CN105797602A - Preparation method for composite nanofiltration membrane with high hydrophilicity, high flux and high separation performance - Google Patents
Preparation method for composite nanofiltration membrane with high hydrophilicity, high flux and high separation performance Download PDFInfo
- Publication number
- CN105797602A CN105797602A CN201410841789.3A CN201410841789A CN105797602A CN 105797602 A CN105797602 A CN 105797602A CN 201410841789 A CN201410841789 A CN 201410841789A CN 105797602 A CN105797602 A CN 105797602A
- Authority
- CN
- China
- Prior art keywords
- membrane
- hydrophilic
- preparation
- mass percentage
- percentage composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a preparation method for a composite nanofiltration membrane with high hydrophilicity, high flux and high separation performance. The preparation method comprises the following steps: step S10, dissolving a polysulfone high polymer material with a polar organic solvent and adding a hydrophilic pore-forming agent to prepare a membrane casting liquid; step S20, subjecting the membrane casting liquid prepared in the step S10 to vacuum defoaming, then uniformly coating a non-woven fabric supporting layer with the membrane casting liquid and carrying out coagulation bath treatment so as to form a substrate membrane with a certain pore size and certain hydrophilicity; and step S30, soaking the substrate membrane prepared in the step S20 in a water phase, carrying out full infiltration and draining successively, then soaking the substrate membrane in an organic phase, removing an organic solvent on the surface of the membrane after a reaction and successively carrying out treatment and drying so as to prepare the composite nanofiltration membrane. The nanofiltration membrane prepared by using the method has the advantages of high flux, good interception performance and good hydrophilicity.
Description
Technical field
The present invention relates to the preparation method of a kind of composite nanometer filtering film and manufacturing process, the preparation method particularly relating to a kind of high-hydrophilic high flux high separability energy composite nanometer filtering film.
Background technology
Nanofiltration (NF) is a kind of new membrane isolation technics between reverse osmosis and ultrafiltration that the eighties in 20th century, Later development got up, and early stage is called " low pressure reverse osmosis " or " loose reverse osmosis ".Nanofiltration is the demand in order to adapt to industry softening water and a kind of novel pressure-driven membrane process reducing cost and growing up.The molecular cut off of NF membrane is between 200-2000, and membrane aperture is about about 1nm, is suitable for separating the dissolved constituent that size is about lnm, therefore is called " nanofiltration ".Nanofiltration membrane separation carries out at normal temperatures, without phase transformation, without chemical reaction, do not destroy biological activity, can effectively retain bivalence and high valence ion, the molecular weight organic molecule higher than 200, and make major part inorganic monovalent salt pass through, separable similar amino acid and protein, realize high score in the separation of amount and low-molecular-weight organic matter, and cost is also lower than traditional handicraft.Thus be widely used in ultra-pure water prepare, food, chemical industry, medicine, biochemistry, environmental protection, the various concentrations in the field such as metallurgy and separation process.
The preparation method of NF membrane has multiple, and main has: L-S phase inversion, blending method, charged method, Ultraviolet irradiation method and composite algorithm etc..
Chinese patent (CN102423643A) utilizes the interface polycondensation between sericin aqueous solution and the organic solution containing aromatic polycarboxylic acyl chlorides to prepare a kind of high throughput anion composite nanometer filtering film;Chinese patent (CN1636626A) prepares nanofiltration film by the interfacial polymerization of terminated polyamidoamines with polyphenyl three formyl chloride organic solution, and this film is water flux 38.3~56.8L/m under 0.6MPa2.h between, to the rejection of 1000mg/L sodium chloride between 41.8~53.8%;Chinese patent (CN102247771A) is respectively to adopt the method for ultraviolet irradiation substep grafting to be prepared for a kind of nanofiltration membrane with negative electric charge containing sulfonic vinyl monomer and the vinyl monomer containing hydroxyl or carboxyl for monomer, and this film flux under 0.4MPa is 28.3~36.6L/m2.h, the rejection to sodium sulfate is 94.8~97.9%, and the rejection to sodium chloride is 60.2~65.3%.
Composite algorithm is that to adopt at present be also at most the method for maximally effective preparation NF membrane, and the method is the ultrathin functional layer that compound one layer has nano aperture on porous counterdie, and counterdie is as supporting layer, and what determine film feature and separating property is ultrathin functional layer.The advantage of composite membrane is can to choose different materials to produce counterdie and composite membrane, makes their performance respectively reach optimization.And composite algorithm median surface polymerization a kind of method preparing NF membrane that is most important of which, current industrialized NF membrane is mainly through interfacial polymerization preparation.Interfacial polymerization is the monomer significantly high by two kinds of reactivities, two mutual exclusive interfaces, polyreaction occurs, thus forming thin layer on many empty supporters.
Being learnt by above content, NF membrane prepared by above several method has greatly improved space in rejection especially water flux.
Summary of the invention
It is an object of the invention to provide a kind of high-hydrophilic high flux and the preparation method of high cutoff performance NF membrane, the nanometer filtering film water flux of preparation is high, cutoff performance is good, and film hydrophilicity is good.
The preparation method of the high-hydrophilic high flux high separability energy composite nanometer filtering film of the present invention, comprises the following steps:
Step S10, polysulfones macromolecular material polar organic solvent is dissolved, and be configured to casting solution after adding hydrophilic porogen;
Step S20, by step S10 prepare casting solution after vacuum defoamation, even application on non-woven fabrics supporting layer, be then passed through coagulating bath process after formed there is certain pore size and certain hydrophilic counterdie;
Step S30, the counterdie prepared in step S20 is immersed in aqueous phase, fully drains after infiltration, be then immersed in organic facies again, after reaction, the organic solvent on film surface removed, after post processing, drying, make composite nanometer filtering film.
In the present invention, in order to enable the casting solution prepared in step S10 to be better combined with non-woven fabrics supporting layer, flux is higher, cutoff performance is better in formation, and the better NF membrane of film hydrophilic, in step S10, in casting solution, the weight/mass percentage composition of polysulfones macromolecular material is 15~22%, it is preferable that 17~20%;The weight/mass percentage composition of hydrophilic porogen is 1~3%.
Preferably, in step S10: described polysulfones macromolecular material is the one or more kinds of mixture in a series of high polymers of common bisphenol-a polysulfone, polyether sulfone, Polyphenylene Sulfone and their different sulfonation degree;
And/or, described polar organic solvent is the mixture of more than a kind of or two of which in DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide;When polar organic solvent adopt described herein several time, it is possible to make polysulfones macromolecular material better dissolve.
And/or, described hydrophilic porogen is polyvinylpyrrolidone, Polyethylene Glycol, hydrophilic titanium dioxide or wherein both above mixture;So that the NF membrane hydrophilic prepared and pore size are more suitable.
Preferably, in step S20, " it is then passed through coagulating bath to process " particularly as follows: put into and coagulating bath being treated, gel completes, then soak 3~5 hours and make the polar organic solvent of remnants diffuse out, described coagulating bath is the mixture of the organic solvent described in pure water or step S30 and water, in order to make gel solidify faster.
Preferably, for the NF membrane obtaining flux height, cutoff performance is good, " certain pore size " described in step S20 is aperture 10~50nm, more preferably 10~30nm;
And/or, in step S20, in order to obtain the better NF membrane of hydrophilicity, it is preferable that the contact angle that described " certain hydrophilic " refers to ultrafilter membrane is 10~40 °, more preferably 5~30 °.
Preferably, in step S30, described aqueous phase is added with piperazine, sodium carbonate, camphorsulfonic acid, triethylamine and dodecylbenzene sodium sulfonate, sodium carbonate function as acid absorbent, promote the carrying out of reaction, the effect of camphorsulfonic acid and triethylamine is the acid-base value in auxiliary adjustment aqueous phase, dodecylbenzene sodium sulfonate act as surfactant, promote reaction monomers piperazine at the uniform adsorption on polysulfones counterdie surface, reduce the counterdie time of staying in aqueous phase besides, be more conducive to industrialization.
Preferably, in the aqueous phase in step S30, the weight/mass percentage composition of described piperazine is 0.5~3%, more preferably 0.7~1.5%;Carrying out to make reaction be more easy to, the weight/mass percentage composition of sodium carbonate is 0.1~1%, more preferably 0.2~0.6%;In aqueous phase, the content of camphorsulfonic acid and triethylamine is that to make the pH value of aqueous phase be 10~11;The weight/mass percentage composition of dodecylbenzene sodium sulfonate is 0.05%~0.2%, within the scope of this, it is possible to promotes reaction monomers piperazine at the uniform adsorption on polysulfones counterdie surface better, reduces the counterdie time of staying in aqueous phase.
In the present invention, the organic facies in step S30 is the mixture that pyromellitic trimethylsilyl chloride is dissolved in that organic solvent prepares;
In order to make pyromellitic trimethylsilyl chloride better be dissolved in organic solvent, described organic solvent is preferably normal hexane, hexamethylene or IsoparG (isoparaffin, lower same)
In order to make reaction have suitable speed and higher conversion ratio, in described organic facies, the weight/mass percentage composition of pyromellitic trimethylsilyl chloride is preferably 0.2~0.8%, more preferably 0.3~0.6%.
In the present invention, in step S30, described " post processing " is particularly as follows: after carrying out pickling or alkali cleaning by ultrafilter membrane, to promote the hydrolysis of acid chloride groups and to wash excessive amine substance, and then immersion treatment in water;Described pickling use the strong acid that acid solution preferred mass percentage composition is 0.2~0.7% or weight/mass percentage composition 3~8% weak organic acid;The aqueous slkali that described alkali cleaning uses is preferably the sodium carbonate liquor that weight/mass percentage composition is 0.3~0.8%.
Preferably, in step S30, counterdie infiltrates 15~25 seconds in aqueous phase, reacts 15~20 seconds, in order to fully react in organic facies;And/or, in step S30, described drying is for being dry 3~5 minutes under 40~60 DEG C of temperature conditions in temperature, and so while ensureing that film is dried, the aperture that can be effectively protected counterdie is not destroyed.
In the present invention, hydrophilic contact angle is weighed, contact angle contact angle instrument measures, there is scanning electron microscope test in ultrafiltration counterdie aperture, the method of testing of NF membrane performance is: when 0.5MPa, temperature 25 DEG C, pH value are 6.5~7.5, the magnesium sulfate of 500ppm is retained test, and flux is 70~150L/m2.h, removal efficiency is 95~98.5%;When 0.5MPa, temperature 25 DEG C, pH value are between 6.5~7.5, the sodium chloride of 500ppm being retained test, flux is 75~170L/m2.h, removal efficiency is 40~60%.
Can be seen that through above-mentioned data, compared to the prior art, the advantage that NF membrane prepared by this method has good hydrophilic property, and NF membrane hydrophilic is more good, the resistance tocrocking of NF membrane is more strong, and NF membrane pure water flux and rejection that again prepared by the method all have significantly high level, and send bright required various raw materials commercialization all elsewhere, process control is relatively easy, is beneficial to industrialization steady production.
Detailed description of the invention
Below in conjunction with embodiment, technical scheme is further elaborated.
Embodiment 1
(1) configuration of casting solution: (manufacturer is: Su Wei Shanghai company limited to take polysulfones, model is: P3500, lower same) 180g, polyvinylpyrrolidone (manufacturer is: Beijing perseverance becomes prosperous Science and Technology Ltd., and model is K30, lower same) 15g, N, dinethylformamide (DMF) 805g, is made into 1kg casting solution, is gradually heating to 60 DEG C of stirring and dissolving 4~6h final vacuum deaerations;
(2) preparation of polysulfones counterdie: it is on 100 μm of polyester non-woven fabric supporting layers that casting solution scraper is coated in thickness uniformly, then put into rapidly in 15 DEG C of pure water, cross 30s after gel completes, film bubble is soaked 3 hours in pure water in case the solvent diffuse of remnants out, standby;
(3) configuration of aqueous phase: take piperazine 10g, natrium carbonicum calcinatum 2g, camphorsulfonic acid 15g, triethylamine 25g, dodecylbenzene sodium sulfonate 0.5g, pure water 947.5g, being made into aqueous phase temperature is 25 DEG C;
(4) configuration of organic facies: take pyromellitic trimethylsilyl chloride 5g, hexamethylene 995g, being made into organic solution temperature is 25 DEG C;
(5) preparation of NF membrane: the polysulfones counterdie obtained in (2) is immersed in the aqueous phase in (3) 20s, then the liquid on surface is drained after being taken out by counterdie, it is immersed in (4) afterwards again in organic facies of configuration to take out after 15s and obtains NF membrane, then pass through blower fan blowing and remove organic solvent;
(6) post processing of NF membrane: after NF membrane is processed 5min with the aqueous citric acid solution that 60 DEG C of weight/mass percentage composition are 5% again with temperature to be 25 DEG C of weight/mass percentage composition be 0.4% sodium bicarbonate solution process 2min, then after cleaning 3min with the pure water of 50 DEG C, NF membrane is immersed in weight/mass percentage composition to be 8% temperature be 2min in the glycerine water solution of 25 DEG C, then take out and dry 4 minutes under 50 DEG C of temperature conditions;
(7) test of polysulfones counterdie: after polysulfones counterdie lyophilization, test its contact angle with contact angle instrument, with its surface apertures of scanning electron microscope test;
(8) test of NF membrane: the method for testing of NF membrane performance is: when 0.5MPa, temperature 25 DEG C, pH value are 6.5, the magnesium sulfate of 500ppm and the sodium chloride of 500ppm are retained test respectively, performance is in Table 1, and the NF membrane of the present embodiment can be infiltrated completely, the advantage with good hydrophilic property.
Embodiment 2
(1) configuration of casting solution: (manufacturer is: Su Wei Shanghai company limited to take polyether sulfone, model is: model is 3000P, lower same) 190g, polyvinylpyrrolidone 10g, N, N-dimethyl acetylamide (DMAc) 800g, is made into 1kg casting solution, is gradually heating to 60 DEG C of stirring and dissolving 4-6h final vacuum deaerations;
(2) preparation of polyether sulfone counterdie: it is on 100 μm of polyester non-woven fabric supporting layers that casting solution scraper is coated in thickness uniformly, then put into rapidly in 15 DEG C of pure water, cross 30s after gel completes, film bubble is soaked 5 hours in pure water in case the solvent diffuse of remnants out, standby;
(3) configuration of aqueous phase: take piperazine 13g, natrium carbonicum calcinatum 2g, camphorsulfonic acid 15g, triethylamine 25g, dodecylbenzene sodium sulfonate 1.5g, pure water 943.5g, being made into aqueous phase temperature is 25 DEG C;
(4) configuration of organic facies: take pyromellitic trimethylsilyl chloride 4g, normal hexane 996g, being made into organic solution temperature is 25 DEG C;
(5) preparation of NF membrane: the polyether sulfone counterdie obtained in (2) is immersed in the aqueous phase in (3) 20s, then the liquid on surface is drained after being taken out by counterdie, it is immersed in (4) afterwards again in organic facies of configuration to take out after 15s and obtains NF membrane, then pass through blower fan blowing and remove organic solvent;
(6) post processing of NF membrane: after NF membrane is processed 5min with the aqueous hydrochloric acid solution that 60 DEG C of weight/mass percentage composition are 0.3% again with temperature to be 25 DEG C of weight/mass percentage composition be 0.3% sodium bicarbonate solution process 2min, then after cleaning 3min with the pure water of 50 DEG C, NF membrane is immersed in weight/mass percentage composition to be 8% temperature be 2min in the glycerine water solution of 25 DEG C, then take out and dry under 50 DEG C of temperature conditions;
(7) test of polyether sulfone counterdie: after polyether sulfone counterdie lyophilization, test its contact angle with contact angle instrument, with its surface apertures of scanning electron microscope test;
(8) test of NF membrane: the method for testing of NF membrane performance is: when 0.5MPa, temperature 25 DEG C, pH value are 6.5, the magnesium sulfate of 500ppm and the sodium chloride of 500ppm are retained test respectively, performance is in Table 1, and the NF membrane of the present embodiment can be infiltrated completely, the advantage with good hydrophilic property.
Embodiment 3
(1) configuration of casting solution: take polysulfones 180g, SPSF (Hangzhou Xiaoshan Jiang Cheng Chemical Co., Ltd., sulfonation degree 10%) 15g, N, dinethylformamide (DMF) 805g, is made into 1kg casting solution, is gradually heating to 60 DEG C of stirring and dissolving 4-6h final vacuum deaerations;
(2) preparation of polysulfones counterdie: it is on 100 μm of polyester non-woven fabric supporting layers that casting solution scraper is coated in thickness uniformly, then put into rapidly in 10 DEG C of pure water, cross 30s after gel completes, film bubble is soaked 4 hours in pure water in case the solvent diffuse of remnants out, standby;
(3) configuration of aqueous phase: take piperazine 10g, natrium carbonicum calcinatum 2g, camphorsulfonic acid 15g, triethylamine 25g, dodecylbenzene sodium sulfonate 0.5g, pure water 947.5g, being made into aqueous phase temperature is 25 DEG C;
(4) configuration of organic facies: take pyromellitic trimethylsilyl chloride 5g, hexamethylene 995g, being made into organic solution temperature is 25 DEG C;
(5) preparation of NF membrane: the polysulfones counterdie obtained in (2) is immersed in the aqueous phase in (3) 20s, then the liquid on surface is drained after being taken out by counterdie, it is immersed in (4) afterwards again in organic facies of configuration to take out after 15s and obtains NF membrane, then pass through blower fan blowing and remove organic solvent;
(6) post processing of NF membrane: after NF membrane is processed 5min with the aqueous citric acid solution that 60 DEG C of weight/mass percentage composition are 7% again with temperature to be 25 DEG C of weight/mass percentage composition be 0.5% sodium bicarbonate solution process 2min, then after cleaning 3min with the pure water of 50 DEG C, NF membrane is immersed in weight/mass percentage composition to be 8% temperature be 2min in the glycerine water solution of 25 DEG C, then take out and dry 5 minutes under 40 DEG C of temperature conditions;
(7) test of polysulfones counterdie: after polysulfones counterdie lyophilization, test its contact angle with contact angle instrument, with its surface apertures of scanning electron microscope test;
(8) test of NF membrane: the method for testing of NF membrane performance is: when 0.5MPa, temperature 25 DEG C, pH value are 6.5, the magnesium sulfate of 500ppm and the sodium chloride of 500ppm are retained test respectively, performance is in Table 1, and the NF membrane of the present embodiment can be infiltrated completely, the advantage with good hydrophilic property.
Embodiment 4
(1) configuration of casting solution: take polysulfones 180g, (manufacturer is Polyethylene Glycol: Beijing perseverance becomes prosperous Science and Technology Ltd., molecular weight 10k) 20g, hydrophilic titanium dioxide 5g, dimethyl sulfoxide (DMSO) 795g, it is made into 1kg casting solution, is gradually heating to 60 DEG C of stirring and dissolving 4~6h final vacuum deaerations;
(2) preparation of polysulfones counterdie: it is on 100 μm of polyester non-woven fabric supporting layers that casting solution scraper is coated in thickness uniformly, then put into rapidly in 12 DEG C of pure water, cross 30s after gel completes, film bubble is soaked 4 hours in pure water in case the solvent diffuse of remnants out, standby;
(3) configuration of aqueous phase: take piperazine 7g, natrium carbonicum calcinatum 2g, camphorsulfonic acid 15g, triethylamine 25g, dodecylbenzene sodium sulfonate 1.0g, pure water 950g, being made into aqueous phase temperature is 20 DEG C;
(4) configuration of organic facies: take pyromellitic trimethylsilyl chloride 3.5g, normal hexane 996.5g, being made into organic solution temperature is 25 DEG C;
(5) preparation of NF membrane: the polysulfones counterdie obtained in (2) is immersed in the aqueous phase in (3) 15s, then the liquid on surface is drained after being taken out by counterdie, it is immersed in (4) afterwards again in organic facies of configuration to take out after 10s and obtains NF membrane, then pass through blower fan blowing and remove organic solvent;
(6) post processing of NF membrane: after NF membrane is processed 5min with the aqueous hydrochloric acid solution that 60 DEG C of weight/mass percentage composition are 0.2% again with temperature to be 40 DEG C of weight/mass percentage composition be 0.3% sodium bicarbonate solution process 2min, then after cleaning 3min with the pure water of 50 DEG C, NF membrane is immersed in weight/mass percentage composition to be 8% temperature be 2min in the glycerine water solution of 25 DEG C, then take out and dry 4 minutes under 50 DEG C of temperature conditions;
(7) test of polysulfones counterdie: after polysulfones counterdie lyophilization, test its contact angle with contact angle instrument, with its surface apertures of scanning electron microscope test;
(8) test of NF membrane: the method for testing of NF membrane performance is: when 0.5MPa, temperature 25 DEG C, pH value are 6.5, the magnesium sulfate of 500ppm and the sodium chloride of 500ppm are retained test respectively, performance is in Table 1, and the NF membrane of the present embodiment can be infiltrated completely, the advantage with good hydrophilic property.
Embodiment 5
(1) configuration of casting solution: take polyether sulfone 200g, (manufacturer is Polyethylene Glycol: Beijing perseverance becomes prosperous Science and Technology Ltd., molecular weight 10k) 10g, N, N-dimethyl acetylamide (DMAc) 790g, it is made into 1kg casting solution, is gradually heating to 60 DEG C of stirring and dissolving 4~6h final vacuum deaerations;
(2) preparation of polyether sulfone counterdie: it is on 100 μm of polyester non-woven fabric supporting layers that casting solution scraper is coated in thickness uniformly, then put into rapidly in 10 DEG C of pure water, cross 30s after gel completes, film bubble is soaked 4 hours in pure water in case the solvent diffuse of remnants out, standby;
(3) configuration of aqueous phase: take piperazine 13g, natrium carbonicum calcinatum 2g, camphorsulfonic acid 15g, triethylamine 25g, dodecylbenzene sodium sulfonate 0.5g, pure water 944.5g, being made into aqueous phase temperature is 25 DEG C;
(4) configuration of organic facies: take pyromellitic trimethylsilyl chloride 4g, Isopar996g, being made into organic solution temperature is 25 DEG C;
(5) preparation of NF membrane: the polyether sulfone counterdie obtained in (2) is immersed in the aqueous phase in (3) 25s, then the liquid on surface is drained after being taken out by counterdie, it is immersed in (4) afterwards again in organic facies of configuration to take out after 20s and obtains NF membrane, then pass through blower fan blowing and remove organic solvent;
(6) post processing of NF membrane: NF membrane first dries 4min with 80 DEG C, the sodium bicarbonate solution being then immersed in temperature to be 25 DEG C of weight/mass percentage composition be 0.6% processes 2min, then after cleaning 3min with the pure water of 50 DEG C, NF membrane is immersed in weight/mass percentage composition to be 8% temperature be 2min in the glycerine water solution of 25 DEG C, then take out and dry 4 minutes under 50 DEG C of temperature conditions;
(7) test of polyether sulfone counterdie: after polyether sulfone counterdie lyophilization, test its contact angle with contact angle instrument, with its surface apertures of scanning electron microscope test;
(8) test of NF membrane: the method for testing of NF membrane performance is: when 0.5MPa, temperature 25 DEG C, pH value are 6.5, the magnesium sulfate of 500ppm and the sodium chloride of 500ppm are retained test respectively, performance is in Table 1, and the NF membrane of the present embodiment can be infiltrated completely, the advantage with good hydrophilic property.
Embodiment 6
(1) configuration of casting solution: (manufacturer is: Su Wei Shanghai company limited to take Polyphenylene Sulfone, weight average molecular weight 60,000) 190g, polyvinylpyrrolidone 10g, N-Methyl pyrrolidone (MNP) 800g, it is made into 1kg casting solution, is gradually heating to 60 DEG C of stirring and dissolving 4~6h final vacuum deaerations;
(2) preparation of Polyphenylene Sulfone counterdie: it is on 100 μm of polyester non-woven fabric supporting layers that casting solution scraper is coated in thickness uniformly, then put into rapidly in 13 DEG C of pure water, cross 30s after gel completes, film bubble is soaked in pure water in case the solvent diffuse of remnants out, standby;
(3) configuration of aqueous phase: take piperazine 13g, natrium carbonicum calcinatum 2g, camphorsulfonic acid 15g, triethylamine 25g, dodecylbenzene sodium sulfonate 0.5g, pure water 944.5g, being made into aqueous phase temperature is 25 DEG C;
(4) configuration of organic facies: take pyromellitic trimethylsilyl chloride 4g, normal hexane 996g, being made into organic solution temperature is 25 DEG C;
(5) preparation of NF membrane: the Polyphenylene Sulfone counterdie obtained in (2) is immersed in the aqueous phase in (3) 20s, then the liquid on surface is drained after being taken out by counterdie, it is immersed in (4) afterwards again in organic facies of configuration to take out after 15s and obtains NF membrane, then pass through blower fan blowing and remove organic solvent;
(6) post processing of NF membrane: NF membrane is processed with the aqueous citric acid solution that 60 DEG C of volumn concentrations are 7% and after then 5min cleans 5min with the pure water of 50 DEG C, NF membrane is immersed in weight/mass percentage composition to be 8% temperature be 2min in the glycerine water solution of 25 DEG C, then take out drying 3 minutes under 60 DEG C of temperature conditions;
(7) test of Polyphenylene Sulfone counterdie: after Polyphenylene Sulfone counterdie lyophilization, test its contact angle with contact angle instrument, with its surface apertures of scanning electron microscope test;
(8) test of NF membrane: the method for testing of NF membrane performance is: when 0.5MPa, temperature 25 DEG C, pH value are 6.5, the magnesium sulfate of 500ppm and the sodium chloride of 500ppm are retained test respectively, performance is in Table 1, and the NF membrane of the present embodiment can be infiltrated completely, the advantage with good hydrophilic property.
Embodiment 7
(1) configuration of casting solution: take polysulfones 180g, (manufacturer is Polyethylene Glycol: Beijing perseverance becomes prosperous Science and Technology Ltd., molecular weight 5k) 30g, N, dinethylformamide (DMF) 790g, it is made into 1kg casting solution, is gradually heating to 60 DEG C of stirring and dissolving 4~6h final vacuum deaerations;
(2) preparation of polysulfones counterdie: it is on 100 μm of polyester non-woven fabric supporting layers that casting solution scraper is coated in thickness uniformly, then put into rapidly in 15 DEG C of pure water, cross 30s after gel completes, film bubble is soaked 4 hours in pure water in case the solvent diffuse of remnants out, standby;
(3) configuration of aqueous phase: take piperazine 15g, natrium carbonicum calcinatum 3g, camphorsulfonic acid 15g, triethylamine 25g, dodecylbenzene sodium sulfonate 0.5g, pure water 941.5g, being made into aqueous phase temperature is 25 DEG C;
(4) configuration of organic facies: take pyromellitic trimethylsilyl chloride 3.5g, Isopar (Exxon Mobil Corporation, IsoparG) 996.5g, being made into organic solution temperature is 25 DEG C;
(5) preparation of NF membrane: the polysulfones counterdie obtained in (2) is immersed in the aqueous phase in (3) 20s, then the liquid on surface is drained after being taken out by counterdie, it is immersed in (4) afterwards again in organic facies of configuration to take out after 15s and obtains NF membrane, then pass through blower fan blowing and remove organic solvent;
(6) post processing of NF membrane: sodium bicarbonate solution NF membrane being immersed in temperature to be 25 DEG C of weight/mass percentage composition be 0.5% processes 2min, then after cleaning 6min with the pure water of 50 DEG C, NF membrane is immersed in weight/mass percentage composition to be 8% temperature be 2min in the glycerine water solution of 25 DEG C, then take out and dry 4 minutes under 50 DEG C of temperature conditions;
(7) test of polysulfones counterdie: after polysulfones counterdie lyophilization, test its contact angle with contact angle instrument, with its surface apertures of scanning electron microscope test;
(8) test of NF membrane: the method for testing of NF membrane performance is: when 0.5MPa, temperature 25 DEG C, pH value are 6.5, the magnesium sulfate of 500ppm and the sodium chloride of 500ppm are retained test respectively, performance is in Table 1, and the NF membrane of the present embodiment can be infiltrated completely, the advantage with good hydrophilic property.
In embodiment 1~7, the performance parameter of ultrafilter membrane and NF membrane is in Table 1
Table 1
Last it is noted that above example is only in order to illustrate technical scheme, it is not intended to limit;Although the present invention being described in detail with reference to previous embodiment, it will be understood by those within the art that: the technical scheme described in foregoing embodiments still can be modified by it, or wherein portion of techniques feature is carried out equivalent replacement;And these amendments or replacement, do not make the essence of appropriate technical solution depart from the spirit and scope of various embodiments of the present invention technical scheme.
Claims (10)
1. the preparation method of a high-hydrophilic high flux high separability energy composite nanometer filtering film, it is characterised in that comprise the following steps:
Step S10, polysulfones macromolecular material polar organic solvent is dissolved, and be configured to casting solution after adding hydrophilic porogen;
Step S20, by step S10 prepare casting solution after vacuum defoamation, even application on non-woven fabrics supporting layer, be then passed through coagulating bath process after formed there is certain pore size and certain hydrophilic counterdie;
Step S30, the counterdie prepared in step S20 is immersed in aqueous phase, fully drains after infiltration, be then immersed in organic facies again, after reaction, the organic solvent on film surface removed, after post processing, drying, make composite nanometer filtering film.
2. the preparation method of high-hydrophilic high flux high separability energy composite nanometer filtering film according to claim 1, it is characterised in that in step S10, in casting solution, the weight/mass percentage composition of polysulfones macromolecular material is 15~22%, it is preferable that 17~20%;The weight/mass percentage composition of hydrophilic porogen is 1~3%.
3. the preparation method of high-hydrophilic high flux high separability energy composite nanometer filtering film according to claim 1, it is characterised in that in step S10:
Described polysulfones macromolecular material is the one or more kinds of mixture in a series of high polymers of common bisphenol-a polysulfone, polyether sulfone, Polyphenylene Sulfone and their different sulfonation degree;
And/or, described polar organic solvent is the mixture of more than a kind of or two of which in DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide;
And/or, described hydrophilic porogen is the mixture of more than polyvinylpyrrolidone, Polyethylene Glycol, hydrophilic titanium dioxide or two of which.
4. the preparation method of high-hydrophilic high flux high separability energy composite nanometer filtering film according to claim 1, it is characterized in that, in step S20, " it is then passed through coagulating bath to process " particularly as follows: put into and coagulating bath being treated, gel completes, then soaking 3~5 hours and make the polar organic solvent of remnants diffuse out, described coagulating bath is the mixture of the organic solvent described in pure water or step S20 and water.
5. the preparation method of high-hydrophilic high flux high separability energy composite nanometer filtering film according to claim 1, it is characterised in that " certain pore size " described in step S20 is aperture 10~50nm, it is preferable that 10~30nm;
And/or, " certain hydrophilic " described in step S20 refers to that the contact angle of counterdie is 10~40 °, it is preferred to 5~30 °.
6. the preparation method of high-hydrophilic high flux high separability energy composite nanometer filtering film according to claim 1, it is characterised in that in step S30, be added with piperazine, sodium carbonate, camphorsulfonic acid, triethylamine and dodecylbenzene sodium sulfonate in described aqueous phase.
7. the preparation method of high-hydrophilic high flux high separability energy composite nanometer filtering film according to claim 6, it is characterised in that in the aqueous phase in step S30, the weight/mass percentage composition of described piperazine is 0.5~3%, it is preferred to 0.7~1.5%;The weight/mass percentage composition of sodium carbonate is 0.1~1%, it is preferred to 0.2~0.6%;In aqueous phase, the content of camphorsulfonic acid and triethylamine is that to make the pH value of aqueous phase be 10~11;The weight/mass percentage composition of dodecylbenzene sodium sulfonate is 0.05%~0.2%.
8. the preparation method of high-hydrophilic high flux high separability energy composite nanometer filtering film according to claim 1, it is characterised in that the organic facies in step S30 is the mixture that pyromellitic trimethylsilyl chloride is dissolved in that organic solvent prepares;
Described organic solvent is preferably normal hexane, hexamethylene or IsoparG;
In described organic facies, the weight/mass percentage composition of pyromellitic trimethylsilyl chloride is preferably 0.2~0.8%, more preferably 0.3~0.6%.
9. the preparation method of high-hydrophilic high flux high separability energy composite nanometer filtering film according to claim 1, it is characterized in that, in step S30, described " post processing " is particularly as follows: carry out pickling by ultrafilter membrane or/and after alkali cleaning, immersion treatment 3~10 minutes in water, then soak 1.5~2.5 minutes with glycerine water solution;
The strong acid that acid solution preferred mass percentage composition is 0.2~0.7% or weight/mass percentage composition that described pickling uses are the weak organic acid of 3~8%;The aqueous slkali that described alkali cleaning uses is preferably the sodium carbonate liquor that weight/mass percentage composition is 0.3~0.8%.
10. the preparation method of high-hydrophilic high flux high separability energy composite nanometer filtering film according to claim 1, it is characterised in that in step S30, counterdie infiltrates 15~25 seconds in aqueous phase, reacts 15~20 seconds in organic facies;And/or, in step S30, described drying for temperature be under 40~60 DEG C of temperature conditions dry 3~5 minutes.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410841789.3A CN105797602A (en) | 2014-12-30 | 2014-12-30 | Preparation method for composite nanofiltration membrane with high hydrophilicity, high flux and high separation performance |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410841789.3A CN105797602A (en) | 2014-12-30 | 2014-12-30 | Preparation method for composite nanofiltration membrane with high hydrophilicity, high flux and high separation performance |
Publications (1)
Publication Number | Publication Date |
---|---|
CN105797602A true CN105797602A (en) | 2016-07-27 |
Family
ID=56981078
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201410841789.3A Pending CN105797602A (en) | 2014-12-30 | 2014-12-30 | Preparation method for composite nanofiltration membrane with high hydrophilicity, high flux and high separation performance |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105797602A (en) |
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107158975A (en) * | 2017-06-01 | 2017-09-15 | 江苏天和制药有限公司 | A kind of positively charged nanofiltration membranes and preparation method thereof |
CN107469639A (en) * | 2017-08-04 | 2017-12-15 | 深圳先进技术研究院 | Composite nanometer filtering film and preparation method thereof |
CN107754618A (en) * | 2017-08-28 | 2018-03-06 | 杭州水处理技术研究开发中心有限公司 | A kind of preparation method of novel lasting hydrophily polysulphone super-filter membrane |
CN108159888A (en) * | 2018-01-09 | 2018-06-15 | 贵阳时代沃顿科技有限公司 | A kind of preparation method of the super hydrophilic ultrafiltration membrane with photocatalysis performance |
CN108905625A (en) * | 2018-07-20 | 2018-11-30 | 安徽原上草节能环保科技有限公司 | A kind of reverse osmosis membrane and its preparation method and application |
CN109550412A (en) * | 2018-12-12 | 2019-04-02 | 湖南恒业城市环境科技有限公司 | A kind of acid resistance polyphenylsulfone ultrafiltration membrane and preparation method thereof |
CN109569329A (en) * | 2018-12-27 | 2019-04-05 | 湖南恒业城市环境科技有限公司 | A kind of high throughput alkali resistance composite polyphenylene sulfone ultrafiltration membrane and preparation method thereof |
CN110327794A (en) * | 2019-06-28 | 2019-10-15 | 杭州天创环境科技股份有限公司 | A kind of preparation method of nanofiltration membrane |
CN111111447A (en) * | 2019-12-26 | 2020-05-08 | 湖南沁森高科新材料有限公司 | Nanofiltration membrane preparation method with adjustable and controllable desalination rate and prepared nanofiltration membrane |
CN111467979A (en) * | 2020-04-29 | 2020-07-31 | 青岛森晨环保科技有限责任公司 | Preparation method of polysulfone photocatalytic ultrafiltration membrane material for wastewater treatment |
CN112742221A (en) * | 2019-10-29 | 2021-05-04 | 珠海恩捷新材料科技有限公司 | Forward osmosis membrane based on hydrophilic modified polyolefin microporous substrate and preparation method |
CN113441020A (en) * | 2021-08-05 | 2021-09-28 | 江西省科学院能源研究所 | Composite nanofiltration membrane and preparation method and application thereof |
CN113499691A (en) * | 2021-07-21 | 2021-10-15 | 苏诺特(苏州)材料科技有限公司 | Method for modifying membrane material for organic solvent concentration |
CN113750800A (en) * | 2021-10-26 | 2021-12-07 | 天津工业大学 | Preparation method of arginine modified composite nanofiltration membrane |
CN114130206A (en) * | 2020-09-04 | 2022-03-04 | 沃顿科技股份有限公司 | Polyamide composite nanofiltration membrane and preparation method thereof |
CN114377566A (en) * | 2021-12-25 | 2022-04-22 | 广东台泉环保科技有限公司 | Nanofiltration membrane for extracting lithium from salt lake and preparation method thereof |
WO2023092781A1 (en) * | 2021-11-25 | 2023-06-01 | 沃顿科技股份有限公司 | Preparation method for reverse osmosis membrane, and reverse osmosis membrane prepared thereby |
CN116834396A (en) * | 2023-06-01 | 2023-10-03 | 广东冠豪新材料研发有限公司 | Non-woven fabric and preparation method and application thereof |
CN117065585A (en) * | 2023-08-22 | 2023-11-17 | 苏州苏瑞膜纳米科技有限公司 | Preparation method of large-flux composite nanofiltration membrane with tunnel structure base membrane and nanofiltration membrane |
CN117107297A (en) * | 2023-10-25 | 2023-11-24 | 山东东岳高分子材料有限公司 | Composite diaphragm for enhancing gas barrier property and used for alkaline water electrolysis hydrogen production and preparation method thereof |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101934201A (en) * | 2009-06-29 | 2011-01-05 | 北京时代沃顿科技有限公司 | High-selectivity composite nanofiltration membrane and preparation method thereof |
CN102294178A (en) * | 2011-08-17 | 2011-12-28 | 浙江大学 | Polyamide nano filter membrane containing zwitterions and preparation method thereof |
CN102489187A (en) * | 2011-11-30 | 2012-06-13 | 杭州北斗星膜制品有限公司 | Preparation method of composite nanofiltration membrane |
CN102489186A (en) * | 2011-11-30 | 2012-06-13 | 杭州水处理技术研究开发中心有限公司 | Preparation method of positively charged composite nano-filtration membrane |
WO2013057492A1 (en) * | 2011-10-18 | 2013-04-25 | Imperial Innovations Limited | Membranes for separation |
CN103111195A (en) * | 2013-03-13 | 2013-05-22 | 株洲时代新材料科技股份有限公司 | High-temperature resistance polyamide composite membrane and preparation method thereof |
CN103933881A (en) * | 2013-01-18 | 2014-07-23 | 中国科学院宁波材料技术与工程研究所 | Method for preparing composite nanofiltration membrane by employing interfacial polymerization process |
-
2014
- 2014-12-30 CN CN201410841789.3A patent/CN105797602A/en active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101934201A (en) * | 2009-06-29 | 2011-01-05 | 北京时代沃顿科技有限公司 | High-selectivity composite nanofiltration membrane and preparation method thereof |
CN102294178A (en) * | 2011-08-17 | 2011-12-28 | 浙江大学 | Polyamide nano filter membrane containing zwitterions and preparation method thereof |
WO2013057492A1 (en) * | 2011-10-18 | 2013-04-25 | Imperial Innovations Limited | Membranes for separation |
CN102489187A (en) * | 2011-11-30 | 2012-06-13 | 杭州北斗星膜制品有限公司 | Preparation method of composite nanofiltration membrane |
CN102489186A (en) * | 2011-11-30 | 2012-06-13 | 杭州水处理技术研究开发中心有限公司 | Preparation method of positively charged composite nano-filtration membrane |
CN103933881A (en) * | 2013-01-18 | 2014-07-23 | 中国科学院宁波材料技术与工程研究所 | Method for preparing composite nanofiltration membrane by employing interfacial polymerization process |
CN103111195A (en) * | 2013-03-13 | 2013-05-22 | 株洲时代新材料科技股份有限公司 | High-temperature resistance polyamide composite membrane and preparation method thereof |
Cited By (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107158975A (en) * | 2017-06-01 | 2017-09-15 | 江苏天和制药有限公司 | A kind of positively charged nanofiltration membranes and preparation method thereof |
CN107469639A (en) * | 2017-08-04 | 2017-12-15 | 深圳先进技术研究院 | Composite nanometer filtering film and preparation method thereof |
CN107754618A (en) * | 2017-08-28 | 2018-03-06 | 杭州水处理技术研究开发中心有限公司 | A kind of preparation method of novel lasting hydrophily polysulphone super-filter membrane |
CN108159888A (en) * | 2018-01-09 | 2018-06-15 | 贵阳时代沃顿科技有限公司 | A kind of preparation method of the super hydrophilic ultrafiltration membrane with photocatalysis performance |
WO2019137054A1 (en) * | 2018-01-09 | 2019-07-18 | 时代沃顿科技有限公司 | Preparation method for super-hydrophilic ultrafiltration membrane having photocatalytic properties |
CN108159888B (en) * | 2018-01-09 | 2020-03-13 | 时代沃顿科技有限公司 | Preparation method of super-hydrophilic ultrafiltration membrane with photocatalytic performance |
CN108905625A (en) * | 2018-07-20 | 2018-11-30 | 安徽原上草节能环保科技有限公司 | A kind of reverse osmosis membrane and its preparation method and application |
CN109550412A (en) * | 2018-12-12 | 2019-04-02 | 湖南恒业城市环境科技有限公司 | A kind of acid resistance polyphenylsulfone ultrafiltration membrane and preparation method thereof |
CN109569329A (en) * | 2018-12-27 | 2019-04-05 | 湖南恒业城市环境科技有限公司 | A kind of high throughput alkali resistance composite polyphenylene sulfone ultrafiltration membrane and preparation method thereof |
CN110327794A (en) * | 2019-06-28 | 2019-10-15 | 杭州天创环境科技股份有限公司 | A kind of preparation method of nanofiltration membrane |
CN110327794B (en) * | 2019-06-28 | 2021-10-26 | 杭州天创环境科技股份有限公司 | Preparation method of nanofiltration membrane |
CN112742221A (en) * | 2019-10-29 | 2021-05-04 | 珠海恩捷新材料科技有限公司 | Forward osmosis membrane based on hydrophilic modified polyolefin microporous substrate and preparation method |
CN112742221B (en) * | 2019-10-29 | 2023-08-18 | 珠海恩捷新材料科技有限公司 | Forward osmosis membrane based on hydrophilic modified polyolefin microporous substrate and preparation method thereof |
CN111111447A (en) * | 2019-12-26 | 2020-05-08 | 湖南沁森高科新材料有限公司 | Nanofiltration membrane preparation method with adjustable and controllable desalination rate and prepared nanofiltration membrane |
CN111467979A (en) * | 2020-04-29 | 2020-07-31 | 青岛森晨环保科技有限责任公司 | Preparation method of polysulfone photocatalytic ultrafiltration membrane material for wastewater treatment |
CN114130206A (en) * | 2020-09-04 | 2022-03-04 | 沃顿科技股份有限公司 | Polyamide composite nanofiltration membrane and preparation method thereof |
CN113499691A (en) * | 2021-07-21 | 2021-10-15 | 苏诺特(苏州)材料科技有限公司 | Method for modifying membrane material for organic solvent concentration |
CN113441020A (en) * | 2021-08-05 | 2021-09-28 | 江西省科学院能源研究所 | Composite nanofiltration membrane and preparation method and application thereof |
CN113750800A (en) * | 2021-10-26 | 2021-12-07 | 天津工业大学 | Preparation method of arginine modified composite nanofiltration membrane |
WO2023092781A1 (en) * | 2021-11-25 | 2023-06-01 | 沃顿科技股份有限公司 | Preparation method for reverse osmosis membrane, and reverse osmosis membrane prepared thereby |
CN114377566A (en) * | 2021-12-25 | 2022-04-22 | 广东台泉环保科技有限公司 | Nanofiltration membrane for extracting lithium from salt lake and preparation method thereof |
CN114377566B (en) * | 2021-12-25 | 2022-09-20 | 广东台泉环保科技有限公司 | Nanofiltration membrane for extracting lithium from salt lake and preparation method thereof |
CN116834396A (en) * | 2023-06-01 | 2023-10-03 | 广东冠豪新材料研发有限公司 | Non-woven fabric and preparation method and application thereof |
CN117065585A (en) * | 2023-08-22 | 2023-11-17 | 苏州苏瑞膜纳米科技有限公司 | Preparation method of large-flux composite nanofiltration membrane with tunnel structure base membrane and nanofiltration membrane |
CN117107297A (en) * | 2023-10-25 | 2023-11-24 | 山东东岳高分子材料有限公司 | Composite diaphragm for enhancing gas barrier property and used for alkaline water electrolysis hydrogen production and preparation method thereof |
CN117107297B (en) * | 2023-10-25 | 2024-01-05 | 山东东岳高分子材料有限公司 | Composite diaphragm for enhancing gas barrier property and used for alkaline water electrolysis hydrogen production and preparation method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105797602A (en) | Preparation method for composite nanofiltration membrane with high hydrophilicity, high flux and high separation performance | |
Plisko et al. | Effect of Pluronic F127 on porous and dense membrane structure formation via non-solvent induced and evaporation induced phase separation | |
Wu et al. | Poly (vinylidene fluoride)/polyethersulfone blend membranes: effects of solvent sort, polyethersulfone and polyvinylpyrrolidone concentration on their properties and morphology | |
Hwang et al. | Fabrication of polyphenylsulfone/polyetherimide blend membranes for ultrafiltration applications: The effects of blending ratio on membrane properties and humic acid removal performance | |
Zheng et al. | Effect of non-solvent additives on the morphology, pore structure, and direct contact membrane distillation performance of PVDF-CTFE hydrophobic membranes | |
Yin et al. | Enhanced mechanical strength and performance of sulfonated polysulfone/Tröger's base polymer blend ultrafiltration membrane | |
Ng et al. | Alteration of polyethersulphone membranes through UV-induced modification using various materials: A brief review | |
CN107174984A (en) | A kind of preparation method of low-pressure high-throughput antipollution hollow fiber nanofiltration membrane | |
JPH02302449A (en) | Preparation of microporous film | |
CN102764596A (en) | Preparation method of hydrophilic ultra-filtration membrane | |
CN111686592A (en) | Composite nanofiltration membrane and preparation method thereof | |
CN105327627B (en) | A kind of block sulfonated polyether aromatic phosphine blending/polyamide of polysulfones is combined the preparation method of forward osmosis membrane | |
CN106693706B (en) | A kind of nanofiltration membrane, preparation method and application | |
Zhu et al. | Fabrication of thin film composite nanofiltration membranes by coating water soluble disulfonated poly (arylene ether sulfone) and in situ crosslinking | |
Liu et al. | High-flux thin-film composite polyelectrolyte hydrogel membranes for ethanol dehydration by pervaporation | |
DK163964B (en) | METHOD AND APPARATUS FOR DEHYDRATIZATION OF WATER SUBSTANCES BY ELECTROOSMOSIS | |
CN106693731A (en) | Method for preparing high-throughput ultrafiltration membrane from nano calcium carbonate doped polysulfone | |
CN104056557A (en) | Polyether sulfone ultrafiltration membrane preparation method capable of improving permeability and selectivity simultaneously | |
CN109012214B (en) | Method for preparing high-permeability ultrafiltration membrane based on chemical pore-forming | |
EP2626127B1 (en) | Polyazole membrane for water purification | |
Li et al. | Preparation and characteristics of polysulfone dialysis composite membranes modified with nanocrystalline cellulose | |
CN103230747B (en) | Preparation method of composite film for water treatment | |
CN109499372A (en) | A kind of high-throughput, stable against biological contamination and anti-oxidant reverse osmosis membrane preparation method | |
CN104785120A (en) | Noumenon hydrophilic hollow fiber membrane and preparation method thereof | |
Zhou et al. | Polysulfate membrane prepared with a novel porogen for enhanced ultrafiltration performance |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160727 |
|
RJ01 | Rejection of invention patent application after publication |