CN105195031A - Hydrogel modified polymer separation membrane preparation method - Google Patents
Hydrogel modified polymer separation membrane preparation method Download PDFInfo
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- CN105195031A CN105195031A CN201510635859.4A CN201510635859A CN105195031A CN 105195031 A CN105195031 A CN 105195031A CN 201510635859 A CN201510635859 A CN 201510635859A CN 105195031 A CN105195031 A CN 105195031A
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Abstract
The invention discloses a hydrogel modified polymer separation membrane preparation method. The method includes the steps: preliminarily polymerizing hydrophilic monomers under ultraviolet irradiation to obtain a hydrophilic prepolymer, mixing the prepolymer with polymers, additives and cross-linking agents, and adopting a membrane forming machine for coating or extruding the mixture to obtain primary polymer membranes; subjecting the primary polymer membranes to cross-linking polymerization under ultraviolet irradiation to obtain a hydrogel modified polymer separation membrane. By preparation of the hydrophilic monomers into the prepolymer, the retention rate in a membrane forming process is increased; by subsequent cross-linking for fixing a hydrophilic gel layer onto the surface and a body of the membrane, excellent hydrophilicity and water retentivity of the membrane can be achieved. Compared with a traditional membrane modification method, the hydrogel modified polymer separation membrane preparation method has the advantage that due to the fact that the hydrophilic layer exists in a gel form, better hydrophilicity and higher stability are realized.
Description
Technical field
The present invention relates to the preparation method of polymer separation film, particularly relate to the preparation method of the polymer-modified diffusion barrier of a kind of hydrogel.
Background technology
Membrane separation technique not only has separation, purifying, the function such as concentrated and refining, and has the advantages such as efficient, energy-conservation, simple to operate and environmental protection, shows extremely wide application prospect in fields such as water treatment, the energy, ambient electronic and biological medicines.As its technological core, membrane material mainly contains two large classes, and a class is inoranic membrane, i.e. ceramic membrane; Another kind of is organic film, i.e. polymer film mainly contains TPO film, polysulfones film, and polyamide-based film etc., occupation rate of market is up to more than 90%.When film is applied to water treatment field, inevitably needs the Problem of Wettability solving film, when film can be spontaneously wet out by water fast, just can reach permeability rate and higher water flux faster.Recent study shows, carrying out hydrophilic modifying to Organic polymer film materials is the effective way improving film serviceability.
The method of modifying of polymer film is mainly divided into physical modification and the large class of chemical modification two.Physical modification mainly contain surface coating and blended.Surface cladding process, namely in film surface coating one deck hydrophilic modifier coating, conventional hydrophilic polymer is polyvinyl alcohol, shitosan, PVP, polyacrylamide, polyacrylic acid and amphipathic copolymer etc.Although the method improves the hydrophily of film to a certain extent, due to coating and film surface interaction more weak, modifier easily runs off in time, causes polymer film hydrophily to decline gradually.Blending and modifying, i.e. blended hydroaropic substance in casting solution, as polyethylene glycol, PVP and glycerine etc., but the general molecular weight of these materials is little, and soluble in water, very easily run off in film use procedure, final modified effect is not good.Chemic modified method is mainly surface grafting method, and surface grafting method first utilizes the means such as chemical surface treatment, plasma treatment, ultraviolet irradiation and ozone treatment to produce free radical isoreactivity site on film surface usually, then grafting functional macromolecule, forms grafting layer.The method mainly exists that percent grafting is low, equipment is complicated, be difficult to the shortcomings such as continuous prodution.Therefore, a kind of simple efficient, applicable industrialization quantity-produced polymer separation film hydrophilic modification method of needs development, gives the hydrophilicity of polymer separation film lasting stability.
For the deficiency that prior art exists, the invention provides a kind of effect better, the polymer-modified diffusion barrier preparation method of the hydrogel that performance is more stable.Hydrophilic monomer preliminary polymerization under ultraviolet light irradiation is first prepared into hydrophilic prepolymer body by this method, more blended in casting solution, makes nascent polymer film; Then by nascent polymer film further cross-linked polymeric under ultraviolet light irradiation, the polymer-modified diffusion barrier of the hydrogel with stable hydrophilic performance is made.The method has fully utilized the advantage of in-situ polymerization and cross-linked polymeric, improves the dispersiveness of hydrophilic substance in film and retention rate.Present invention, avoiding patent CN104479354A and paper (M.m.Tao, F.Liu, J.Mater.Chem., 2012,22,9131) problems such as the in-situ polymerization described in prepares the casting solution lack of homogeneity that hydrophilic polymer microporous barrier exists, and film ratio of defects is high.The polymer-modified diffusion barrier of hydrogel prepared by the present invention, structure is homogeneous, ratio of defects is low, hydrophilicity significantly improves, and has greatly widened the range of application of film.
Summary of the invention
The object of the invention is the preparation method providing the polymer-modified diffusion barrier of a kind of hydrogel.For achieving the above object, the technical solution adopted in the present invention step is as follows:
(1) under nitrogen protection, by mass percent be 10 ~ 50% hydrophilic monomer and mass percent be 1% initator to be dissolved in mass percent be in the solvent of 49 ~ 89%, after dissolving completely, irradiation 1 ~ 10 minute under ultraviolet light, generates hydrophilic prepolymer body;
(2) by mass percent be 15 ~ 25% masking polymer, the additive of 10 ~ 20%, the crosslinking agent of 1% and 5 ~ 10% hydrophilic prepolymer body, be dissolved in the solvent of mass percent 44 ~ 69% at 60 DEG C, after abundant dissolving, standing and defoaming obtains casting solution, casting solution is coated with through film-forming machine or extrudes, immerse curing molding in pure water bath, 25 DEG C of washings, obtain nascent polymer diffusion barrier;
(3) nascent polymer diffusion barrier to be placed under ultraviolet light cross-linking radiation 1 ~ 10 minute, after taking out washing, backlight is dried, and obtains the polymer-modified diffusion barrier of hydrogel.
Described hydrophilic monomer is one or both in hydroxyethyl methacrylate, NVP, acrylic acid, NIPA, NMA, acrylamide, DAAM or 2-acrylamide-2-methylpro panesulfonic acid.
Described initator is any one in benzoin dimethylether, benzophenone, TMDPO, 2-hydroxy-2-methyl-1-phenylacetone or methyl benzoylformate.
Described solvent is any one in DMA, DMF, dimethyl sulfoxide (DMSO) or triethyl phosphate.
Described masking polymer is any one in polyether sulfone, polysulfones, Kynoar or polyvinyl chloride.
Described additive is one or more in polyethylene glycol, polyvinylpyrrolidone, glycerine, oxireme-propylene oxide-oxireme triblock copolymer, APES, silicone oil.
Described crosslinking agent is any one in GDMA, glutaraldehyde or N, N-methylene-bisacrylamide.
The shape of the polymer-modified diffusion barrier of described hydrogel is flat or hollow fiber form.
The invention has the beneficial effects as follows:
The present invention fully utilizes the advantage of in-situ copolymerization and cross-linking reaction, first hydrophilic monomer is introduced in film with performed polymer form, in film surface and body, network-like hydrogel layer is formed again by UV-crosslinked, efficiently solve that hydroaropic substance retention rate in hydrophilic modification diffusion barrier is low, poor stability and the problem such as film ratio of defects is high, give the hydrophilicity of polymer microporous film lasting stability.Simultaneously production technology of the present invention is simple, can continuous operation, is applicable to suitability for industrialized production.
Detailed description of the invention
Embodiment hereafter will make more detailed description to the present invention, but described embodiment is not construed as limiting the invention.From disclosed by the invention content associated to or derive all distortion, all think protection scope of the present invention.
Embodiment 1:
Under nitrogen protection the hydroxyethyl methacrylate of 10wt% and 1wt% benzoin dimethylether are dissolved in 89wt%N, in N-dimethylacetylamide, after dissolving completely, irradiation 1 minute under 365nm ultraviolet light, generates hydroxyethyl methacrylate performed polymer; By 15wt% polyether sulfone, 5wt% polyethylene glycol, 3wt% polyvinylpyrrolidone, 2wt% APES, 1wt% GDMA and 5wt% hydroxyethyl methacrylate performed polymer, 69wt%N is dissolved at 60 DEG C, in N-dimethylacetylamide, standing and defoaming obtains casting solution, casting solution is coated with through film-forming machine, immerse curing molding in pure water bath, 25 DEG C of washings, obtain nascent polyether sulfone flat-plate separation film; To come into being polyether sulfone flat-plate separation film, to be placed under 365nm ultraviolet light cross-linking radiation 1 minute, after taking out washing, backlight is dried, and obtains hydrogel modified poly (ether-sulfone) flat-plate separation film.
Film properties is: pure water flux 1000kg/m
2h, contact angle 60 °, reduced to 10 ° at 60 seconds, flux recovery rate 60%, and tensile strength is 4MPa, and elongation at break is 263%, BSA rejection 80%.
Embodiment 2:
Under nitrogen protection the NVP of 50wt% and 1wt% benzophenone are dissolved in 49wt%N, in dinethylformamide, until completely dissolved, irradiation 10 minutes under 365nm ultraviolet light, generates NVP performed polymer; By 25wt% polysulfones, 10wt% polyethylene glycol, 5wt% polyvinylpyrrolidone, 3wt% glycerine, 2wt% silicone oil, 1wt% glutaraldehyde and 10wt%%N-vinyl pyrrolidone performed polymer, evenly 44wt%N is dissolved at 60 DEG C, in dinethylformamide, standing and defoaming obtains casting solution, casting solution is extruded through film-forming machine, immerse curing molding in pure water bath, 25 DEG C of washings, obtain nascent polysulfone hollow fibre diffusion barrier; To come into being polysulfone hollow fibre diffusion barrier, to be placed under 365nm ultraviolet light cross-linking radiation 10 minutes, after taking out washing, backlight is dried, and obtains hydrogel modified polysulfone hollow fiber separating film.
Film properties is: pure water flux 800kg/m
2h, contact angle 50 °, reduced to 5 ° at 60 seconds, flux recovery rate 65%, and tensile strength is 4.2MPa, and elongation at break is 254%, BSA rejection 70%.
Embodiment 3:
Be dissolved in 69wt% triethyl phosphate by 30wt% acrylamide and 1wt% benzophenone under nitrogen protection, until completely dissolved, irradiation 5 minutes under 365nm ultraviolet light, generates acrylamide performed polymer; By 20wt% Kynoar, 5wt% polyethylene glycol, 4wt% polyvinylpyrrolidone, 4wt% Pluronic F-127-polycyclic oxypropylene-Pluronic F-127 triblock copolymer, 1wt% glycerine, 1wt% silicone oil, 1wt%N, N-methylene-bisacrylamide and 8wt% acrylamide performed polymer, evenly be dissolved at 60 DEG C in 56wt% triethyl phosphate, standing and defoaming obtains casting solution, casting solution is coated with through film-forming machine, immerse curing molding in pure water bath, 25 DEG C of washings, obtain nascent polyvinylidene fluoride flat separation film; To come into being polyvinylidene fluoride flat separation film, to be placed under 365nm ultraviolet light cross-linking radiation 5 minutes, after taking out washing, backlight is dried, and obtains hydrogel modified polyvinilidene fluoride flat-plate separation film.
Film properties is: pure water flux 850kg/m
2h, contact angle 55 °, reduced to 5 ° at 40 seconds, flux recovery rate 55%, and tensile strength is 4MPa, and elongation at break is 244%, BSA rejection 85%.
Embodiment 4:
Under nitrogen protection by 35wt% acrylic acid and 1wt%2,4,6-trimethyl benzoyl diphenyl base phosphine oxide is dissolved in 64wt% dimethyl sulfoxide (DMSO), and until completely dissolved, irradiation 6 minutes under 365nm ultraviolet light, generates acrylate prepolymer; By 18wt% polyvinyl chloride, 5wt% polyethylene glycol, 4wt% polyvinylpyrrolidone, 2wt% APES, 1wt% silicone oil, 3wt% Pluronic F-127-polycyclic oxypropylene-Pluronic F-127 triblock copolymer, 1wt%N, N-methylene-bisacrylamide and 8wt% acrylate prepolymer, evenly be dissolved at 60 DEG C in 58wt% dimethyl sulfoxide (DMSO), standing and defoaming obtains casting solution, casting solution is extruded through film-forming machine, immerse curing molding in pure water bath, 25 DEG C of washings, obtain nascent polyvinyl chloride hollow fiber diffusion barrier; To come into being polyvinyl chloride hollow fiber diffusion barrier, to be placed under 365nm ultraviolet light cross-linking radiation 6 minutes, after taking out washing, backlight is dried, and obtains hydrogel modified polyvinyl chloride hollow fiber separating film.
Film properties is: pure water flux 700kg/m
2h, contact angle 65 °, reduced to 10 ° at 70 seconds, flux recovery rate 50%, and tensile strength is 3.6MPa, and elongation at break is 220%, BSA rejection 75%.
Embodiment 5:
Under nitrogen protection 15wt% acrylamide, 25wt%2-acrylamide-2-methylpro panesulfonic acid and 1wt%2-hydroxy-2-methyl-1-phenylacetone are dissolved in 59wt%N, in N-dimethylacetylamide, until completely dissolved, irradiation 10 minutes under 365nm ultraviolet light, generates acrylamide and 2-acrylamide-2-methylpro panesulfonic acid performed polymer; By 18wt% Kynoar, 5wt% polyethylene glycol, 5wt% APES, 2wt% silicone oil, 3wt% Pluronic F-127-polycyclic oxypropylene-Pluronic F-127 triblock copolymer, 1wt% GDMA and 10wt% acrylamide and 2-acrylamide-2-methylpro panesulfonic acid performed polymer, evenly 56wt%N is dissolved at 60 DEG C, in N-dimethylacetylamide, standing and defoaming obtains casting solution, preparation liquid is coated with through film-forming machine, immerse curing molding in pure water bath, 25 DEG C of washings, obtain nascent polyvinylidene fluoride flat separation film; To come into being polyvinylidene fluoride flat separation film, to be placed under 365nm ultraviolet light cross-linking radiation 10 minutes, after taking out washing, backlight is dried, and obtains hydrogel modified polyvinilidene fluoride flat-plate separation film.
Film properties is: pure water flux 900kg/m
2h, contact angle 55 °, reduced to 10 ° at 40 seconds, flux recovery rate 60%, and tensile strength is 3.5MPa, and elongation at break is 210%, BSA rejection 90%.
Embodiment 6:
Under nitrogen protection 40wt%N-N-isopropylacrylamide and 1wt%2-hydroxy-2-methyl-1-phenylacetone are dissolved in 59wt%N, in N-dimethylacetylamide, until completely dissolved, irradiation 8 minutes under 365nm ultraviolet light, generates NIPA performed polymer; By 18wt% Kynoar, 5wt% polyethylene glycol, 3wt% polyvinylpyrrolidone, 2wt% glycerine, 2wt% APES, 2wt% silicone oil, 0.5wt.% GDMA, 0.5wt%N, N-methylene-bisacrylamide and 10wt%N-N-isopropylacrylamide performed polymer, evenly 57wt%N is dissolved at 60 DEG C, in dinethylformamide, standing and defoaming makes casting solution, casting solution is extruded through film-forming machine, immerse curing molding in pure water bath, 25 DEG C of washings, obtain nascent polyvinylidene fluoride hollow fiber diffusion barrier; To come into being polyvinylidene fluoride hollow fiber diffusion barrier, to be placed under 365nm ultraviolet light cross-linking radiation 10 minutes, after taking out washing, backlight is dried, and obtains hydrogel modified polyvinilidene fluoride hollow fiber separating film.
Film properties is: pure water flux 600kg/m
2h, contact angle 69 °, reduced to 20 ° at 80 seconds, flux recovery rate 50%, and tensile strength is 4.5MPa, and elongation at break is 260%, BSA rejection 82%.
Embodiment 7:
Under nitrogen protection 25wt% DAAM, 25wt% NMA and 1wt% methyl benzoylformate are dissolved in 49wt%N, in N-dimethylacetylamide, until completely dissolved, irradiation 10 minutes under 365nm ultraviolet light, generates DAAM and NMA performed polymer, by 18wt% polyether sulfone, 5wt% polyethylene glycol, 4wt% polyvinylpyrrolidone, 4wt% Pluronic F-127-polycyclic oxypropylene-Pluronic F-127 triblock copolymer, 1wt% APES, 1wt% silicone oil, 0.5wt% GDMA, 0.5wt%N, N-methylene-bisacrylamide and 10wt% DAAM and NMA performed polymer, evenly 56wt%N is dissolved at 60 DEG C, in N-dimethylacetylamide, standing and defoaming makes casting solution, casting solution is coated with through film-forming machine, immerse curing molding in pure water bath, 25 DEG C of washings, obtain nascent polyether sulfone flat-plate separation film, to come into being polyether sulfone flat-plate separation film, to be placed under 365nm ultraviolet light cross-linking radiation 1 minute, after taking out washing, backlight is dried, and obtains hydrogel modified poly (ether-sulfone) flat-plate separation film.
Film properties is: pure water flux 850kg/m
2h, contact angle 60 °, reduced to 5 ° at 50 seconds, flux recovery rate 58%, and tensile strength is 4MPa, and elongation at break is 240%, BSA rejection 93%.
Claims (8)
1. a preparation method for the polymer-modified diffusion barrier of hydrogel, is characterized in that comprising the steps:
(1) under nitrogen protection, by mass percent be 10 ~ 50% hydrophilic monomer and mass percent be 1% initator to be dissolved in mass percent be in the solvent of 49 ~ 89%, after dissolving completely, irradiation 1 ~ 10 minute under ultraviolet light, generates hydrophilic prepolymer body;
(2) by mass percent be 15 ~ 25% masking polymer, the additive of 10 ~ 20%, the crosslinking agent of 1% and 5 ~ 10% hydrophilic prepolymer body, be dissolved in the solvent of mass percent 44 ~ 69% at 60 DEG C, after abundant dissolving, standing and defoaming obtains casting solution, casting solution is coated with through film-forming machine or extrudes, immerse curing molding in pure water bath, 25 DEG C of washings, obtain nascent polymer diffusion barrier;
(3) nascent polymer diffusion barrier to be placed under ultraviolet light cross-linking radiation 1 ~ 10 minute, after taking out washing, backlight is dried, and obtains the polymer-modified diffusion barrier of hydrogel.
2. according to the preparation method of the polymer-modified diffusion barrier of a kind of hydrogel according to claim 1, it is characterized in that, described hydrophilic monomer is one or both in hydroxyethyl methacrylate, NVP, acrylic acid, NIPA, NMA, acrylamide, DAAM or 2-acrylamide-2-methylpro panesulfonic acid.
3. according to the preparation method of the polymer-modified diffusion barrier of a kind of hydrogel according to claim 1; it is characterized in that; described initator is benzoin dimethylether, benzophenone, 2; any one in 4,6-trimethyl benzoyl diphenyl base phosphine oxide, 2-hydroxy-2-methyl-1-phenylacetone or methyl benzoylformate.
4. according to the preparation method of the polymer-modified diffusion barrier of a kind of hydrogel according to claim 1, it is characterized in that, described solvent is any one in DMA, DMF, dimethyl sulfoxide (DMSO) or triethyl phosphate.
5. according to the preparation method of the polymer-modified diffusion barrier of a kind of hydrogel according to claim 1, it is characterized in that, described masking polymer is any one in polyether sulfone, polysulfones, Kynoar or polyvinyl chloride.
6. according to the preparation method of the polymer-modified diffusion barrier of a kind of hydrogel according to claim 1, it is characterized in that, described additive is one or more in polyethylene glycol, polyvinylpyrrolidone, glycerine, oxireme-propylene oxide-oxireme triblock copolymer, APES, silicone oil.
7. according to the preparation method of the polymer-modified diffusion barrier of a kind of hydrogel according to claim 1, it is characterized in that, described crosslinking agent is any one in GDMA, glutaraldehyde or N, N-methylene-bisacrylamide.
8. the preparation method of the polymer-modified diffusion barrier of a kind of hydrogel according to claim 1, is characterized in that, the shape of the polymer-modified diffusion barrier of described hydrogel is flat or hollow fiber form.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1159770A (en) * | 1994-07-28 | 1997-09-17 | 米利波尔公司 | Porous composite membrane and making process |
| CN101862604A (en) * | 2010-06-28 | 2010-10-20 | 厦门绿邦膜技术有限公司 | Method for preparing hydrophilic porous membrane |
| EP1945380B1 (en) * | 2005-11-08 | 2011-02-16 | SurModics, Inc. | Ultra-thin photo-polymeric coatings and uses thereof |
| CN103418254A (en) * | 2012-05-21 | 2013-12-04 | 中国科学院化学研究所 | Method of hydrophilic modification of polyvinylidene fluoride membrane |
| CN104707486A (en) * | 2015-03-03 | 2015-06-17 | 浙江大学 | Preparation method for high-strength hydrogel filtering membrane |
-
2015
- 2015-09-30 CN CN201510635859.4A patent/CN105195031B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1159770A (en) * | 1994-07-28 | 1997-09-17 | 米利波尔公司 | Porous composite membrane and making process |
| EP1945380B1 (en) * | 2005-11-08 | 2011-02-16 | SurModics, Inc. | Ultra-thin photo-polymeric coatings and uses thereof |
| CN101862604A (en) * | 2010-06-28 | 2010-10-20 | 厦门绿邦膜技术有限公司 | Method for preparing hydrophilic porous membrane |
| CN103418254A (en) * | 2012-05-21 | 2013-12-04 | 中国科学院化学研究所 | Method of hydrophilic modification of polyvinylidene fluoride membrane |
| CN104707486A (en) * | 2015-03-03 | 2015-06-17 | 浙江大学 | Preparation method for high-strength hydrogel filtering membrane |
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| CN109092067A (en) * | 2018-10-08 | 2018-12-28 | 湖北中泉环保技术有限公司 | A kind of casting film agent and preparation method thereof |
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