CN103990384A - Preparation method of novel organic-inorganic hybridization micropore separation membrane - Google Patents
Preparation method of novel organic-inorganic hybridization micropore separation membrane Download PDFInfo
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Abstract
The invention discloses a preparation method of a novel organic-inorganic hybridization micropore separation membrane. The preparation method comprises the following steps: grafting a polymer on the surface of nano silicon dioxide through reversible addition-fragmentation chain transfer to obtain polymer-grafted-silicon dioxide organic-inorganic hybridization nanometer particles, dispersing the polymer-grafted-silicon dioxide organic-inorganic hybridization nanometer particles in a quaternization reagent solution, stirring for 0.5-24 hours, realizing quaternization of the grafted polymer to obtain quaternization hybridization nanometer particles; with the quaternization hybridization nanometer particles as a dispersing phase, and a polymer membrane material as a main phase, preparing the organic-inorganic hybridization micropore separation membrane through a non-solvent inductive phase separation method. According to the preparation method, the agglomeration behavior of inorganic nanometer particles can be effectively inhibited, the dispersibility of the inorganic nanometer particles in a polymer matrix is promoted, the interaction of an organic phase and an inorganic phase is increased, the stability of the inorganic nanometer particles in the polymer matrix is improved, and multiple performances of hydrophilia, permselectivity, anti-fouling performance and antibacterial property of the separation membrane can be remarkably improved.
Description
Technical field
The invention belongs to membrane separation technique field, relate in particular to a kind of preparation method of novel organic-inorganic hybrid microporous separation membrane.
Background technology
Membrane separation technique day by day develops into the key technology that solves water resources problems, has obtained the great attention of countries in the world, and film is the core of membrane process.Current most membrane technology all depends on polymer film, polymer film has the advantages such as raw material sources are extensive, easily processing, cost is low, pliability is good, be widely used in the fields such as feedwater/draining processing, sewage disposal, desalinization, but, polymer film still comes with some shortcomings, shorter etc. such as non-refractory, not organic solvent-resistant and chemical attack, life-span.And, most polymers membrane material hydrophobicity is stronger, in aqueous phase separation process, the materials such as the protein in water, bacterium and humic acid easily adsorb/are deposited on film surface by hydrophobic interaction, cause film to pollute, reduce water flux and the water outlet quality of film, affect the performance of film, shorten the service life of film.Therefore, usually need it to carry out modification, improve the performances such as its separation property, hydrophily, resistance tocrocking.Moreover, when polymer film is during for the field relevant with biology such as haemodialysis, also should improve its blood compatibility.
The method of modifying of polymer film is varied, mainly comprises the methods such as surface grafting, surface treatment, surface coating and blending and modifying.Surface graft modification method, modified effect is lasting, and selectable monomeric species is many, but technological process is long, belongs to twice-modified method, easily polymer film matrix particle is damaged.Equally, surface-treated method easily causes the damage of polymer-based film.The method of modifying that surface applies, is the method for modifying of usually using in industry, and in this method, the kind of matrix and shape are unrestricted, and coating speed is fast, is beneficial to large-scale production, but due to a little less than the active force between coating and matrix and easily peel off.Blending modification method, film forming and modification complete simultaneously, do not need after-treatment, simple and easy to do, are the method for modifying that is widely used at present research, but the conventional modifier such as PEG and PVP easily runs off in long-term use procedure, and modified effect is not lasting.
In recent years, risen the method with inorganic nano particle modified polymer film.Inorganic nano-particle is incorporated in the surface or body of polymer film, prepares hybrid organic-inorganic film (J. Membr. Sci., 337 (2009): 257-265; Polymer, 47 (2006): 2683-2688; J. Membr. Sci., 366 (2011): 97-103; J. Membr. Sci., 389 (2012): 155-161; J. Membr. Sci., 437 (2013): 216-226), can effectively improve the heat endurance of polymeric membrane, adjust parent-hydrophobic balance, controlling diaphragm swelling, pore structure and the distribution of improvement and modified membrane, improve the solvent resistance of film, selective and permeability, strengthening the mechanical strength of film, is the effective way of preparation, development of new peplomer.But, owing to having high surface energy and large specific area, easily there is agglomeration in inorganic nano-particle, the structure of hybridized film and performance are caused to adverse effect, and a little less than organic and inorganic two alternate interactions, the inorganic nano-particle that diffusion barrier adds in long-term use procedure easily runs off, and causes secondary pollution.In order to solve above-mentioned significant problem, usually need the surface of inorganic nano-particle to modify and be used further to prepare hybrid organic-inorganic film, to one of inorganic nano particle modified the most frequently used method, be at inorganic nano-particle surface grafting polymerization thing.
The olefin monomer that contains tertiary amine group is grafted on to Nano particles of silicon dioxide surface, generate inorganic-organic hybridization nano particle, then under gentle condition, there is quaterisation, be transformed into quaternised inorganic-organic hybridization nano particle, using it as decentralized photo, take polymeric film material as principal phase, by non-solvent, induce phase separation method to prepare hybrid organic-inorganic film, not only can effectively suppress the reunion behavior of inorganic nano-particle, promote its dispersiveness in polymeric matrix, increase the interaction of organic and inorganic two-phase, improve the stability of inorganic nano-particle in polymeric matrix, and can give full play to the speciality of quaternary ammonium type polymer, the significant hydrophily that improves film, select permeability, many performances such as resistance tocrocking and antibiotic property.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of novel organic-inorganic hybrid microporous separation membrane is provided.
The inventive method comprises the steps:
Step (1). at nano-silica surface by reversible addition-fracture chain transfer polymerization (RAFT) graft polymers, centrifugation 3～10 times, obtain the inorganic-organic hybridization nano particle of the polymer-grafting-silica of purifying, wherein, the mass content of graft polymers is 5～60 ﹪;
The diameter of described nano silicon is 30～100 nanometers;
Described graft polymers is poly-(dimethylaminoethyl methacrylate), poly-(diethyl aminoethyl methacrylate), poly-(dimethylaminoethyl acrylate), poly-(acrylic acid diethylamino ethyl ester), P4VP, poly-(2-vinylpyridine), copolymer is forged in poly-(methyl methacrylate)-poly-(dimethylaminoethyl methacrylate) embedding, copolymer is forged in poly-(methyl methacrylate)-poly-(diethylaminoethyl methacrylate) embedding, copolymer is forged in poly-(methyl methacrylate)-poly-(dimethylaminoethyl acrylate) embedding, copolymer is forged in poly-(methyl methacrylate)-poly-(acrylic acid diethylamino ethyl ester) embedding, copolymer is forged in poly-(methyl methacrylate)-P4VP embedding or copolymer is forged in poly-(methyl methacrylate)-poly-(2-vinylpyridine) embedding, weight average molecular weight is 2, 000～600, 000 gram/mol.
Step (2). the inorganic-organic hybridization nano particle that step (1) is obtained is dispersed in quaternizing agent solution, wherein the mass content of inorganic-organic hybridization nano particle is 0.5～10 ﹪, at 10～80 ℃, stir 0.5～24 hour, realize the quaternized of graft polymers, eccentric cleaning 3～10 times, obtains the quaternized hybridized nanometer particle of purifying;
The methanol solution that described quaternizing agent solution is quaternizing agent, the aqueous solution of quaternizing agent or the acetone soln of quaternizing agent; Wherein in quaternizing agent solution, the mass content of quaternizing agent is 1～10 ﹪;
Described quaternizing agent is 2-bromoacetic acid, 3-bromo-propionic acid, 5-bromine valeric acid, PS, iodomethane or bromoethane;
Step (3). using the quaternized hybridized nanometer particle of step (2) as decentralized photo, take polymeric film material as principal phase, by non-solvent, induce phase separation method to prepare novel inorganic, realize the functionalization of hydridization diffusion barrier simultaneously, concrete way is quaternized hybridized nanometer particle, the N that step (2) is prepared, N '-dimethylacetylamide, polymeric film material, pore-foaming agent mix, at 10～80 ℃, stir 4～24 hours, vacuum defoamation 5～30 minutes, at 10～80 ℃ standing 0.5～12 hour, obtain casting solution; Wherein in casting solution, the mass content of polymeric film material is 12～30 ﹪, N, and the mass content of N '-dimethylacetylamide is 50～85 ﹪, the mass content of pore-foaming agent is 0.5～20 ﹪; By non-solvent, induce phase separation method that casting solution is made to film, then film is immersed in the deionized water of 10～60 ℃ 6～72 hours, take out, obtain novel inorganic.
Described polymeric film material is polysulfones, polyether sulfone or Kynoar;
Described pore-foaming agent is the mixed solution of polyethylene glycol and water; The mass ratio of polyethylene glycol and water is 10:1～1:10.
The inorganic that the present invention prepares is novel hybrid inorganic-organic microfiltration membranes or milipore filter.
beneficial effect of the present invention:olefin monomer containing tertiary amine group is grafted on to Nano particles of silicon dioxide surface, generate inorganic-organic hybridization nano particle, then under gentle condition, there is quaterisation, be transformed into quaternised inorganic-organic hybridization nano particle, using it as decentralized photo, take polymeric film material as principal phase, by non-solvent, induce phase separation method to prepare hybrid organic-inorganic film, not only can effectively suppress the reunion behavior of inorganic nano-particle, promote its dispersiveness in polymeric matrix, increase the interaction of organic and inorganic two-phase, improve the stability of inorganic nano-particle in polymeric matrix, and can improve significantly the hydrophily of diffusion barrier, select permeability, many performances such as resistance tocrocking and antibiotic property.In the present invention, masking is synchronizeed and is carried out with film modification, and production efficiency is high, cost is low, is beneficial to large-scale Development and Production, has the prospect of wide industrial applications.
The specific embodiment
The present invention is that to take the quaternised hybrid inorganic-organic Nano particles of silicon dioxide in surface be decentralized photo, take polymeric film material as principal phase, by non-solvent, induces phase separation method to prepare novel inorganic, realizes its functionalization simultaneously.
Below in conjunction with embodiment, the present invention is described in more detail, but described embodiment is not construed as limiting the invention.From disclosed by the invention content associated to or all distortion of deriving, all think protection scope of the present invention.
Embodiment 1.
60g poly-(dimethylaminoethyl methacrylate) is grafted on to the Nano particles of silicon dioxide surface that 40g diameter is 100 nanometers by reversible addition-fracture chain transfer polymerization (RAFT), centrifugation 10 times, obtain poly-(dimethylaminoethyl methacrylate)-grafting-silica inorganic-organic hybridization nano particle of purifying, the weight average molecular weight of graft polymers is 600,000 grams/mol; Poly-(dimethylaminoethyl methacrylate)-grafting-silica inorganic-organic hybridization nano particle of 0.5g is dispersed in the acetone soln (in the acetone soln of 5-bromine valeric acid, the mass percent concentration of 5-bromine valeric acid is 10 ﹪) of 99.5g 5-bromine valeric acid, at 10 ℃, stir 24 hours, realize the quaternized of poly-(dimethylaminoethyl methacrylate), centrifugation 10 times, obtains the quaternised inorganic-organic hybridization nano particle of purifying; By 10g inorganic-organic hybridization nano particle, 50g N, N '-dimethylacetylamide, 30g polysulfones, 10g pore-foaming agent (in pore-foaming agent, the mass ratio of polyethylene glycol and water is 10:1), stir 24 hours vacuum defoamation 30 minutes at 10 ℃, at 10 ℃ standing 12 hours, obtain casting solution; By non-solvent, induce phase separation method masking, film is immersed in the deionized water of 10 ℃ 72 hours, take out, obtaining take quaternized inorganic-organic hybridization nano particle is decentralized photo, the novel organic-inorganic hybrid microfiltration membranes that the polysulfones of take is principal phase.
The water contact angle of the novel organic-inorganic hybrid microfiltration membranes that embodiment 1 is prepared, water flux and bovine serum albumin(BSA) rejection see attached list 1, this novel organic-inorganic hybrid microfiltration membranes water contact angle be 37 °, water flux is 459 Lm
-2h
-1, to bovine serum albumin(BSA) rejection, be 71 ﹪.
Embodiment 2.
5g poly-(diethyl aminoethyl methacrylate) is grafted on to the Nano particles of silicon dioxide surface that 95g diameter is 30 nanometers by reversible addition-fracture chain transfer polymerization (RAFT), centrifugation 3 times, obtain poly-(diethyl aminoethyl methacrylate)-grafting-silica inorganic-organic hybridization nano particle of purifying, the weight average molecular weight of graft polymers is 2,000 grams/mol; Poly-(diethyl aminoethyl methacrylate)-grafting-silica inorganic-organic hybridization nano particle of 10g is dispersed in the aqueous solution (in the aqueous solution of 3-bromo-propionic acid, the mass percent concentration of 3-bromo-propionic acid is 1 ﹪) of 90g 3-bromo-propionic acid, at 80 ℃, stir 0.5 hour, centrifugation 3 times, obtains the quaternized inorganic-organic hybridization nano particle of purifying; By the quaternized inorganic-organic hybridization nano particle of 0.5g, 85gN, N '-dimethylacetylamide, 12g Kynoar, 2.5g pore-foaming agent (in pore-foaming agent, polyethylene glycol is 1:10 with the mass ratio of water) mix, at 80 ℃, stir 4 hours, vacuum defoamation 5 minutes, at 80 ℃ standing 0.5 hour, obtain casting solution; By non-solvent, induce phase separation method masking, film is immersed in the deionized water of 60 ℃ 6 hours, take out, obtaining take quaternized inorganic-organic hybridization nano particle is decentralized photo, the novel organic-inorganic hybrid microfiltration membranes that the Kynoar of take is principal phase.
Embodiment 3.
45g poly-(acrylic acid diethylamino ethyl ester) is grafted on to the Nano particles of silicon dioxide surface that 55g diameter is 50 nanometers by reversible addition-fracture chain transfer polymerization (RAFT), centrifugation 6 times, obtain poly-(first acrylic acid diethylamino ethyl ester)-grafting-silica inorganic-organic hybridization nano particle of purifying, the weight average molecular weight of graft polymers is 400,000 grams/mol; Poly-(the first acrylic acid diethylamino ethyl ester)-grafting-silica inorganic-organic hybridization nano particle of 5g is dispersed in to 95g 1, the aqueous solution (1 of 3-N-morpholinopropanesulfonic acid lactone, in the aqueous solution of 3-N-morpholinopropanesulfonic acid lactone 1, the mass percent concentration of 3-N-morpholinopropanesulfonic acid is 2 ﹪) in stir 8 hours at 40 ℃, realize the quaternized of poly-(acrylic acid lignocaine ethyl ester), centrifugation 5 times, obtains the quaternized inorganic-organic hybridization nano particle of purifying; By the quaternized inorganic-organic hybridization nano particle of 2g, 79.5gN, N '-dimethylacetylamide, 18g polyether sulfone, 0.5g pore-foaming agent (in pore-foaming agent, polyethylene glycol is 1:1 with the mass ratio of water) mix, at 60 ℃, stir 12 hours, vacuum defoamation 10 minutes, at 60 ℃ standing 2 hours, obtain casting solution; By non-solvent, induce phase separation method masking, film is immersed in the deionized water of 30 ℃ 48 hours, take out, obtaining take amphoteric ion type inorganic-organic hybridization nano particle is decentralized photo, the novel organic-inorganic hybrid milipore filter that the polyether sulfone of take is principal phase.
The water contact angle of the novel organic-inorganic hybrid milipore filter that embodiment 3 is prepared, water flux and bovine serum albumin(BSA) rejection see attached list 1, and the water contact angle of this novel organic-inorganic hybrid milipore filter is 42 °, and water flux is Lm
-2h
-1, to bovine serum albumin(BSA) rejection, be 88 ﹪.
Embodiment 4.
17g P4VP is grafted on to the Nano particles of silicon dioxide surface that 83g diameter is 70 nanometers by reversible addition-fracture chain transfer polymerization (RAFT), centrifugation 8 times, obtain P4VP-grafting-silica inorganic-organic hybridization nano particle of purifying, the weight average molecular weight of graft polymers is 25,000 grams/mol; 8g P4VP-grafting-silica inorganic-organic hybridization nano particle is dispersed in the methanol solution (in the methanol solution of iodomethane, the mass percent concentration of iodomethane is 4 ﹪) of 92g iodomethane, at 30 ℃, stir 10 hours, realize the quaternized of P4VP, centrifugation 7 times, obtains the quaternized inorganic-organic hybridization nano particle of purifying; By the quaternized inorganic-organic hybridization nano particle of 4g, 64gN, N '-dimethylacetylamide, 24g polysulfones, 8g pore-foaming agent (in pore-foaming agent, polyethylene glycol is 3:7 with the mass ratio of water) mix, and stir 8 hours vacuum defoamation 15 minutes at 40 ℃, at 40 ℃ standing 10 hours, obtain casting solution; By non-solvent, induce phase separation method masking, film is immersed in the deionized water of 40 ℃ 24 hours, take out, obtaining take quaternized inorganic-organic hybridization nano particle is decentralized photo, the novel organic-inorganic hybrid milipore filter that the polysulfones of take is principal phase.
Embodiment 5.
45g poly-(dimethylaminoethyl acrylate) is grafted on to the Nano particles of silicon dioxide surface that 55g diameter is 80 nanometers by reversible addition-fracture chain transfer polymerization (RAFT), centrifugation 7 times, obtain poly-(dimethylaminoethyl acrylate)-grafting-silica inorganic-organic hybridization nano particle of purifying, the weight average molecular weight of graft polymers is 350,000 grams/mol; Poly-(dimethylaminoethyl acrylate)-grafting-silica inorganic-organic hybridization nano particle of 3g is dispersed in the methanol solution (in the methanol solution of iodomethane, the mass percent concentration of iodomethane is 4 ﹪) of 97g iodomethane, at 35 ℃, stir 16 hours, realize the quaternized of poly-(dimethylaminoethyl acrylate), centrifugation 4 times, obtains the quaternized inorganic-organic hybridization nano particle of purifying; By the quaternised inorganic-organic hybridization nano particle of 7g, 73gN, N '-dimethylacetylamide, 16g Kynoar, 4g pore-foaming agent (in pore-foaming agent, polyethylene glycol is 3:2 with the mass ratio of water) mix, at 50 ℃, stir 10 hours, vacuum defoamation 20 minutes, at 50 ℃ standing 3 hours, obtain casting solution; By non-solvent, induce phase separation method masking, film is immersed in the deionized water of 50 ℃ 60 hours, take out, obtaining take quaternized inorganic-organic hybridization nano particle is decentralized photo, the novel organic-inorganic hybrid milipore filter that the Kynoar of take is principal phase.
The water contact angle of the novel organic-inorganic hybrid milipore filter that embodiment 5 is prepared, water flux and bovine serum albumin(BSA) rejection see attached list 1, and this novel organic-inorganic hybrid milipore filter water contact angle is 44 °, and water flux is 183 Lm
-2h
-1, to bovine serum albumin(BSA) rejection, be 57 ﹪.
Embodiment 6.
58g poly-(2-vinylpyridine) is grafted on to the Nano particles of silicon dioxide surface that 42g diameter is 90 nanometers by reversible addition-fracture chain transfer polymerization (RAFT), centrifugation 8 times, obtain poly-(2-vinylpyridine)-grafting-silica inorganic-organic hybridization nano particle of purifying, the weight average molecular weight of graft polymers is 550,000 grams/mol; Poly-(the 2-vinylpyridine)-grafting-silica inorganic-organic hybridization nano particle of 3g is dispersed in the methanol solution (in the methanol solution of iodomethane, the mass percent concentration of iodomethane is 4 ﹪) of 97g iodomethane, at 35 ℃, stir 16 hours, realize the quaternized of poly-(2-vinylpyridine), centrifugation 4 times, obtains the quaternized inorganic-organic hybridization nano particle of purifying; By the quaternized inorganic-organic hybridization nano particle of 7g, 63gN, N '-dimethylacetylamide, 10g Kynoar, 20g pore-foaming agent (in pore-foaming agent, polyethylene glycol is 3:2 with the mass ratio of water) mix, at 50 ℃, stir 10 hours, vacuum defoamation 20 minutes, at 50 ℃ standing 3 hours, obtain casting solution; By non-solvent, induce phase separation method masking, film is immersed in the deionized water of 50 ℃ 60 hours, take out, obtaining take quaternized inorganic-organic hybridization nano particle is decentralized photo, the novel organic-inorganic hybrid microfiltration membranes that the Kynoar of take is principal phase.
Embodiment 7.
20g poly-(methyl methacrylate)-poly-(dimethylaminoethyl methacrylate) embedding is forged to copolymer and by reversible addition-fracture chain transfer polymerization (RAFT), be grafted on the Nano particles of silicon dioxide surface that 80g diameter is 70 nanometers, centrifugation 4 times, copolymer-grafting-silica inorganic-organic hybridization nano particle is forged in poly-(methyl methacrylate)-poly-(dimethylaminoethyl methacrylate) embedding that obtains purifying, the weight average molecular weight of graft polymers is 150,000 grams/mol; 2g poly-(methyl methacrylate)-poly-(dimethylaminoethyl methacrylate) embedding is forged to copolymer-grafting-silica inorganic-organic hybridization nano particle and is dispersed in the acetone soln (in the acetone soln of 5-bromine valeric acid, the mass percent concentration of 5-bromine valeric acid is 10 ﹪) of 98g 5-bromine valeric acid, at 30 ℃, stir 12 hours, the quaternized of copolymer forged in realize poly-(methyl methacrylate)-poly-(dimethylaminoethyl methacrylate) embedding, centrifugation 3 times, obtains the quaternized inorganic-organic hybridization nano particle of purifying; By the quaternized inorganic-organic hybridization nano particle of 4g, 65gN, N '-dimethylacetylamide, 13g Kynoar, 18g pore-foaming agent (in pore-foaming agent, polyethylene glycol is 3:2 with the mass ratio of water) mix, at 50 ℃, stir 10 hours, vacuum defoamation 20 minutes, at 50 ℃ standing 3 hours, obtain casting solution; By non-solvent, induce phase separation method masking, film is immersed in the deionized water of 50 ℃ 60 hours, take out, obtaining take quaternized inorganic-organic hybridization nano particle is decentralized photo, the novel organic-inorganic hybrid microfiltration membranes that the Kynoar of take is principal phase.
The water contact angle of the novel organic-inorganic hybrid microfiltration membranes that embodiment 7 is prepared, water flux and bovine serum albumin(BSA) rejection see attached list 1, and this novel organic-inorganic hybrid microfiltration membranes water contact angle is 59 °, and water flux is 4512 Lm
-2h
-1, to bovine serum albumin(BSA) rejection, be 38 ﹪.
Embodiment 8.
50g poly-(methyl methacrylate)-poly-(diethyl aminoethyl methacrylate) embedding is forged to copolymer and by reversible addition-fracture chain transfer polymerization (RAFT), be grafted on the Nano particles of silicon dioxide surface that 50g diameter is 30 nanometers, centrifugation 3 times, copolymer-grafting-silica inorganic-organic hybridization nano particle is forged in poly-(methyl methacrylate)-poly-(diethyl aminoethyl methacrylate) embedding that obtains purifying, the weight average molecular weight of graft polymers is 12,000 grams/mol; 10g poly-(methyl methacrylate)-poly-(diethyl aminoethyl methacrylate) embedding is forged to copolymer-grafting-silica inorganic-organic hybridization nano particle and is dispersed in the aqueous solution (in the aqueous solution of 3-bromo-propionic acid, the mass percent concentration of 3-bromo-propionic acid is 1 ﹪) of 90g 3-bromo-propionic acid, at 80 ℃, stir 0.5 hour, the quaternized of copolymer forged in realize poly-(methyl methacrylate)-poly-(diethyl aminoethyl methacrylate) embedding, centrifugation 3 times, obtains the quaternized inorganic-organic hybridization nano particle of purifying; By the quaternized inorganic-organic hybridization nano particle of 0.5g, 85gN, N '-dimethylacetylamide, 12g Kynoar, 2.5g pore-foaming agent (in pore-foaming agent, polyethylene glycol is 1:10 with the mass ratio of water) mix, at 80 ℃, stir 4 hours, vacuum defoamation 5 minutes, at 80 ℃ standing 0.5 hour, obtain casting solution; By non-solvent, induce phase separation method masking, film is immersed in the deionized water of 60 ℃ 6 hours, take out, obtaining take quaternized inorganic-organic hybridization nano particle is decentralized photo, the novel organic-inorganic hybrid milipore filter that the Kynoar of take is principal phase.
Embodiment 9.
25g poly-(methyl methacrylate)-poly-(acrylic acid diethylamino ethyl ester) embedding is forged to copolymer and by reversible addition-fracture chain transfer polymerization (RAFT), be grafted on the Nano particles of silicon dioxide surface that 75g diameter is 50 nanometers, centrifugation 6 times, copolymer-grafting-silica inorganic-organic hybridization nano particle is forged in poly-(methyl methacrylate)-poly-(the acrylic acid diethylamino ethyl ester) embedding that obtains purifying, the weight average molecular weight of graft polymers is 400,000 grams/mol; 5g poly-(methyl methacrylate)-poly-(acrylic acid diethylamino ethyl ester) embedding is forged to copolymer-grafting-silica inorganic-organic hybridization nano particle and be dispersed in 95g 1, the aqueous solution (1 of 3-N-morpholinopropanesulfonic acid lactone, in the aqueous solution of 3-N-morpholinopropanesulfonic acid lactone 1, the mass percent concentration of 3-N-morpholinopropanesulfonic acid is 2 ﹪) in stir 8 hours at 40 ℃, the quaternized of copolymer forged in realize poly-(methyl methacrylate)-poly-(acrylic acid diethylamino ethyl ester) embedding, centrifugation 5 times, obtains the quaternized inorganic-organic hybridization nano particle of purifying; By the quaternized inorganic-organic hybridization nano particle of 2g, 79.5gN, N '-dimethylacetylamide, 18g polyether sulfone, 0.5g pore-foaming agent (in pore-foaming agent, polyethylene glycol is 1:1 with the mass ratio of water) mix, at 60 ℃, stir 12 hours, vacuum defoamation 10 minutes, at 60 ℃ standing 2 hours, obtain casting solution; By non-solvent, induce phase separation method masking, film is immersed in the deionized water of 30 ℃ 48 hours, take out, obtaining take amphoteric ion type inorganic-organic hybridization nano particle is decentralized photo, the novel organic-inorganic hybrid milipore filter that the polyether sulfone of take is principal phase.
The water contact angle of the novel organic-inorganic hybrid milipore filter that embodiment 9 is prepared, water flux and bovine serum albumin(BSA) rejection see attached list 1, and this novel organic-inorganic hybrid milipore filter water contact angle is 53 °, and water flux is 79 Lm
-2h
-1, to bovine serum albumin(BSA) rejection, be 91 ﹪.
Embodiment 10.
Poly-(methyl methacrylate-) P4VP embedding of 15g is forged to copolymer and by reversible addition-fracture chain transfer polymerization (RAFT), be grafted on the Nano particles of silicon dioxide surface that 85g diameter is 70 nanometers, centrifugation 8 times, copolymer-grafting-silica inorganic-organic hybridization nano particle is forged in poly-(methyl methacrylate-) P4VP embedding that obtains purifying, the weight average molecular weight of graft polymers is 25,000 grams/mol; Poly-(methyl methacrylate-) P4VP embedding of 8g is forged to copolymer-grafting-silica inorganic-organic hybridization nano particle to be dispersed in the methanol solution (in the methanol solution of iodomethane, the mass percent concentration of iodomethane is 4 ﹪) of 92g iodomethane, at 30 ℃, stir 10 hours, realize poly-(methyl methacrylate)-P4VP embedding and forge the quaternized of copolymer, centrifugation 7 times, obtains the quaternized inorganic-organic hybridization nano particle of purifying; By the quaternized inorganic-organic hybridization nano particle of 4g, 64gN, N '-dimethylacetylamide, 24g polysulfones, 8g pore-foaming agent (in pore-foaming agent, polyethylene glycol is 3:7 with the mass ratio of water) mix, and stir 8 hours vacuum defoamation 15 minutes at 40 ℃, at 40 ℃ standing 10 hours, obtain casting solution; By non-solvent, induce phase separation method masking, film is immersed in the deionized water of 40 ℃ 24 hours, take out, obtaining take quaternized inorganic-organic hybridization nano particle is decentralized photo, the novel organic-inorganic hybrid microfiltration membranes that the polysulfones of take is principal phase.
Embodiment 11.
30g poly-(methyl methacrylate)-poly-(dimethylaminoethyl acrylate) block copolymer is grafted on to the Nano particles of silicon dioxide surface that 70g diameter is 80 nanometers by reversible addition-fracture chain transfer polymerization (RAFT), centrifugation 7 times, obtain poly-(methyl methacrylate)-poly-(dimethylaminoethyl acrylate) block copolymer-grafting-silica inorganic-organic hybridization nano particle of purifying, the weight average molecular weight of graft polymers is 350,000 grams/mol; 3g poly-(methyl methacrylate)-poly-(dimethylaminoethyl acrylate) block copolymer-grafting-silica inorganic-organic hybridization nano particle is dispersed in the methanol solution (in the methanol solution of bromoethane, the mass percent concentration of bromoethane is 4 ﹪) of 97g bromoethane, at 35 ℃, stir 16 hours, the quaternized of copolymer forged in realize poly-(methyl methacrylate)-poly-(dimethylaminoethyl acrylate) embedding, centrifugation 4 times, obtains the quaternized inorganic-organic hybridization nano particle of purifying; By the quaternised inorganic-organic hybridization nano particle of 7g, 73gN, N '-dimethylacetylamide, 16g Kynoar, 4g pore-foaming agent (in pore-foaming agent, polyethylene glycol is 3:2 with the mass ratio of water) mix, at 50 ℃, stir 10 hours, vacuum defoamation 20 minutes, at 50 ℃ standing 3 hours, obtain casting solution; By non-solvent, induce phase separation method masking, film is immersed in the deionized water of 50 ℃ 60 hours, take out, obtaining take quaternized inorganic-organic hybridization nano particle is decentralized photo, the novel organic-inorganic hybrid milipore filter that the Kynoar of take is principal phase.
The water contact angle of the novel organic-inorganic hybrid milipore filter that embodiment 11 is prepared, water flux and bovine serum albumin(BSA) rejection see attached list 1, and the water contact angle of this novel organic-inorganic hybrid milipore filter is 61 °, and water flux is 143 Lm
-2h
-1, to bovine serum albumin(BSA) rejection, be 64 ﹪.
Embodiment 12.
55g poly-(methyl methacrylate)-poly-(2-vinylpyridine) block copolymer is grafted on to the Nano particles of silicon dioxide surface that 45g diameter is 90 nanometers by reversible addition-fracture chain transfer polymerization (RAFT), centrifugation 8 times, obtain poly-(methyl methacrylate)-poly-(2-vinylpyridine) block copolymer-grafting-silica inorganic-organic hybridization nano particle of purifying, the weight average molecular weight of graft polymers is 550,000 grams/mol; 3g poly-(methyl methacrylate)-poly-(2-vinylpyridine) block copolymer-grafting-silica inorganic-organic hybridization nano particle is dispersed in the methanol solution (in the methanol solution of 2-bromoacetic acid, the mass percent concentration of 2-bromoacetic acid is 4 ﹪) of 97g2-bromoacetic acid, at 35 ℃, stir 16 hours, the quaternized of copolymer forged in realize poly-(methyl methacrylate)-poly-(2-vinylpyridine) embedding, centrifugation 4 times, obtains the quaternized inorganic-organic hybridization nano particle of purifying; By the quaternized inorganic-organic hybridization nano particle of 7g, 63gN, N '-dimethylacetylamide, 10g Kynoar, 20g pore-foaming agent (in pore-foaming agent, polyethylene glycol is 3:2 with the mass ratio of water) mix, at 50 ℃, stir 10 hours, vacuum defoamation 20 minutes, at 50 ℃ standing 3 hours, obtain casting solution; By non-solvent, induce phase separation method masking, film is immersed in the deionized water of 50 ℃ 60 hours, take out, obtaining take quaternized inorganic-organic hybridization nano particle is decentralized photo, the novel organic-inorganic hybrid microfiltration membranes that the Kynoar of take is principal phase.
Water contact angle, water flux and the rejection of table 1 novel organic-inorganic hybrid diffusion barrier
Note: 25 ℃ of probe temperatures, test pressure 0.1MPa.
Above-described embodiment is not that the present invention is not limited only to above-described embodiment for restriction of the present invention, as long as meet requirement of the present invention, all belongs to protection scope of the present invention.
Claims (6)
1. a preparation method for novel organic-inorganic hybrid microporous separation membrane, is characterized in that the method comprises the following steps:
Step (1). at nano-silica surface, by reversible addition-fracture chain transfer polymerization graft polymers, centrifugation 3～10 times, obtains the inorganic-organic hybridization nano particle of the polymer-grafting-silica of purifying; Wherein in inorganic-organic hybridization nano particle, the mass content of graft polymers is 5～60 ﹪;
Step (2). the inorganic-organic hybridization nano particle that step (1) is obtained is dispersed in quaternizing agent solution, wherein the mass content of inorganic-organic hybridization nano particle is 0.5～10 ﹪, at 10～80 ℃, stir 0.5～24 hour, realize the quaternized of graft polymers, eccentric cleaning 3～10 times, obtains the quaternized hybridized nanometer particle of purifying;
Step (3). by the quaternized hybridized nanometer particle of step (2), N, N '-dimethylacetylamide, polymeric film material, pore-foaming agent mix, and stir 4～24 hours vacuum defoamation 5～30 minutes at 10～80 ℃, at 10～80 ℃ standing 0.5～12 hour, obtain casting solution; Wherein in casting solution, the mass content of polymeric film material is 12～30 ﹪, N, and the mass content of N '-dimethylacetylamide is 50～85 ﹪, the mass content of pore-foaming agent is 0.5～20 ﹪; By non-solvent, induce phase separation method that casting solution is made to film, then film is immersed in the deionized water of 10～60 ℃ 6～72 hours, take out, obtain novel hybrid inorganic-organic microporous separation membrane.
2. the preparation method of a kind of novel organic-inorganic hybrid microporous separation membrane as claimed in claim 1, is characterized in that the diameter of step (1) nano silicon is 30～100 nanometers.
3. the preparation method of a kind of novel organic-inorganic hybrid microporous separation membrane as claimed in claim 1, it is characterized in that step (1) graft polymers is for poly-(dimethylaminoethyl methacrylate), poly-(diethyl aminoethyl methacrylate), poly-(dimethylaminoethyl acrylate), poly-(acrylic acid diethylamino ethyl ester), P4VP, poly-(2-vinylpyridine), copolymer is forged in poly-(methyl methacrylate)-poly-(dimethylaminoethyl methacrylate) embedding, copolymer is forged in poly-(methyl methacrylate)-poly-(diethylaminoethyl methacrylate) embedding, copolymer is forged in poly-(methyl methacrylate)-poly-(dimethylaminoethyl acrylate) embedding, copolymer is forged in poly-(methyl methacrylate)-poly-(acrylic acid diethylamino ethyl ester) embedding, copolymer is forged in poly-(methyl methacrylate)-P4VP embedding or copolymer is forged in poly-(methyl methacrylate)-poly-(2-vinylpyridine) embedding, weight average molecular weight is 2, 000～600, 000 gram/mol.
4. the preparation method of a kind of novel organic-inorganic hybrid microporous separation membrane as claimed in claim 1, is characterized in that methanol solution, the aqueous solution of quaternizing agent or the acetone soln of quaternizing agent that step (2) quaternizing agent solution is quaternizing agent; Wherein in quaternizing agent solution, the mass content of quaternizing agent is 1～10 ﹪;
Described quaternizing agent is 2-bromoacetic acid, 3-bromo-propionic acid, 5-bromine valeric acid, PS, iodomethane or bromoethane.
5. the preparation method of a kind of novel organic-inorganic hybrid microporous separation membrane as claimed in claim 1, is characterized in that step (3) polymeric film material is polysulfones, polyether sulfone or Kynoar.
6. the preparation method of a kind of novel organic-inorganic hybrid microporous separation membrane as claimed in claim 1, is characterized in that step (3) pore-foaming agent is the mixed solution of polyethylene glycol and water; The mass ratio of polyethylene glycol and water is 10:1～1:10.
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