CN102961975A - Preparation method of hydrophilic hollow vinylidene fluoride fiber film - Google Patents
Preparation method of hydrophilic hollow vinylidene fluoride fiber film Download PDFInfo
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- CN102961975A CN102961975A CN2012105146829A CN201210514682A CN102961975A CN 102961975 A CN102961975 A CN 102961975A CN 2012105146829 A CN2012105146829 A CN 2012105146829A CN 201210514682 A CN201210514682 A CN 201210514682A CN 102961975 A CN102961975 A CN 102961975A
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Abstract
The invention provides a preparation method of a hydrophilic hollow vinylidene fluoride fiber film. The preparation method is characterized by comprising the special steps of: blending vinylidene fluoride, a compound diluting agent and amphiphilic block copolymer to prepare a film casting liquid; squeezing the film casting liquid through a spinning nozzle to form a primary hollow fiber, feeding the formed primary hollow fiber into a solidification liquid for solidification and regeneration, placing the obtained hollow fiber film into an extraction agent for extracting the diluting agent, soaking and cleaning in pure water, and treating with a hole protection agent, so as to obtain the finished product namely the hydrophilic hollow vinylidene fluoride fiber film. According to the preparation method provided by the invention, the hydrophilic modification can be realized by blending the amphiphilic block copolymer, so that the anti-pollution property of the film can be finally improved.
Description
Technical field
The present invention relates to a kind of preparation method of hydrophilicity kynoar hollow-fibre membrane, belong to material science.
Background technology
Kynoar (PVDF) has excellent chemical stability, heat endurance, ultraviolet light resistant and enough mechanical strengths as a kind of novel membrane material, has been widely used in the embrane method recycling of water resource technology.Pvdf Microporous Hollow Fiber Membrane has Non-energy-consumption, environmental protection, and filtering accuracy is high, the materials such as can filtering all bacteriums, virus, iron rust, and can keep the characteristics of the trace element of needed by human.In recent years, be widely used research at aspects such as micro-filtration, ultrafiltration, film distillation, gas separation, desalinizations.But present commercial polyvinylidene fluoride film major part all is hydrophobic membrane, and hydrophobic membrane inevitably can cause following problem in the process of operation: the one, and surface energy is low, and wettability is very poor, so that separation process needs larger driving force; The 2nd, when separating oil/aqueous systems, pollutant easily adsorbs in film surface and fenestra, so that membrane flux descends with the prolongation of running time, cause separating property to descend, reduce the service life of film, increased operating cost, restricted its application at the film separation field; The 3rd, when being used for biomedicine field (such as haemodialysis), accelerated the gathering of antibiotic fragment on the film surface at the protein of film adsorption, cause a series of biological respinse, for example form thrombus and immune response.Therefore the hydrophilic modification of pvdf membrane has important practical significance.At present, can be summed up as the modification of membrane material body and membrane surface modification two large classes to the method for PVDF diffusion barrier hydrophilic modifying, the former improves film properties by preparation liquid is carried out hydrophilicity-imparting treatment; The latter reaches the modification purpose by introducing hydrophilic radical on the surface of finished film.
Summary of the invention
The preparation method who the purpose of this invention is to provide the good Pvdf Microporous Hollow Fiber Membrane of a kind of hydrophilicity, the problem of easily in film surface and fenestra, adsorbing to overcome pollutant.
In order to achieve the above object, the invention provides a kind of preparation method of hydrophilicity kynoar hollow-fibre membrane, it is characterized in that, concrete steps are: with Kynoar, composite thinning agent and amphipathic nature block polymer blend preparation casting solution; Casting solution is extruded through spinning head and is formed nascent doughnut, formed nascent doughnut entered solidify regeneration in the coagulating bath, the hollow-fibre membrane that obtains is put into extractant extract diluent, place again the pure water soaking and washing, and with protecting hole agent processing, obtain hydrophilicity kynoar hollow-fibre membrane finished product.
Further, the preparation method of described amphipathic nature block polymer is: preparation polydimethylacrylamiin homopolymers, the modification of polydimethylacrylamiin homopolymers is obtained nitrine end group polydimethylacrylamiin, preparation Terminal Acetylenes alkyl poly dimethyl methane siloxanes, nitrine end group polydimethylacrylamiin and Terminal Acetylenes alkyl poly dimethyl methane siloxanes are carried out the click chemistry reaction, obtain containing the amphipathic nature block polymer of polydimethylacrylamiin group and poly dimethyl methane siloxane group.
Further, the preparation method of described polydimethylacrylamiin homopolymers is: the DMAA monomer is dissolved in to make concentration in the solvent be 50～90% solution, add initator and catalyst system, the addition of initator is 0.1～2% of DMAA solution quality, the addition of catalyst system is 0.1～2% of DMAA solution quality, 55～115 ℃ of lower reactions 6～36 hours, obtain the polydimethylacrylamiin homopolymers.Described solvent is preferably one or both the mixture in cyclohexanone, toluene, carrene and the dimethyl formamide.The proportioning of solvent and DMAA monomer is 1: 1～1: 9, and is preferred 7/1～1/7, more preferably 5/1～1/5, more preferably 3/1～1/3.
Further, the method of modifying of described polydimethylacrylamiin homopolymers is: polydimethylacrylamiin and sodium azide are joined in the solvent, wherein polydimethylacrylamiin concentration is 10-60%, the weight ratio of polydimethylacrylamiin and sodium azide is 1: 1～1: 19,25-80 ℃ of lower reaction 12-72 hour, obtain nitrine end group polydimethylacrylamiin.The proportioning of polydimethylacrylamiin and sodium azide is 1: 1～1: 19, and is preferred 7/1～1/7, more preferably 5/1～1/5, more preferably 3/1～1/3.
Further, the preparation method of described Terminal Acetylenes alkyl poly dimethyl methane siloxanes is: terminal hydroxy group poly dimethyl methane siloxanes and 3-propargyl bromide are joined in the solvent, being mixed with terminal hydroxy group poly dimethyl methane siloxane concentrations is the solution of 20-80%, the weight ratio of terminal hydroxy group poly dimethyl methane siloxanes and 3-propargyl bromide is 9: 1～1: 9, under stirring condition, add potassium tert-butoxide, the weight ratio of terminal hydroxy group poly dimethyl methane siloxanes and potassium tert-butoxide is 5: 1～1: 5,-10～100 ℃ of reactions 6-24 hour, obtain Terminal Acetylenes alkyl poly dimethyl methane siloxanes.Terminal hydroxy group poly dimethyl methane siloxanes and 3-propargyl bromide proportioning are 9: 1～1: 9, and be preferred 7/1～1/7, more preferably 5/1～1/5.
Further, the concrete steps of described click chemistry reaction are: according to the method for click chemistry, nitrine end group polydimethylacrylamiin and Terminal Acetylenes alkyl poly dimethyl methane siloxanes are dissolved in the solvent, being mixed with end azido polydimethylacrylamiin concentration is 2-20%, the solubility of Terminal Acetylenes alkyl poly dimethyl methane siloxanes is the solution of 2-20%, the weight ratio of nitrine end group polydimethylacrylamiin and Terminal Acetylenes alkyl poly dimethyl methane siloxanes is 9: 1-1: 9, under the effect of catalyst system, react at the 25-105 ℃ of lower click chemistry that occurs, reaction time 2-48 hour, purifying obtains containing the amphipathic nature block polymer of polydimethylacrylamiin group and poly dimethyl methane siloxane group.The weight ratio of nitrine end group polydimethylacrylamiin and Terminal Acetylenes alkyl poly dimethyl methane siloxanes is 9/1～1/9, and is preferred 7/1～1/7, more preferably 5/1～1/5.
Further, described composite thinning agent is comprised of the first diluent and the second diluent.Described the first diluent is preferably one or more the mixture in acrylic acid carbonic ester, GBL (gamma-butyrolacton), three triacetin fat and the phthalic acid ester.Described the second diluent is preferably one or more the mixture in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), acetone, 1-METHYLPYRROLIDONE, triethyl phosphate and the trimethyl phosphate.The proportioning of the first diluent and the second diluent is 9/1～1/9, is preferably 8/1～1/8, more preferably 7/1～1/7.
Further, the compound method of described casting solution is: in the mass percent of casting solution total amount, with Kynoar powder 12%～50%, composite thinning agent 48～87.5%, amphipathic nature block polymer 0.5%～2% is put into intermingling apparatus, be that 70～220 ℃, mixing speed are agitating heating blend under the condition of 80～120r/min in temperature, the blend time is 1～6 hour, and then vacuum defoamation is 0～4 hour, obtains the casting solution of transparent and homogeneous.Kynoar is powder, and inherent viscosity η value is 1.58～2.40, and the lower of this value is limited to 1.58, is preferably 1.8; Be limited to 2.4 on this value, be preferably 2.0.Kynoar content is 12%～45%, is preferably 14%～40%, more preferably 16%～35%, more preferably 18%～30%.The addition of amphipathic nature block polymer is 0.5%-2%, preferred 0.6%, 0.8%, 1.0%, 1.2%.
Further, before blend, with solid material in advance in 60 ℃ baking oven dry 24 hours to remove moisture.
Further, described extractant is the mixture of alcohol or alcohol and intensive polar solvent.Described alcohol is monohydric alcohol, polyalcohol or its mixture.Described monohydric alcohol can be methyl alcohol, absolute ethyl alcohol etc., and described polyalcohol can be ethylene glycol etc.Described intensive polar solvent is dimethyl sulfoxide (DMSO), dimethyl formamide, dimethylacetylamide etc.
Further, described guarantor's hole agent is alcohol or its aqueous solution.Described alcohol is preferably one or more the mixture in methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol and the glycerine.
Further, described spinning head is comprised of two concentric tubes, and spinning head connects measuring pump, measuring pump connects the spinning still, casting solution places the spinning still, under the spinning pressure of measuring pump with the rotating speed of 5～10r/min, 0.3～0.6MPa, extrudes from spinning head and to form nascent doughnut.
Further, enter after the dry-spinning path of described nascent doughnut through 0～200mm and solidify regeneration in the coagulating bath, described coagulating bath is that water-bath or extractant are bathed, and the temperature of coagulating bath is 0～30 ℃.
Further, the time of described hollow-fibre membrane soaking and washing in pure water is 24～48 hours, and the described guarantor hole agent processing time is 8～12 hours.
Casting solution vacuum defoamation of the present invention is processed, formed operating temperature and the time that cleaning and dipping, guarantor's hole agent are processed in doughnut, extractant processing, the water through spinning head all is well-known to those skilled in the art, can determine by simple test.
The cross section of the hydrophilicity kynoar hollow-fibre membrane finished product of gained of the present invention is the spongelike structure with the mesh that is cross-linked with each other, and the diameter of fenestra is 0.1～1 μ m.The lower 0.1 μ m that is limited to of film hole diameter is preferably 0.15,0.2,0.25,0.3,0.35 or 0.4 μ m; Be limited to 1 μ m on it, be preferably 0.95,0.9,0.85,0.8,0.75,0.7,0.65 or 0.6 μ m.If film hole diameter is less than 0.1 μ m, then the water flux of hollow-fibre membrane is tending towards descending, and affects the wastewater treatment ability; If film hole diameter greater than 1 μ m, then the separation accuracy of hollow-fibre membrane is tending towards reducing, and might affect the mechanical strength of hollow-fibre membrane.
The present invention is take the mechanism that is separated as the basis, and traditional thermally induced phase separation uses a kind of single diluent usually when the preparation casting solution; And the present invention adopts two kinds of diluents to carry out composite when the preparation casting solution, this is one of innovation of the present invention, in addition, the present invention has added a kind of amphipathic polymer when the preparation casting solution, the film that obtains at last directly just has certain hydrophily, and this obviously is different from traditional thermally induced phase separation.
Amphipathic nature block polymer of the present invention adopts polydimethylacrylamiin as hydrophilic segment, adopts dimethyl silicone polymer as hydrophobic segment.
The hollow-fibre membrane cross section of adopting technique of the present invention to produce presents loose network-like structure, and fenestra is cross-linked with each other and is evenly distributed, but effective guarantee water flux, mechanical strength and rejection.
Compared with prior art, the invention has the beneficial effects as follows:
Amphipathic nature block polymer among the present invention, namely have the hydrophilic end of the chain and have again the hydrophobic end of the chain, in the process of film forming, the hydrophilic end of the chain is effectively on the enrichment film, so that the hydrophilicity of film improves greatly, thereby reduced in the separation process suction-operated to materials such as albumen.
Pvdf Microporous Hollow Fiber Membrane of the present invention outside mask has very thin one deck compacted zone, can play the effect of holding back, make it have higher filtering accuracy, simultaneously, can also greatly improve film strength, finally make film have higher-strength and than high score from precision, be applicable to urban water fully and purify.
Description of drawings
Fig. 1 is the amphipathic nature block polymer structure chart;
Fig. 2 is hydrophilicity kynoar doughnut film production line sketch;
Fig. 3 is the spinning head sectional view;
Fig. 4 is hydrophilicity kynoar hollow-fibre membrane scanning electron microscope (SEM) photograph.
Fig. 5 is that the hydrophilicity kynoar hollow-fibre membrane is near the inner surface scanning electron microscope (SEM) photograph of film;
Fig. 6 is that the hydrophilicity kynoar hollow-fibre membrane is near the outer surface scanning electron microscope (SEM) photograph of film.
The specific embodiment
Below in conjunction with specific embodiment and accompanying drawing, the invention will be further described.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.
" part " described in the present invention except specifying, all refers to " weight portion "; Described percentage composition except specifying, all refers to the quality percentage composition.
Kynoar in the various embodiments of the present invention (PVDF, model FR904, inherent viscosity η are 1.58～2.40) is available from the Shanghai rich new material of three love Co., Ltd; Other reagent are all available from China Medicine (Group) Shanghai Chemical Reagent Co..
Step among the embodiment of the invention 3-12 (2) adopts hydrophilicity kynoar doughnut film production line as shown in Figure 2, and described hydrophilicity kynoar doughnut film production line comprises measuring pump 1, spinning head 2, coagulating bath 3, the first drafting system 4, the second drafting system 5 and coiler device 6.As shown in Figure 3, spinning head 2 is comprised of two concentric tubes, and spinning head 2 connects measuring pump 1, and measuring pump 1 connects the spinning still, and spinning solution 7 flows into spinning head 2 from measuring pump 1.
The testing evaluation method of the technical indicator of the Pvdf Microporous Hollow Fiber Membrane that obtains in the various embodiments of the present invention is:
The cross section microscopic pattern: dry film is after liquid nitrogen Fracture or direct sputtered platinum, with Japanese JSM-5600LV type scanning electron microscope test;
Membrane flux: routinely detection method, such as the test of the method described in the following document: Liu Yongjian etc., " membrane science and technology ", 1998,18 (4): 42～45.
Rejection: routinely detection method test, such as can be with reference to the method for describing in the following document: Li Nana etc., the research of PVDF/PVA blend film." functional material ", 38 volumes the 12nd phase 1975-1980 page or leaf in 2007.
Ultimate tensile strength: after dry film being cut into the strip of certain size, with the new WDW3020 type microcomputer control formula electronic universal tester test of Changchun section.
Inherent viscosity (10
2Ml/g): the Ubbelohde viscometer method.
Embodiment 1
(1) preparation of polydimethylacrylamiin homopolymers:
The DMAA monomer is dissolved in to make concentration in the cyclohexanone be 50% DMAA solution, drop into initator bromo acid allyl ester and catalyst system cuprous iodide/three-(N under the vacuum condition, the N-dimethylaminoethyl) amine, the addition of initator is 0.1% of DMAA solution quality, in the catalyst system, the addition of cuprous iodide is 0.1% of DMAA solution quality, three-(N, the N-dimethylaminoethyl) addition of amine is 0.6% of DMAA solution quality, 55 ℃ of lower reactions 6 hours, obtain the polydimethylacrylamiin homopolymers;
(2) modification of polydimethylacrylamiin homopolymers:
1 part of polydimethylacrylamiin and 2 parts of sodium azide are dissolved in 10 parts of toluene, 50 ℃ of lower reactions 12 hours, obtain nitrine end group polydimethylacrylamiin;
(3) hydrophobic chain segment Terminal Acetylenes alkyl poly dimethyl methane siloxanes is synthetic:
Terminal hydroxy group poly dimethyl methane siloxanes and 3-propargyl bromide are added in the dimethylacetamide solvent, be mixed with terminal hydroxy group poly dimethyl methane siloxane concentrations and be 20% solution, the weight ratio of terminal hydroxy group poly dimethyl methane siloxanes and 3-propargyl bromide is 9: 1, under stirring condition, add potassium tert-butoxide, the weight ratio of terminal hydroxy group poly dimethyl methane siloxanes and potassium tert-butoxide is 20: 1, room temperature reaction 24 hours, obtain Terminal Acetylenes alkyl poly dimethyl methane siloxanes.
(4) click chemistry reaction:
Method according to click chemistry, nitrine end group polydimethylacrylamiin and Terminal Acetylenes alkyl poly dimethyl methane siloxanes are dissolved in the cyclohexanone solvent, being mixed with end azido polydimethylacrylamiin concentration is 5%, the solubility of Terminal Acetylenes alkyl poly dimethyl methane siloxanes is 20% solution, the weight ratio of nitrine end group polydimethylacrylamiin and Terminal Acetylenes alkyl poly dimethyl methane siloxanes is 1: 9, under the effect of catalyst system sodium ascorbate/cupric sulfate pentahydrate, react at 105 ℃ of lower click chemistries that occur, 8 hours reaction time, the mass ratio of sodium ascorbate and cupric sulfate pentahydrate is 4: 1, the addition of sodium ascorbate is 0.2% of solution system, obtain as shown in Figure 1 the amphipathic nature block polymer that contains polydimethylacrylamiin group and poly dimethyl methane siloxane group finally by deposition and purification, wherein used precipitating reagent is n-hexane.
(1) preparation of polydimethylacrylamiin homopolymers:
Take volume ratio as 1: 1 cyclohexanone and the mixed solvent of toluene as solvent, make concentration and be 10% DMAA solution, add successively initator chloro isobutyric acid allyl ester under the vacuum condition, catalyst system cuprous bromide/pentamethyl diethyl triamine, wherein the addition of initator is 2% of DMAA solution quality, the addition of cuprous bromide is 1% of DMAA solution quality in the catalyst system, the addition of pentamethyl diethyl triamine is 1% of DMAA solution quality, 80 ℃ of lower reactions 36 hours, obtain the polydimethylacrylamiin homopolymers;
(2) modification of polydimethylacrylamiin homopolymers:
1 part of polydimethylacrylamiin and 10 parts of sodium azide are dissolved in 50 parts of toluene, 60 ℃ of lower reactions 24 hours, obtain nitrine end group polydimethylacrylamiin, conversion ratio is 80%;
(3) hydrophobic chain segment Terminal Acetylenes alkyl poly dimethyl methane siloxanes is synthetic:
Terminal hydroxy group poly dimethyl methane siloxanes and 3-propargyl bromide are joined in the cyclohexanone solvent, be mixed with terminal hydroxy group poly dimethyl methane siloxane concentrations and be 15%, 3-propargyl bromide solubility is 45% solution, under stirring condition, add potassium tert-butoxide, addition is 1/10th of terminal hydroxy group poly dimethyl methane siloxanes, room temperature reaction 24 hours, obtain Terminal Acetylenes alkyl poly dimethyl methane siloxanes.
(4) click chemistry reaction:
Method according to click chemistry, nitrine end group polydimethylacrylamiin and Terminal Acetylenes alkyl poly dimethyl methane siloxanes are dissolved in the cyclohexanone solvent, being mixed with nitrine end group polydimethylacrylamiin concentration is 20%, Terminal Acetylenes alkyl poly dimethyl methane siloxanes solubility is 5% solution, under the effect of catalyst system cuprous iodide/pentamethyl diethyl triamine, react at 25 ℃ of lower click chemistries that occur, 2 hours reaction time, wherein the mass ratio of cuprous iodide/pentamethyl diethyl triamine is 1: 3, the addition of cuprous iodide is 1% of solution system, finally by deposition and purification, used precipitating reagent is n-hexane, obtains containing the amphipathic nature block polymer (not shown) of polydimethylacrylamiin group and poly dimethyl methane siloxane group.
Embodiment 3
(1) preparation of polydimethylacrylamiin homopolymers:
Take volume ratio as 1: 1 cyclohexanone and the mixed solvent of toluene as solvent, make concentration and be 10% DMAA solution, add successively initator chloro isobutyric acid allyl ester under the vacuum condition, catalyst system stannous chloride/pentamethyl diethyl triamine, wherein the addition of initator is 2% of DMAA solution quality, the addition of stannous chloride is 1% of DMAA solution quality in the catalyst system, the addition of pentamethyl diethyl triamine is 1% of DMAA solution quality, 80 ℃ of lower reactions 36 hours, obtain the polydimethylacrylamiin homopolymers;
(2) modification of polydimethylacrylamiin homopolymers:
1 part of polydimethylacrylamiin and 10 parts of sodium azide are dissolved in 50 parts of toluene, 60 ℃ of lower reactions 24 hours, obtain nitrine end group polydimethylacrylamiin, conversion ratio is 80%;
(3) hydrophobic chain segment Terminal Acetylenes alkyl poly dimethyl methane siloxanes is synthetic:
Terminal hydroxy group poly dimethyl methane siloxanes and 3-propargyl bromide are joined in the cyclohexanone solvent, be mixed with terminal hydroxy group poly dimethyl methane siloxane concentrations and be 15%, 3-propargyl bromide solubility is 45% solution, under stirring condition, add potassium tert-butoxide, addition is 1/10th of terminal hydroxy group poly dimethyl methane siloxanes, room temperature reaction 24 hours, obtain Terminal Acetylenes alkyl poly dimethyl methane siloxanes.
(4) click chemistry reaction:
Method according to click chemistry, nitrine end group polydimethylacrylamiin and Terminal Acetylenes alkyl poly dimethyl methane siloxanes are dissolved in the cyclohexanone solvent, being mixed with nitrine end group polydimethylacrylamiin concentration is 20%, Terminal Acetylenes alkyl poly dimethyl methane siloxanes solubility is 5% solution, under the effect of catalyst system sodium ascorbate/cupric sulfate pentahydrate, react at 25 ℃ of lower click chemistries that occur, 2 hours reaction time, the mass ratio of sodium ascorbate and cupric sulfate pentahydrate is 3: 1 in the catalyst system, the addition of sodium ascorbate is 15% of solution system, finally by deposition and purification, obtain containing the amphipathic nature block polymer (not shown) of polydimethylacrylamiin group and poly dimethyl methane siloxane group, wherein used precipitating reagent is n-hexane.
Embodiment 4
(1) preparation of polydimethylacrylamiin homopolymers:
Take volume ratio as 1: 2 cyclohexanone and the mixed solvent of toluene as solvent, make concentration and be 15% DMAA solution, add successively initator chloro isobutyric acid allyl ester under the vacuum condition, catalyst system stannous chloride/three-(N, the N-dimethylaminoethyl) amine, wherein the addition of initator is 2% of DMAA solution quality, the addition of stannous chloride is 5% of DMAA solution quality in the catalyst system, three-(N, the N-dimethylaminoethyl) addition of amine is 4% of DMAA solution quality, 80 ℃ of lower reactions 36 hours, obtain the polydimethylacrylamiin homopolymers;
(2) modification of polydimethylacrylamiin homopolymers:
1 part of polydimethylacrylamiin and 10 parts of sodium azide are dissolved in 50 parts of toluene, 60 ℃ of lower reactions 24 hours, obtain nitrine end group polydimethylacrylamiin, conversion ratio is 80%;
(3) hydrophobic chain segment Terminal Acetylenes alkyl poly dimethyl methane siloxanes is synthetic:
Terminal hydroxy group poly dimethyl methane siloxanes and 3-propargyl bromide are joined in the cyclohexanone solvent, be mixed with terminal hydroxy group poly dimethyl methane siloxane concentrations and be 15%, 3-propargyl bromide solubility is 45% solution, under stirring condition, add potassium tert-butoxide, addition is 1/10th of terminal hydroxy group poly dimethyl methane siloxanes, room temperature reaction 24 hours, obtain Terminal Acetylenes alkyl poly dimethyl methane siloxanes.
(4) click chemistry reaction:
Method according to click chemistry, nitrine end group polydimethylacrylamiin and Terminal Acetylenes alkyl poly dimethyl methane siloxanes are dissolved in the cyclohexanone solvent, being mixed with nitrine end group polydimethylacrylamiin concentration is 20%, Terminal Acetylenes alkyl poly dimethyl methane siloxanes solubility is 5% solution, under the effect of catalyst system sodium ascorbate/cupric sulfate pentahydrate, react at 25 ℃ of lower click chemistries that occur, 2 hours reaction time, the mass ratio of sodium ascorbate and cupric sulfate pentahydrate is 2: 1 in the catalyst system, the addition of sodium ascorbate is 0.2% of solution system, finally by deposition and purification, used precipitating reagent is n-hexane, obtains containing the amphipathic nature block polymer (not shown) of polydimethylacrylamiin group and poly dimethyl methane siloxane group.
Embodiment 5
(1) preparation of polydimethylacrylamiin homopolymers:
Take volume ratio as 1: 2 cyclohexanone and the mixed solvent of toluene as solvent, make concentration and be 15% DMAA solution, add successively initator chloro isobutyric acid allyl ester under the vacuum condition, catalyst system cuprous bromide/three-(N, the N-dimethylaminoethyl) amine, wherein the addition of initator is 2% of DMAA solution quality, the addition of cuprous bromide is 10% of DMAA solution quality in the catalyst system, three-(N, the N-dimethylaminoethyl) addition of amine is 8% of DMAA solution quality, 80 ℃ of lower reactions 36 hours, obtain the polydimethylacrylamiin homopolymers;
(2) modification of polydimethylacrylamiin homopolymers:
1 part of polydimethylacrylamiin and 10 parts of sodium azide are dissolved in 50 parts of toluene, 60 ℃ of lower reactions 24 hours, obtain nitrine end group polydimethylacrylamiin, conversion ratio is 80%;
(3) hydrophobic chain segment Terminal Acetylenes alkyl poly dimethyl methane siloxanes is synthetic:
Terminal hydroxy group poly dimethyl methane siloxanes and 3-propargyl bromide are joined in the cyclohexanone solvent, be mixed with terminal hydroxy group poly dimethyl methane siloxane concentrations and be 15%, 3-propargyl bromide solubility is 45% solution, under stirring condition, add potassium tert-butoxide, addition is 1/10th of terminal hydroxy group poly dimethyl methane siloxanes, room temperature reaction 24 hours, obtain Terminal Acetylenes alkyl poly dimethyl methane siloxanes.
(4) click chemistry reaction:
Method according to click chemistry, nitrine end group polydimethylacrylamiin and Terminal Acetylenes alkyl poly dimethyl methane siloxanes are dissolved in the cyclohexanone solvent, being mixed with nitrine end group polydimethylacrylamiin concentration is 20%, Terminal Acetylenes alkyl poly dimethyl methane siloxanes solubility is 5% solution, under the effect of catalyst system cuprous iodide/pentamethyl diethyl triamine, react at 25 ℃ of lower click chemistries that occur, 2 hours reaction time, the mass ratio of cuprous iodide and pentamethyl diethyl triamine is 3: 2 in the catalyst system, the addition of cuprous iodide is 0.2% of solution system, finally by deposition and purification, used precipitating reagent is n-hexane, obtains containing the amphipathic nature block polymer (not shown) of polydimethylacrylamiin group and poly dimethyl methane siloxane group.
Embodiment 6
(1) with solid material in advance in 60 ℃ baking oven dry 24 hours to remove moisture, in the mass percent of casting solution total amount, the synthetic amphipathic nature block polymer 0.8% of Kynoar powder 15%, gamma-butyrolacton 37.36%, repefral 30%, dimethyl formamide 16.84% and embodiment 1 wherein; Putting into intermingling apparatus, is that 100 ℃, mixing speed are under the condition of 80r/min in temperature, the agitating heating blend, and the blend time is 1.5 hours, then vacuum defoamation is 2 hours, obtains the casting solution of transparent and homogeneous.
(2) casting solution after the deaeration processing is put into the spinning still, adopt production line as shown in Figure 2, control measuring pump 1 rotating speed is 8r/min, under the spinning pressure of 0.5MPa, casting solution is extruded the nascent doughnut of formation from spinning head 2, be under the condition of 4m/min through the dry-spinning path of 6cm at the coiling draw speed, enter in the coagulating bath 3 and solidify regeneration, coagulating bath 3 is 25 ℃ 20% ethanol water for temperature, carry out twice two-way (radial and axial) stretching and appropriateness retraction through the first drafting system 4 and the second drafting system 5 again, radial and axial total draw ratio is respectively 1 and 2, obtains doughnut, reels with coiler device 6.Carefully doughnut is put into the absolute ethyl alcohol extraction and removed diluent in 24 hours, process through 2 road pure water soaking and washing again, per pass pure water soaking and washing was processed 12 hours, protected the hole with 50% glycerin solution again and processed 8 hours, can obtain hydrophilicity kynoar hollow-fibre membrane finished product.
Record the internal diameter of PVDF hollow-fibre membrane: 0.55mm, external diameter: 0.9mm, bubble point pressure: 0.40MPa, hot strength: 7.5 ± 0.5MPa, elongation at break: 160 ± 5%, water contact angle: 35 °, the flux to 25 ℃ of pure water under 0.1MPa pressure is 800L/m
2H.Hollow-fibre membrane section S EM figure sees Fig. 4～Fig. 6, can find out obviously that its cross section is loose spongelike structure, and described structure has the mesh that is cross-linked with each other, and the equivalent diameter of mesh (being fenestra) is 0.1～1.0 μ m.
(1) with solid material in advance in 60 ℃ baking oven dry 24 hours to remove moisture, in the mass percent of casting solution total amount, the synthetic amphipathic nature block polymer 0.8% of Kynoar powder 20%, three triacetin fat 63.4%, dimethylacetylamide 15.8% and embodiment 1 wherein; Putting into intermingling apparatus, is that 100 ℃, mixing speed are under the condition of 100r/min in temperature, the agitating heating blend, and the blend time is 3 hours, then vacuum defoamation is 4 hours, obtains the casting solution of transparent and homogeneous;
(2) casting solution after the deaeration processing is put into the spinning still, adopt production line as shown in Figure 2, control measuring pump 1 rotating speed is 8r/min, under the spinning pressure of 0.5MPa, casting solution is extruded the nascent doughnut of formation from spinning head 2, be under the condition of 50m/min through the dry-spinning path of 8cm at the coiling draw speed, enter in the coagulating bath 3 and solidify regeneration, coagulating bath 3 is 25 ℃ 20% ethanol water for temperature, carry out twice two-way (radial and axial) stretching and appropriateness retraction through the first drafting system 4 and the second drafting system 5 again, radial and axial total draw ratio is respectively 1 and 1, obtains doughnut, reels with coiler device 6.Carefully doughnut is put into the absolute ethyl alcohol extraction and removed diluent in 24 hours, process through 2 road pure water soaking and washing again, per pass pure water soaking and washing was processed 12 hours, protect the hole with the aqueous solution that contains 10% glycerine, 30% ethanol again and processed 8 hours, both can obtain hydrophilicity kynoar hollow-fibre membrane finished product.
Record the internal diameter of PVDF hollow-fibre membrane: 0.60mm, external diameter: 0.9mm, bubble point pressure: 0.30MPa, hot strength: 8.0 ± 0.5MPa, elongation at break: 180 ± 5%, water contact angle: 40 ± 0.5 °, the flux to 25 ℃ of pure water under 0.1MPa pressure is 850L/m
2H.The cross section of film is loose spongelike structure, and described structure has the mesh that is cross-linked with each other, and the equivalent diameter of mesh (being fenestra) is 0.1～1.0 μ m (not shown).
Embodiment 8
(1) with solid material in advance in 60 ℃ baking oven dry 24 hours to remove moisture, in the mass percent of casting solution total amount, the synthetic amphipathic nature block polymer 0.8% of Kynoar powder 25%, gamma-butyrolacton 29.4%, acrylic acid carbonic ester 20%, three triacetin fat 10%, 1-METHYLPYRROLIDONE 14.8% and embodiment 1 wherein; Putting into intermingling apparatus, is that 120 ℃, mixing speed are agitating heating blend under the condition of 90r/min in temperature, and the blend time is 4 hours, and then vacuum defoamation is 4 hours, obtains the casting solution of transparent and homogeneous;
(2) casting solution after the deaeration processing is put into the spinning still, adopt production line as shown in Figure 2, control measuring pump 1 rotating speed is 6r/min, under the spinning pressure of 0.5MPa, casting solution is extruded the nascent doughnut of formation from spinning head 2, be under the condition of 60m/min through the dry-spinning path of 2cm at the coiling draw speed, enter in the coagulating bath 3 and solidify regeneration, coagulating bath 3 is 25 ℃ 20% ethanol water for temperature, carry out twice two-way (radial and axial) stretching and appropriateness retraction through the first drafting system 4 and the second drafting system 5 again, radial and axial total draw ratio is respectively 1.5 and 2, obtains doughnut, reels with coiler device 6.Carefully doughnut is put into the absolute ethyl alcohol extraction and removed diluent in 24 hours, process through 2 road pure water soaking and washing again, per pass pure water soaking and washing was processed 14 hours, protect the hole with the aqueous solution that contains 20% glycerine, 10% ethylene glycol again and processed 8 hours, both can obtain hydrophilicity kynoar hollow-fibre membrane finished product.
Record the internal diameter of PVDF hollow-fibre membrane: 0.6mm, external diameter: 0.9mm, bubble point pressure: 0.40MPa, hot strength: 8.5 ± 0.5MPa, elongation at break: 190 ± 5%, water contact angle: 45 ± 0.5 °, the flux to 25 ℃ of pure water under 0.1MPa pressure is 780L/m
2H.The cross section of film is loose spongelike structure, and described structure has the mesh that is cross-linked with each other, and the equivalent diameter of mesh (being fenestra) is 0.1～0.8 μ m (not shown).
Embodiment 9
(1) with solid material in advance in 60 ℃ baking oven dry 24 hours to remove moisture, in the mass percent of casting solution total amount, the synthetic amphipathic nature block polymer 0.8% of Kynoar powder 25%, three triacetin fat 49.4%, repefral 10%, 1-METHYLPYRROLIDONE 14.8% and embodiment 1 wherein; Putting into intermingling apparatus, is that 120 ℃, mixing speed are agitating heating blend under the condition of 90r/min in temperature, and the blend time is 5 hours, and then vacuum defoamation is 4 hours, obtains the casting solution of transparent and homogeneous;
(2) casting solution after the deaeration processing is put into the spinning still, adopt production line as shown in Figure 2, control measuring pump 1 rotating speed is 10r/min, under the spinning pressure of 0.5MPa, casting solution is extruded the nascent doughnut of formation from spinning head 2, be under the condition of 90m/min through the dry-spinning path of 14cm at the coiling draw speed, enter in the coagulating bath 3 and solidify regeneration, coagulating bath 3 is 25 ℃ 20% ethanol water for temperature, carry out twice two-way (radial and axial) stretching and appropriateness retraction through the first drafting system 4 and the second drafting system 5 again, radial and axial total draw ratio is respectively 1 and 2, obtains doughnut, reels with coiler device 6.Carefully doughnut is put into the absolute ethyl alcohol extraction and removed diluent in 24 hours, process through 2 road pure water soaking and washing again, per pass pure water soaking and washing was processed 12 hours, protect the hole with the solution that contains 20% methyl alcohol, 40% isopropyl alcohol again and processed 8 hours, both can obtain hydrophilicity kynoar hollow-fibre membrane finished product.
Record the internal diameter of PVDF hollow-fibre membrane: 0.60mm, external diameter: 0.9mm, bubble point pressure: 0.35MPa, hot strength: 9.0 ± 0.5MPa, elongation at break: 200 ± 5%, water contact angle: 39 ± 0.5 °, the flux to 25 ℃ of pure water under 0.1MPa pressure is 720L/m
2H.The cross section of film is loose spongelike structure, and described structure has the mesh that is cross-linked with each other, and the equivalent diameter of mesh (being fenestra) is 0.1～0.8 μ m (not shown).
Embodiment 10
(1) with solid material in advance in 60 ℃ baking oven dry 24 hours to remove moisture, in the mass percent of casting solution total amount, with Kynoar powder 30%, gamma-butyrolacton: 15.2%; The amphipathic nature block polymer 1.0% that acrylic acid carbonic ester 20%, repefral 10%, dibutyl phthalate 10%, dimethylacetylamide 13.8% and embodiment 1 synthesize; Putting into intermingling apparatus, is that 120 ℃, mixing speed are agitating heating blend under the condition of 80r/min in temperature, and the blend time is 4 hours, and then vacuum defoamation is 4 hours, obtains the casting solution of transparent and homogeneous;
(2) casting solution after the deaeration processing is put into the spinning still, adopt production line as shown in Figure 2, control measuring pump 1 rotating speed is 10r/min, under the spinning pressure of 0.5MPa, casting solution is extruded the nascent doughnut of formation from spinning head 2, be under the condition of 6m/min through the dry-spinning path of 20cm at the coiling draw speed, enter in the coagulating bath 3 and solidify regeneration, coagulating bath 3 is 25 ℃ polymer solution in water for temperature, carry out twice two-way (radial and axial) stretching and appropriateness retraction through the first drafting system 4 and the second drafting system 5 again, radial and axial total draw ratio is respectively 1.5 and 2, obtain doughnut, reel with coiler device 6, carefully doughnut is put into the absolute ethyl alcohol extraction and removed diluent in 24 hours, process through 2 road pure water soaking and washing, per pass pure water soaking and washing was processed 12 hours, again with containing 5% isopropyl alcohol, the aqueous solution of 10% ethylene glycol is protected the hole and was processed 8 hours, both can obtain hydrophilicity kynoar hollow-fibre membrane finished product.
Record the internal diameter of PVDF hollow-fibre membrane: 0.50mm, external diameter: 0.8mm, bubble point pressure: 0.50MPa, hot strength: 10.0 ± 0.5MPa, elongation at break: 220 ± 5%, water contact angle: 45 ± 0.5 °, the flux to 25 ℃ of pure water under 0.1MPa pressure is 600L/m
2H.The cross section of film is loose spongelike structure, and described structure has the mesh that is cross-linked with each other, and the equivalent diameter of mesh (being fenestra) is 0.1～0.6 μ m (not shown).
Embodiment 11
(1) with solid material in advance in 60 ℃ baking oven dry 24 hours to remove moisture, in the mass percent of casting solution total amount, wherein Kynoar powder 35%, three triacetin fat: 32.67%; Dioctyl phthalate 10%; Dimethylacetylamide: 5.33%; 1-METHYLPYRROLIDONE: 16% and the synthetic amphipathic nature block polymer 1.0% of embodiment 2; Putting into intermingling apparatus, is that 120 ℃, mixing speed are agitating heating blend under the condition of 110r/min in temperature, and the blend time is 4.5 hours, and then vacuum defoamation is 4 hours, obtains the casting solution of transparent and homogeneous;
(2) casting solution after the deaeration processing is put into the spinning still, adopt production line as shown in Figure 2, control measuring pump 1 rotating speed is 9r/min, under the spinning pressure of 0.5MPa, casting solution is extruded the nascent doughnut of formation from spinning head 2, be under the condition of 90m/min through the dry-spinning path of 6cm at the coiling draw speed, enter in the coagulating bath 3 and solidify regeneration, coagulating bath 3 is 25 ℃ 20% polymer solution in water for temperature, carry out twice two-way (radial and axial) stretching and appropriateness retraction through the first drafting system 4 and the second drafting system 5 again, radial and axial total draw ratio is respectively 1.5 and 2, obtains doughnut, reels with coiler device 6.Carefully doughnut is put into the absolute ethyl alcohol extraction and removed diluent in 24 hours, process through 2 road pure water soaking and washing again, per pass pure water soaking and washing was processed 14 hours, protect the hole with the aqueous solution that contains 30% methyl alcohol, 30% ethylene glycol again and processed 8 hours, both can obtain hydrophilicity kynoar hollow-fibre membrane finished product.
Record the internal diameter of PVDF hollow-fibre membrane: 0.60mm, external diameter: 0.9mm, bubble point pressure: 0.50MPa, hot strength: 9.8 ± 0.5MPa, elongation at break: 230 ± 5%, water contact angle: 49 ± 0.5 °, the flux to 25 ℃ of pure water under 0.1MPa pressure is 680L/m
2H.The cross section of film is loose spongelike structure, and described structure has the mesh that is cross-linked with each other, and the equivalent diameter of mesh (being fenestra) is 0.1～0.6 μ m (not shown).
Embodiment 12
(1) with solid material in advance in 60 ℃ baking oven dry 24 hours to remove moisture, in the mass percent of casting solution total amount, the synthetic amphipathic nature block polymer 1.5% of Kynoar powder 40%, acrylic acid carbonic ester 10%, gamma-butyrolacton 15%, three triacetin fat 10%, repefral 5%, dibutyl phthalate 5%, dinonyl phthalate 2.8%, dimethylacetylamide 3.7%, triethyl phosphate 7% and embodiment 2 wherein; Putting into intermingling apparatus, is that 160 ℃, mixing speed are agitating heating blend under the condition of 85r/min in temperature, and the blend time is 5 hours, and then vacuum defoamation is 3 hours, obtains the casting solution of transparent and homogeneous;
(2) casting solution after the deaeration processing is put into the spinning still, adopt production line as shown in Figure 2, control measuring pump 1 rotating speed is 10r/min, under the spinning pressure of 0.6MPa, casting solution is extruded the nascent doughnut of formation from spinning head 2, the dry-spinning path of process 10cm under the condition 15m/min that the coiling draw speed is, enter in the coagulating bath 3 and solidify regeneration, coagulating bath 3 is 30 ℃ 20% ethanol water for temperature, carry out twice two-way (radial and axial) stretching and appropriateness retraction through the first drafting system 4 and the second drafting system 5 again, radial and axial total draw ratio is respectively 2 and 2.5, obtains doughnut, reels with coiler device 6.Carefully doughnut is put into the absolute ethyl alcohol extraction and removed diluent in 24 hours, process through 2 road pure water soaking and washing again, per pass pure water soaking and washing was processed 15 hours, with containing 10% ethanol, 15% glycerin solution guarantor hole processing 8 hours, both can obtain hydrophilicity kynoar hollow-fibre membrane finished product again.
Record the internal diameter of PVDF hollow-fibre membrane: 0.70mm, external diameter: 1.0mm, bubble point pressure: 1.50MPa, hot strength: 11.5 ± 0.5MPa, elongation at break: 280 ± 5%, water contact angle: 50 ± 0.5 °, the flux to 25 ℃ of pure water under 0.1MPa pressure is 480L/m
2H.The cross section of film is loose spongelike structure, and described structure has the mesh that is cross-linked with each other, and the equivalent diameter of mesh (being fenestra) is 0.3～0.8 μ m (not shown).
Embodiment 13
(1) with solid material in advance in 60 ℃ baking oven dry 24 hours to remove moisture, in the mass percent of casting solution total amount, the synthetic amphipathic nature block polymer 1.5% of Kynoar powder 45%, three triacetin fat 26.8%, acrylic acid carbonic ester 5%, gamma-butyrolacton 10%, dimethylacetylamide 2.7%, dimethyl formamide 3%, dimethyl sulfoxide (DMSO) 2%, acetone 2%, 1-METHYLPYRROLIDONE 1%, triethyl phosphate 1% and embodiment 2 wherein; Putting into intermingling apparatus, is that 200 ℃, mixing speed are agitating heating blend under the condition of 120r/min in temperature, and the blend time is 4 hours, and then vacuum defoamation is 3.5 hours, obtains the casting solution of transparent and homogeneous;
(2) casting solution after the deaeration processing is put into the spinning still, adopt production line as shown in Figure 2, control measuring pump 1 rotating speed is 10r/min, under the spinning pressure of 0.6MPa, casting solution is extruded the nascent doughnut of formation from spinning head 2, be under the condition of 45m/min through the dry-spinning path of 8cm at the coiling draw speed, enter in the coagulating bath 3 and solidify regeneration, coagulating bath 3 is 30 ℃ 20% ethanol water for temperature, carry out twice two-way (radial and axial) stretching and appropriateness retraction through the first drafting system 4 and the second drafting system 5 again, radial and axial total draw ratio is respectively 1.5 and 2, obtains doughnut, reels with coiler device 6.Carefully doughnut is put into the absolute ethyl alcohol extraction and removed diluent in 24 hours, process through 2 road pure water soaking and washing again, per pass pure water soaking and washing was processed 8 hours, protected the hole with 50% glycol water again and processed 8 hours, both can obtain hydrophilicity kynoar hollow-fibre membrane finished product.
Record the internal diameter of PVDF hollow-fibre membrane: 0.70mm, external diameter: 1.0mm, bubble point pressure: 0.90MPa, hot strength: 12.7 ± 0.5MPa, elongation at break: 186 ± 5%, water contact angle: 42 ± 0.5 °, the flux to 25 ℃ of pure water under 0.1MPa pressure is 440L/m
2H.The cross section of film is loose spongelike structure, and described structure has the mesh that is cross-linked with each other, and the equivalent diameter of mesh (being fenestra) is 0.4～0.9 μ m (not shown).
Embodiment 14
(1) with solid material in advance in 60 ℃ baking oven dry 24 hours to remove moisture, mass percent in the casting solution total amount, the synthetic amphipathic nature block polymer 1.5% of Kynoar powder 30%, three triacetin fat 21.65%, GBL (gamma-butyrolacton) 20%, repefral 20%, 1-METHYLPYRROLIDONE 6.85% and embodiment 2 wherein; Putting into intermingling apparatus, is that 160 ℃, mixing speed are agitating heating blend under the condition of 85r/min in temperature, and the blend time is 3 hours, and then vacuum defoamation is 4 hours, obtains the casting solution of transparent and homogeneous;
(2) casting solution after the deaeration processing is put into the spinning still, adopt production line as shown in Figure 2, control measuring pump 1 rotating speed is 10r/min, under the spinning pressure of 0.6MPa, casting solution is extruded the nascent doughnut of formation from spinning head 2, be under the condition of 130m/min through the dry-spinning path of 16cm at the coiling draw speed, enter in the coagulating bath 3 and solidify regeneration, coagulating bath 3 is 30 ℃ 20% ethanol water for temperature, carry out twice two-way (radial and axial) stretching and appropriateness retraction through the first drafting system 4 and the second drafting system 5 again, radial and axial total draw ratio is respectively 1 and 2, obtains doughnut, reels with coiler device 6.Carefully doughnut is put into the absolute ethyl alcohol extraction and removed diluent in 24 hours, process through 2 road pure water soaking and washing again, per pass pure water soaking and washing was processed 16 hours, protected the hole with 50% isopropanol water solution again and processed 8 hours, both can obtain hydrophilicity kynoar hollow-fibre membrane finished product.
Record the internal diameter of PVDF hollow-fibre membrane: 0.50mm, external diameter: 0.90mm, bubble point pressure: 0.90MPa, hot strength: 10.6 ± 0.5MPa, elongation at break: 200 ± 5%, water contact angle: 38 ± 0.5 °, the flux to 25 ℃ of pure water under 0.1MPa pressure is 580L/m
2H.The cross section of film is loose spongelike structure, and described structure has the mesh that is cross-linked with each other, and the equivalent diameter of mesh (being fenestra) is 0.3～0.9 μ m (not shown).
(1) with solid material in advance in 60 ℃ baking oven dry 24 hours to remove moisture, in the mass percent of casting solution total amount, the amphipathic nature block polymer 1.5% that Kynoar powder 50%, gamma-butyrolacton 43.65%, dimethylacetylamide 4.85% and embodiment 2 is synthetic; Putting into intermingling apparatus, is that 220 ℃, mixing speed are agitating heating blend under the condition of 100r/min in temperature, and the blend time is 6 hours, and then vacuum defoamation is 4 hours, obtains the casting solution of transparent and homogeneous
(2) casting solution after the deaeration processing is put into the spinning still, adopt production line as shown in Figure 2, control measuring pump 1 rotating speed is 10r/min, under the spinning pressure of 0.6MPa, casting solution is extruded the nascent doughnut of formation from spinning head 2, the dry-spinning path of process 16cm under the condition of coiling draw speed 150m/min, enter in the coagulating bath 3 and solidify regeneration, coagulating bath 3 is 30 ℃ 20% ethanol water for temperature, carry out twice two-way (radial and axial) stretching and appropriateness retraction through the first drafting system 4 and the second drafting system 5 again, radial and axial total draw ratio is respectively 2 and 2, obtains doughnut, reels with coiler device 6.Carefully doughnut is put into the absolute ethyl alcohol extraction and removed diluent in 24 hours, process through 2 road pure water soaking and washing again, per pass pure water soaking and washing was processed 24 hours, protected the hole with 50% methanol aqueous solution again and processed 8 hours, both can obtain hydrophilicity kynoar hollow-fibre membrane finished product
Record the internal diameter of PVDF hollow-fibre membrane: 0.60mm, external diameter: 0.8mm, bubble point pressure: 0.70MPa, hot strength: 13.5 ± 0.5MPa, elongation at break: 256 ± 5%, water contact angle: 58 ± 0.5 °, the flux to 25 ℃ of pure water under 0.1MPa pressure is 440L/m
2H.The cross section of film is loose spongelike structure, and described structure has the mesh that is cross-linked with each other, and the equivalent diameter of mesh (being fenestra) is 0.1～0.9 μ m (not shown).
Should be understood that those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (10)
1. the preparation method of a hydrophilicity kynoar hollow-fibre membrane is characterized in that, concrete steps are: with Kynoar, composite thinning agent and amphipathic nature block polymer blend preparation casting solution; Casting solution is extruded through spinning head and is formed nascent doughnut, formed nascent doughnut entered solidify regeneration in the coagulating bath, the hollow-fibre membrane that obtains is put into extractant extract diluent, place again the pure water soaking and washing, and with protecting hole agent processing, obtain hydrophilicity kynoar hollow-fibre membrane finished product.
2. the preparation method of hydrophilicity kynoar hollow-fibre membrane as claimed in claim 1, it is characterized in that, the preparation method of described amphipathic nature block polymer is: preparation polydimethylacrylamiin homopolymers, the modification of polydimethylacrylamiin homopolymers is obtained nitrine end group polydimethylacrylamiin, preparation Terminal Acetylenes alkyl poly dimethyl methane siloxanes, nitrine end group polydimethylacrylamiin and Terminal Acetylenes alkyl poly dimethyl methane siloxanes are carried out the click chemistry reaction, obtain containing the amphipathic nature block polymer of polydimethylacrylamiin group and poly dimethyl methane siloxane group.
3. the preparation method of hydrophilicity kynoar hollow-fibre membrane as claimed in claim 2, it is characterized in that, the preparation method of described polydimethylacrylamiin homopolymers is: the DMAA monomer is dissolved in to make concentration in the solvent be 50～90% DMAA solution, add initator and catalyst system, the addition of initator is 0.1～2% of DMAA solution quality, the addition of catalyst system is 0.1～2% of DMAA solution quality, 55～115 ℃ of lower reactions 6～36 hours, obtain the polydimethylacrylamiin homopolymers.Described solvent is preferably one or both the mixture in cyclohexanone, toluene, carrene and the dimethyl formamide.
4. the preparation method of hydrophilicity kynoar hollow-fibre membrane as claimed in claim 2, it is characterized in that, the method of modifying of described polydimethylacrylamiin homopolymers is: polydimethylacrylamiin and sodium azide are joined in the solvent, be mixed with polydimethylacrylamiin concentration and be 10～60% solution, the weight ratio of polydimethylacrylamiin and sodium azide is 1: 1～1: 19,25-80 ℃ of lower reaction 12～72 hours, obtain nitrine end group polydimethylacrylamiin.
5. the preparation method of hydrophilicity kynoar hollow-fibre membrane as claimed in claim 2, it is characterized in that, the preparation method of described Terminal Acetylenes alkyl poly dimethyl methane siloxanes is: terminal hydroxy group poly dimethyl methane siloxanes and 3-propargyl bromide are joined in the solvent, be mixed with terminal hydroxy group poly dimethyl methane siloxane concentrations and be 20～80% solution, the weight ratio of terminal hydroxy group poly dimethyl methane siloxanes and 3-propargyl bromide is 9: 1～1: 9, under stirring condition, add potassium tert-butoxide, the weight ratio of terminal hydroxy group poly dimethyl methane siloxanes and potassium tert-butoxide is 5: 1～1: 5,-10～100 ℃ of reactions 6～24 hours, obtain Terminal Acetylenes alkyl poly dimethyl methane siloxanes.
6. the preparation method of hydrophilicity kynoar hollow-fibre membrane as claimed in claim 2, it is characterized in that, the concrete steps of described click chemistry reaction are: according to the method for click chemistry, nitrine end group polydimethylacrylamiin and Terminal Acetylenes alkyl poly dimethyl methane siloxanes are dissolved in the solvent, being mixed with nitrine end group polydimethylacrylamiin concentration is 2-20%, Terminal Acetylenes alkyl poly dimethyl methane siloxane concentrations is the solution of 20-2%, the weight ratio of nitrine end group polydimethylacrylamiin and Terminal Acetylenes alkyl poly dimethyl methane siloxanes is 9: 1-1: 9, under the effect of catalyst system, react at the 25-105 ℃ of lower click chemistry that occurs, reaction time 2-48 hour, purifying obtains containing the amphipathic nature block polymer of polydimethylacrylamiin group and poly dimethyl methane siloxane group.
7. the preparation method of hydrophilicity kynoar hollow-fibre membrane as claimed in claim 1 is characterized in that, described composite thinning agent is comprised of the first diluent and the second diluent.
8. the preparation method of hydrophilicity kynoar hollow-fibre membrane as claimed in claim 7, it is characterized in that, the compound method of described casting solution is: in the mass percent of casting solution total amount, with Kynoar powder 12%～50%, composite thinning agent 48～87.5%, amphipathic nature block polymer 0.5%～2%, put into intermingling apparatus, be that 70～220 ℃, mixing speed are agitating heating blend under the condition of 80～120r/min in temperature, the blend time is 1～6 hour, then vacuum defoamation is 1～4 hour, obtains the casting solution of transparent and homogeneous.
9. the preparation method of hydrophilicity kynoar hollow-fibre membrane as claimed in claim 7 is characterized in that, before blend, with solid material in advance in 60 ℃ baking oven dry 24 hours to remove moisture.
10. the preparation method of hydrophilicity kynoar hollow-fibre membrane as claimed in claim 1, it is characterized in that, the cross section of the hydrophilicity kynoar hollow-fibre membrane finished product of gained is the spongelike structure with the mesh that is cross-linked with each other, and the equivalent diameter of mesh is 0.1～1 μ m.
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| CN103736408B (en) * | 2013-12-31 | 2015-11-18 | 中科院广州化学有限公司 | A kind of polysulfone porous membrane to temperature, acidity response and preparation method thereof and application |
| CN103861480A (en) * | 2014-03-21 | 2014-06-18 | 东华大学 | Preparation method of hydrophilic polyvinylidene fluoride flat sheet membrane and hollow fiber membrane |
| CN110193290A (en) * | 2019-05-30 | 2019-09-03 | 江苏大学 | A kind of preparation method and application based on click chemistry trace lincomycin molecular compound film |
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| CN111389233B (en) * | 2020-03-20 | 2022-07-01 | 北京碧水源膜科技有限公司 | Preparation method of microfiltration membrane repairing liquid for functional layer damage and microfiltration membrane repairing method |
| CN112044282A (en) * | 2020-09-11 | 2020-12-08 | 天津工业大学 | Method for preparing hollow fiber loose nanofiltration membrane by air self-absorption mode |
| CN115212736A (en) * | 2022-07-15 | 2022-10-21 | 中国科学院烟台海岸带研究所 | Separation membrane for seawater industrial aquaculture water treatment |
| CN115715934A (en) * | 2022-12-05 | 2023-02-28 | 阿克菲姆膜材(嘉兴)有限公司 | Ethylene-chlorotrifluoroethylene copolymer hollow fiber membrane and membrane casting solution thereof |
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