invention, comprising:
(1) high molecular polymer is dissolved in solvent, stirs, obtain spinning solution, then carry out electrostatic spinning, obtain nano fibrous membrane;
(2) by above-mentioned nano fibrous membrane and non-weaving cloth compound, non-weaving cloth/nanometer film/non-weaving cloth composite membrane is obtained;
(3) above-mentioned non-weaving cloth/nanometer film/non-weaving cloth composite membrane is carried out adhesion process, obtain nanofiber composite hyperfiltration membrane.In described step (1), high molecular polymer is one or more in polypropylene, polyarylate, polyaniline, polycaprolactone, polyurethane, polysulfones, polyacrylonitrile, poly-aspartate, polyvinyl chloride, polyamide, polystyrene, shitosan, Kynoar, nylon 6;
In described step (1), solvent is water, dimethyl sulfoxide (DMSO), formic acid, ethanol, methyl alcohol, acetic acid, N, one or more in dinethylformamide, DMA, trifluoroacetic acid, oxolane, acetone, carrene, chloroform, hexafluoroisopropanol.
In described step (1), the mass percentage concentration of spinning solution is 6%-25%.
In described step (1), the technique of electrostatic spinning is: voltage is 1 ~ 50KV, syringe needle is 0.1 ~ 2m to reception template distance, spinnerette diameters is 1 μm ~ 2mm, spinning speed is 0.1 ~ 20mL/h, the spinning time is 8 ~ 10h, environment temperature is 20 ~ 60 DEG C, and envionmental humidity is 20 ~ 80%.
Non-weaving cloth is melt-blown, spunbond, acupuncture or hydro-entangled non-woven fabric in described step (2).
In described step (3), adhesion process is the one in ultrasonic bonds, hot calendering bonding, compression molding heat bonding.
The parameter of described ultrasonic bonds is: operating air pressure 5 ~ 7Kg/cm
2, vibration frequency is 20 ~ 35KHz, and the rotating speed of output wheel is 0.1 ~ 2m/min.
Described hot calendering bonding parameter is: the linear pressure up and down between hot roll is 0.2 ~ 1MPa, and upper and lower hot roll temperature is 90 ~ 105 DEG C, and hot rolling speed is 0.1 ~ 0.5m/min.
Described compression molding heat bonding parameter is: the linear pressure up and down between flat board is 9 ~ 18MPa, and upper and lower hot roll temperature is 90 ~ 105 DEG C, and the processing time is 120s.
The preparation method of a kind of nanofiber composite hyperfiltration membrane according to claim 1, it is characterized in that: the powerful excursion of described nanofiber composite hyperfiltration membrane is between 50N ~ 60N, elongation at break, between 50% ~ 75%, is 60-70 times of pure nanometer film brute force.
Filtering oily sewage test is carried out after the cutting of nanofiber composite hyperfiltration membrane:
(1) strength test instrument adopts YG065H type fabric strength instrument, and sample holder length is 200mm, draw speed 100mm/min, and 5 data surveyed by each sample. and test environment temperature is 20 DEG C, and humidity is 65%.
(2) the oil-polluted water test parameter of composite membrane is: adopt the cup type filter of Model8400 type to carry out dead-end filtration test, nano fibrous membrane being cut into respectively area is 41.8cm
2circle after put into ultrafiltration cup, the 0.1MPa that pressurizes after then passing into nitrogen 0.2MPa precompressed 0.5h tests, and the rotating speed of ultrafiltration cup rotor is 300r/min.
(3) the pure water flux test of composite membrane: pass into deionized water in fluid reservoir, the unit of account time is by the water volume of unit plane integrated membrane.
(4) the oil emulsion rejection test of composite membrane: preparation mass concentration is the oil emulsion solution of 1g/L, stirs 3min with agitator with the rotating speed of 20000r/min.The oil emulsion solution of preparation is put into fluid reservoir, and after nanofiber membrane filtration 1min, the liquid got stoste He filter out, tests the COD of two kinds of liquid with dichromate titration, calculates rejection R value.
(5) the oil emulsion rejection of the composite membrane described in described step (5) is up to 98.56%, and pure water flux is at 4004L/ (m
2h) more than.
The present invention is by electrospun nanofibers film, by certain ultrasonic wave or hot rolling or compression molding thermal bonding technology will be adopted after non-weaving cloth/electrostatic spinning nano fiber film/nonwoven cloth compound, prepare high-tenacity nano material, this bonding mode is very little to the destruction of Static Spinning nanometer film, nanometer film brute force can be improved, composite membrane can be made again to keep the feature of nano fibrous membrane high rejection and high purity water flux.
The present invention adopts ultrasonic wave or hot rolling or compression molding thermal bonding technology to prepare non-weaving cloth/electrostatic spinning nano fiber film/nonwoven cloth composite membrane, technique is simple, with low cost, nanometer film brute force improves significantly, to filtering oily sewage rejection up to 98.56%, pure water flux is at 4004L/ (m
2h), more than, the fields such as medicine, food, environmental protection, bioengineering are applicable to.Therefore, the present invention greatly can promote the development and application commercially of electrostatic spinning nano fiber film.
beneficial effect
(1) adhesion technique that the present invention is used is very simple, quick, without the need to complicated processing, can prepare high-tenacity nano fibrous membrane easily and fast, at an easy rate;
(2) the present invention can prepare the uniform high-tenacity nano fibrous membrane (30cm × 30cm) of larger area;
(3) the present invention is by controlling adhesion technique, and the bondability of regulation and control nanometer film and base cloth, in filtration, bio-medical industry, especially has extraordinary booster action to the exploitation of functional product;
(4) the powerful excursion of nano composite membrane prepared of the present invention is between 50N ~ 60N, and elongation at break, between 50% ~ 75%, is about 60 times of pure nanometer film brute force;
(5) the oil emulsion rejection of nano composite membrane prepared of the present invention is up to 98.56%, and pure water flux is at 4004L/ (m
2h) more than.
Accompanying drawing explanation
Fig. 1 is that the present invention prepares patterned fibrous device used;
In Fig. 2, A is compression molding heat bonding nanometer film strength test figure; B is the strength test figure of hot rolling nanometer film; C is the stress strain curve of compression molding heat bonding nanometer film; D is the stress strain curve of hot rolling nanometer film;
Fig. 3 PAN nanofiber membrane SEM and diameter distribution profile, A, B represent nanometer film after hot rolling process, adopt nanometer film prepared by embodiment 2 technique, and C, D represent nanometer film after compression molding heat bonding process, adopt nanometer film prepared by embodiment 4 technique, E, F representative is without the nanometer film of any process; Illustration wherein in B is the diameter distribution profile of nanometer film after hot rolling process; Illustration in D is the diameter distribution profile of nanometer film after compression molding heat bonding process; Illustration in F is the diameter distribution profile of the nanometer film without any process;
Static Spinning nanometer film/non-weaving cloth composite membrane prepared by Fig. 4 hot rolling and compression molding thermal bond pattern is powerful, intensity, the wherein powerful and percentage elongation of the Static Spinning nanometer film/non-weaving cloth composite membrane prepared of (a) hot rolling and compression molding thermal bond pattern, it is 100 DEG C that FP1 represents compression molding bonding temperature, it is 90 DEG C that FP1 represents compression molding bonding temperature, it is 100 DEG C that HR1 represents hot-rolled temperature, it is 102 DEG C that HR2 represents hot-rolled temperature, it is 104 DEG C that HR3 represents hot-rolled temperature, and it is 106 DEG C that HR4 represents hot-rolled temperature; Composite membrane fracture strength prepared by (b) hot rolling and compression molding thermal bond pattern.
Fig. 5 ultrafiltration apparatus figure, wherein 1, high pure nitrogen 2, pressure-reducing valve 3, control valve 4, fluid reservoir 5, Pressure gauge 6, ultrafiltration cup 7, beaker 8, electronic balance.
Detailed description of the invention
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.Composite membrane brute force and filtering oily sewage test in the present invention:
(1) strength test instrument adopts YG065H type fabric strength instrument, and sample holder length is 200mm, draw speed 100mm/min, and 5 data surveyed by each sample. and test environment temperature is 20 DEG C, and humidity is 65%.
(2) the oil-polluted water test parameter of composite membrane is: adopt the cup type filter of Model8400 type to carry out dead-end filtration test, nano fibrous membrane being cut into respectively area is 41.8cm
2circle after put into ultrafiltration cup, the 0.1MPa that pressurizes after then passing into nitrogen 0.2MPa precompressed 0.5h tests, and the rotating speed of ultrafiltration cup rotor is 300r/min.
(3) the pure water flux test of composite membrane: pass into deionized water in fluid reservoir, the unit of account time is by the water volume of unit plane integrated membrane.
(4) the oil emulsion rejection test of composite membrane: preparation mass concentration is the oil emulsion solution of 1g/L, stirs 3min with agitator with the rotating speed of 20000r/min.The oil emulsion solution of preparation is put into fluid reservoir, and after nanofiber membrane filtration 1min, the liquid got stoste He filter out, tests the COD of two kinds of liquid with dichromate titration, calculates rejection R value.
Embodiment 1
1.4g polyacrylonitrile is dissolved in the DMF of 8.6g, stirs 8h to dissolving completely, obtaining polyacrylonitrile/DMF spinning solution that concentration is 14% (gram/gram).Select the syringe of 10ml, the syringe needle of 0.5mm internal diameter, extract polyacrylonitrile/DMF spinning solution, be fixed on micro-injection pump.Carry out electrospinning by electrostatic spinning apparatus as shown in Figure 1, parameter is: voltage 13KV, receiving range 20cm, and injection rate is 0.3ml/h, and environment temperature is 25 DEG C, and envionmental humidity is 45%.
Adopt ultrasonic bonds technique by after non-weaving cloth/electrostatic spinning nano fiber film/nonwoven cloth compound, prepare high-tenacity nano material, ultrasonic bonds parameter is operating air pressure 6Kg/cm
2, vibration frequency is 30KHz, and the rotating speed of output wheel is 0.2m/min.Table 1 is the non-weaving cloth/electrostatic spinning nano fiber film/nonwoven cloth composite membrane brute force and filtering oily sewage test data that obtain.
Embodiment 2
1.2g polyacrylonitrile is dissolved in the DMF of 8.8g, stirs 8h to dissolving completely, obtaining polyacrylonitrile/DMF spinning solution that concentration is 12% (gram/gram).Select the syringe of 10ml, the syringe needle of 0.5mm internal diameter, extract polyacrylonitrile/DMF spinning solution, be fixed on micro-injection pump.Carry out electrospinning by electrostatic spinning apparatus as shown in Figure 1, parameter is: voltage 12KV, receiving range 20cm, and injection rate is 0.6ml/h, and environment temperature is 25 DEG C, and envionmental humidity is 55%.
Hot calendering bonding technique is adopted by after non-weaving cloth/electrostatic spinning nano fiber film/nonwoven cloth compound, prepare high-tenacity nano material, hot calendering bonding parameter is the linear pressure between upper and lower hot roll is 0.2MPa, and upper and lower hot roll temperature is 100 DEG C, and hot rolling speed is 0.2m/min.Table 2 is the non-weaving cloth/electrostatic spinning nano fiber film/nonwoven cloth composite membrane brute force and filtering oily sewage test data that obtain.
Embodiment 3
1.4g Kynoar is dissolved in the DMF of 8.6g, stirs 8h to dissolving completely, obtaining Kynoar/DMF spinning solution that concentration is 14% (gram/gram).Select the syringe of 10ml, the syringe needle of 0.5mm internal diameter, extract Kynoar/DMF spinning solution, be fixed on micro-injection pump.Carry out electrospinning by electrostatic spinning apparatus as shown in Figure 1, parameter is: voltage 13KV, receiving range 20cm, and injection rate is 0.6ml/h, and environment temperature is 25 DEG C, and envionmental humidity is 45%.
Compression molding thermal bonding technology is adopted by after non-weaving cloth/electrostatic spinning nano fiber film/nonwoven cloth compound, prepare high-tenacity nano material, compression molding heat bonding parameter is the linear pressure between upper and lower flat board is 11MPa, and upper and lower hot roll temperature is 90 DEG C, and the processing time is 120s.Table 3 is the non-weaving cloth/electrostatic spinning nano fiber film/nonwoven cloth composite membrane brute force and filtering oily sewage test data that obtain.
Embodiment 4
0.7g Kynoar and 0.7g polyacrylonitrile are dissolved in the DMF of 8.6g, stir 8h to dissolving completely, obtaining Kynoar/DMF spinning solution that concentration is 14% (gram/gram).Select the syringe of 10ml, the syringe needle of 0.5mm internal diameter, extract Kynoar/DMF spinning solution, be fixed on micro-injection pump.Carry out electrospinning by electrostatic spinning apparatus as shown in Figure 1, parameter is: voltage 12KV, receiving range 15cm, and injection rate is 0.4ml/h, and environment temperature is 25 DEG C, and envionmental humidity is 40%.
Compression molding thermal bonding technology is adopted by after non-weaving cloth/electrostatic spinning nano fiber film/nonwoven cloth compound, prepare high-tenacity nano material, compression molding heat bonding parameter is the linear pressure between upper and lower flat board is 13MPa, and upper and lower hot roll temperature is 95 DEG C, and the processing time is 120s.Table 4 is the non-weaving cloth/electrostatic spinning nano fiber film/nonwoven cloth composite membrane brute force and filtering oily sewage test data that obtain.
Embodiment 5
Concentration 1.4g nylon 6 being dissolved in 8.6g is in the formic acid solution of 88%, stirring 8h to dissolving completely, obtaining Kynoar/DMF/DMA spinning solution that concentration is 14% (gram/gram).Select the syringe of 10ml, the syringe needle of 0.5mm internal diameter, extract Kynoar/DMF spinning solution, be fixed on micro-injection pump.Carry out electrospinning by electrostatic spinning apparatus as shown in Figure 1, parameter is: voltage 12KV, receiving range 20cm, and injection rate is 0.8ml/h, and environment temperature is 25 DEG C, and envionmental humidity is 55%.
Hot calendering bonding technique is adopted by after non-weaving cloth/electrostatic spinning nano fiber film/nonwoven cloth compound, prepare high-tenacity nano material, hot calendering bonding parameter is the linear pressure between upper and lower hot roll is 0.3MPa, and upper and lower hot roll temperature is 102 DEG C, and hot rolling speed is 0.3m/min.Table 5 is the non-weaving cloth/electrostatic spinning nano fiber film/nonwoven cloth composite membrane brute force and filtering oily sewage test data that obtain.
Embodiment 6
2g polystyrene is dissolved in the DMF of 6g and the oxolane of 2g, stirs 8h to dissolving completely, obtaining Kynoar/DMF/oxolane spinning solution that concentration is 20% (gram/gram).Select the syringe of 10ml, the syringe needle of 0.5mm internal diameter, extract Kynoar/DMF spinning solution, be fixed on micro-injection pump.Carry out electrospinning by electrostatic spinning apparatus as shown in Figure 1, parameter is: voltage 13KV, receiving range 15cm, and injection rate is 0.3ml/h, and environment temperature is 25 DEG C, and envionmental humidity is 45%.
Adopt ultrasonic bonds technique by after non-weaving cloth/electrostatic spinning nano fiber film/nonwoven cloth compound, prepare high-tenacity nano material, ultrasonic bonds parameter is operating air pressure 7Kg/cm
2, vibration frequency is 30KHz, and the rotating speed of output wheel is 0.3m/min.Table 6 is the non-weaving cloth/electrostatic spinning nano fiber film/nonwoven cloth composite membrane brute force and filtering oily sewage test data that obtain.
Embodiment 7
By broad to 1g nylon, 0.5g polystyrene and 0.5g polyacrylonitrile in the N of 6g, in the oxolane of dinethylformamide and 2g, stirring 8h to dissolving completely, obtaining Kynoar/DMF/oxolane spinning solution that concentration is 20% (gram/gram).Select the syringe of 10ml, the syringe needle of 0.5mm internal diameter, extract Kynoar/DMF spinning solution, be fixed on micro-injection pump.Carry out electrospinning by electrostatic spinning apparatus as shown in Figure 1, parameter is: voltage 14KV, receiving range 18cm, and injection rate is 0.5ml/h, and environment temperature is 25 DEG C, and envionmental humidity is 55%.
Hot calendering bonding technique is adopted by after non-weaving cloth/electrostatic spinning nano fiber film/nonwoven cloth compound, prepare high-tenacity nano material, hot calendering bonding parameter is the linear pressure between upper and lower hot roll is 0.4MPa, and upper and lower hot roll temperature is 95 DEG C, and hot rolling speed is 0.2m/min.Table 7 is the non-weaving cloth/electrostatic spinning nano fiber film/nonwoven cloth composite membrane strength test data obtained.
Table 1
Note: sample 1,2 is the ultrasonic bonds non-weaving cloth/electrostatic spinning nano fiber film/nonwoven cloth composite membrane adopting embodiment 1 technique to prepare.
Table 2
Note: sample 1,2 is the hot calendering bonding non-weaving cloth/electrostatic spinning nano fiber film/nonwoven cloth composite membrane adopting embodiment 2 technique to prepare.
Table 3
Note: sample 1,2 is the compression molding thermal non-woven fabric/electrostatic spinning nano fiber film/nonwoven cloth composite membrane adopting embodiment 3 technique to prepare.
Table 4
Note: sample 1,2 is the compression molding thermal non-woven fabric/electrostatic spinning nano fiber film/nonwoven cloth composite membrane adopting embodiment 4 technique to prepare.
Table 5
Note: sample 1,2 is the hot calendering bonding non-weaving cloth/electrostatic spinning nano fiber film/nonwoven cloth composite membrane adopting embodiment 5 technique to prepare.
Table 6
Note: sample 1,2 is the ultrasonic bonds non-weaving cloth/electrostatic spinning nano fiber film/nonwoven cloth composite membrane adopting embodiment 6 technique to prepare.
Table 7
Note: sample 1,2 is the hot calendering bonding non-weaving cloth/electrostatic spinning nano fiber film/nonwoven cloth composite membrane adopting embodiment 7 technique to prepare.
Claims (10)
1. a preparation method for nanofiber composite hyperfiltration membrane, comprising:
(1) high molecular polymer is dissolved in solvent, stirs, obtain spinning solution, then carry out electrostatic spinning, obtain nano fibrous membrane;
(2) by above-mentioned nano fibrous membrane and non-weaving cloth compound, non-weaving cloth/nanometer film/non-weaving cloth composite membrane is obtained;
(3) above-mentioned non-weaving cloth/nanometer film/non-weaving cloth composite membrane is carried out adhesion process, obtain nanofiber composite hyperfiltration membrane.
2. the preparation method of a kind of nanofiber composite hyperfiltration membrane according to claim 1, is characterized in that: in described step (1), high molecular polymer is one or more in polypropylene, polyarylate, polyaniline, polycaprolactone, polyurethane, polysulfones, polyacrylonitrile, poly-aspartate, polyvinyl chloride, polyamide, polystyrene, shitosan, Kynoar, nylon 6; Solvent is one or more in water, dimethyl sulfoxide (DMSO), formic acid, ethanol, methyl alcohol, acetic acid, DMF, DMA, trifluoroacetic acid, oxolane, acetone, carrene, chloroform, hexafluoroisopropanol.
3. the preparation method of a kind of nanofiber composite hyperfiltration membrane according to claim 1, is characterized in that: in described step (1), the mass percentage concentration of spinning solution is 6%-25%.
4. the preparation method of a kind of nanofiber composite hyperfiltration membrane according to claim 1, it is characterized in that: in described step (1), the technique of electrostatic spinning is: voltage is 1 ~ 50KV, syringe needle is 0.1 ~ 2m to reception template distance, spinnerette diameters is 1 μm ~ 2mm, spinning speed is 0.1 ~ 20mL/h, the spinning time is 8 ~ 10h, and environment temperature is 20 ~ 60 DEG C, and envionmental humidity is 20 ~ 80%.
5. the preparation method of a kind of nanofiber composite hyperfiltration membrane according to claim 1, is characterized in that: non-weaving cloth is melt-blown, spunbond, acupuncture or hydro-entangled non-woven fabric in described step (2).
6. the preparation method of a kind of nanofiber composite hyperfiltration membrane according to claim 1, is characterized in that: in described step (3), adhesion process is the one in ultrasonic bonds, hot calendering bonding, compression molding heat bonding.
7. the preparation method of a kind of nanofiber composite hyperfiltration membrane according to claim 6, is characterized in that: the parameter of described ultrasonic bonds is: operating air pressure 5 ~ 7Kg/cm
2, vibration frequency is 20 ~ 35KHz, and the rotating speed of output wheel is 0.1 ~ 2m/min.
8. the preparation method of a kind of nanofiber composite hyperfiltration membrane according to claim 6, it is characterized in that: described hot calendering bonding parameter is: the linear pressure up and down between hot roll is 0.2 ~ 1MPa, upper and lower hot roll temperature is 90 ~ 105 DEG C, and hot rolling speed is 0.1 ~ 0.5m/min.
9. the preparation method of a kind of nanofiber composite hyperfiltration membrane according to claim 6, it is characterized in that: described compression molding heat bonding parameter is: the linear pressure up and down between flat board is 9 ~ 18MPa, upper and lower hot roll temperature is 90 ~ 105 DEG C, and the processing time is 120s.
10. the preparation method of a kind of nanofiber composite hyperfiltration membrane according to claim 1, it is characterized in that: the powerful excursion of described nanofiber composite hyperfiltration membrane is between 50N ~ 60N, elongation at break, between 50% ~ 75%, is 60-70 times of pure nanometer film brute force.
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| CN106237717A (en) * | 2016-08-30 | 2016-12-21 | 东华大学 | A kind of efficient low-resistance electrostatic spinning nano fiber air filting material and mass preparation method |
| CN106541683A (en) * | 2016-11-01 | 2017-03-29 | 东莞巨微新材料科技有限公司 | A kind of preparation method of the multilayered structure nano-fiber composite film filtered for particulate in air |
| CN108031309A (en) * | 2017-12-22 | 2018-05-15 | 中国海诚工程科技股份有限公司 | A kind of MBR plate membranes of composite electrostatic spinning filter layer and preparation method thereof |
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| CN109012228A (en) * | 2018-08-23 | 2018-12-18 | 安徽实力环保科技有限公司 | A method of sewage is handled with titania glass web-Static Spinning composite nano-fiber membrane |
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| CN106237717A (en) * | 2016-08-30 | 2016-12-21 | 东华大学 | A kind of efficient low-resistance electrostatic spinning nano fiber air filting material and mass preparation method |
| US20210361831A1 (en) * | 2016-10-28 | 2021-11-25 | Bioengineering Laboratories S.r.l | Hybrid scaffold suitable for regenerating animal tissues and process for producing the scaffold |
| CN106541683A (en) * | 2016-11-01 | 2017-03-29 | 东莞巨微新材料科技有限公司 | A kind of preparation method of the multilayered structure nano-fiber composite film filtered for particulate in air |
| CN108950700A (en) * | 2017-05-19 | 2018-12-07 | 南京理工大学 | A kind of electrostatic spinning apparatus and method preparing fluffy state nanofiber |
| CN108031309A (en) * | 2017-12-22 | 2018-05-15 | 中国海诚工程科技股份有限公司 | A kind of MBR plate membranes of composite electrostatic spinning filter layer and preparation method thereof |
| WO2020033564A1 (en) * | 2018-08-10 | 2020-02-13 | Bha Altair, Llc | Filtration media with extended surface area |
| US11925891B2 (en) | 2018-08-10 | 2024-03-12 | Parker-Hannifin Corporation | Filtration media with extended surface area |
| CN109012228A (en) * | 2018-08-23 | 2018-12-18 | 安徽实力环保科技有限公司 | A method of sewage is handled with titania glass web-Static Spinning composite nano-fiber membrane |
| CN111686593A (en) * | 2019-03-13 | 2020-09-22 | 西陇科学股份有限公司 | Novel adjustable and controllable ultrathin organic polymer composite membrane and preparation method thereof |
| CN110478980A (en) * | 2019-06-28 | 2019-11-22 | 昆山同日工业自动化有限公司 | A kind of nanofiber filtration material and preparation method thereof |
| CN112316494A (en) * | 2020-10-27 | 2021-02-05 | 洪月恒 | Preparation method of separation membrane applied to separation of oil-water emulsion |
| CN112588133A (en) * | 2020-11-22 | 2021-04-02 | 山东优膜膜科技有限公司 | Alkali-resistant ultrafiltration membrane and preparation method thereof |
| CN113584893A (en) * | 2021-08-03 | 2021-11-02 | 上海工程技术大学 | Nano-fiber medical heat-preservation protective clothing fabric and preparation method thereof |
| CN114541043A (en) * | 2022-02-25 | 2022-05-27 | 青岛科技大学 | Preparation method of real-time vulcanized elastomer fiber membrane |
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