CN103990384B - A kind of preparation method of hybrid inorganic-organic microporous separation membrane - Google Patents
A kind of preparation method of hybrid inorganic-organic microporous separation membrane Download PDFInfo
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Abstract
The present invention discloses a kind of preparation method of novel organic-inorganic hybrid microporous separation membrane.The method is by reversible addion-fragmentation chain transfer graft polymerization polymer at nano-silica surface, obtain the inorganic-organic hybridization nano particle of polymer-grafting-silica, then be dispersed in quaternizing agent solution and stirred 0.5 ~ 24 hour, realize the quaternized of graft polymers, obtain quaternized hybridized nanometer particle; Using quaternized hybridized nanometer particle as decentralized photo, take polymeric film material as principal phase, prepare inorganic by non-solvent induction phase separation method.The inventive method can not only suppress the reunion behavior of inorganic nano-particle effectively, 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 many performances such as the hydrophily of diffusion barrier, selective penetrated property, resistance tocrocking and antibiotic property can be improved significantly.
Description
Technical field
The invention belongs to technical field of membrane separation, particularly relate 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 solving water resources problems, and obtain the great attention of countries in the world, film is then the core of membrane process.Current most membrane technology all depends on polymer film, polymer film has the advantages such as raw material sources extensively, are easily processed, cost is low, pliability is good, be widely used in the fields such as feedwater/drainage sunk well, sewage disposal, desalinization, but, polymer film still comes with some shortcomings, and such as non-refractory, not organic solvent-resistant and chemical attack, life-span are shorter etc.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 fouling membrane, reduce water flux and the water outlet quality of film, affect the performance of film, shorten the service life of film.Therefore, usually need to carry out modification to it, improve the performances such as its separation property, hydrophily, resistance tocrocking.Moreover, when polymer film is used for the field relevant with biology such as haemodialysis, also its blood compatibility should be improved.
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 damages polymer film matrix particle.Equally, surface-treated method easily causes the damage of polymer-based film.The method of modifying of surface coating is the method for modifying usually used in industry, in this method the kind of matrix and shape unrestricted, coating speed is fast, is beneficial to large-scale production, but due to the active force between coating and matrix weak and easily peel off.Blending modification method, film forming and modification complete simultaneously, do not need after-treatment, simple and easy to do, and be the method for modifying being widely used at present studying, but the modifier that PEG and PVP etc. commonly use easily runs off in Long-Time Service process, modified effect is not lasting.
In recent years, the method with inorganic nano particle modified polymer film has been risen.In surface inorganic nano-particle being incorporated into polymer film or body, prepare 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), effectively can improve the heat endurance of polymeric membrane, adjustment parent-hydrophobic balance, controlling diaphragm is swelling, the pore structure of improvement and modified membrane and distribution, improves solvent resistance, the selective and permeability of film, strengthening the mechanical strength of film, is the effective way of preparation, development of new peplomer.But, inorganic nano-particle is owing to having high surface energy and large specific area easily agglomeration occurs, adverse effect is caused to the Structure and Properties of hybridized film, and due to organic and inorganic two alternate interactions weak, 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 needing to carry out modification to the surface of inorganic nano-particle and being used further to prepare hybrid organic-inorganic film, is at inorganic nano-particle surface grafting polymerization thing to one of inorganic nano particle modified the most frequently used method.
Olefin monomer containing tertiary amine group is grafted on Nano particles of silicon dioxide surface, generate inorganic-organic hybridization nano particle, then there is quaterisation under mild conditions, be transformed into quaternised inorganic-organic hybridization nano particle, using it as decentralized photo, take polymeric film material as principal phase, hybrid organic-inorganic film is prepared by non-solvent induction phase separation method, effectively can not only 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 the speciality of quaternary ammonium type polymer can be given full play to, the hydrophily of significant raising film, selective penetrated property, 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 addion-fragmentation 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), poly-(methyl methacrylate)-poly-(dimethylaminoethyl methacrylate) block copolymer, poly-(methyl methacrylate)-poly-(diethylaminoethyl methacrylate) block copolymer, poly-(methyl methacrylate)-poly-(dimethylaminoethyl acrylate) block copolymer, poly-(methyl methacrylate)-poly-(acrylic acid diethylamino ethyl ester) block copolymer, poly-(methyl methacrylate)-P4VP block copolymer or poly-(methyl methacrylate)-poly-(2-vinylpyridine) block copolymer, weight average molecular weight is 2, 000 ~ 600, 000 gram/mol.
Step (2). inorganic-organic hybridization nano particle dispersion step (1) obtained is in quaternizing agent solution, wherein the mass content of inorganic-organic hybridization nano particle is 0.5 ~ 10 ﹪, stir 0.5 ~ 24 hour at 10 ~ 80 DEG C, realize the quaternized of graft polymers, eccentric cleaning 3 ~ 10 times, obtains the quaternized hybridized nanometer particle of purifying;
Described quaternizing agent solution is the acetone soln of the methanol solution of quaternizing agent, the aqueous solution of quaternizing agent or 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, novel inorganic is prepared by non-solvent induction phase separation method, realize the functionalization of hybrid separation membrane simultaneously, concrete way is the quaternized hybridized nanometer particle, the N that step (2) are prepared, N '-dimethyl acetamide, polymeric film material, pore-foaming agent mix, stir 4 ~ 24 hours at 10 ~ 80 DEG C, vacuum defoamation 5 ~ 30 minutes, leave standstill 0.5 ~ 12 hour at 10 ~ 80 DEG C, obtain casting solution; Wherein in casting solution, the mass content of polymeric film material is 12 ~ 30 ﹪, N, and the mass content of N '-dimethyl acetamide is 50 ~ 85 ﹪, and the mass content of pore-foaming agent is 0.5 ~ 20 ﹪; By non-solvent induction phase separation method, casting solution is made film, then film to be immersed in the deionized water of 10 ~ 60 DEG C 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: the olefin monomer containing tertiary amine group is grafted on Nano particles of silicon dioxide surface, generate inorganic-organic hybridization nano particle, then there is quaterisation under mild conditions, be transformed into quaternised inorganic-organic hybridization nano particle, using it as decentralized photo, take polymeric film material as principal phase, hybrid organic-inorganic film is prepared by non-solvent induction phase separation method, effectively can not only 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 the hydrophily of diffusion barrier can be improved significantly, selective penetrated property, many performances such as resistance tocrocking and antibiotic property.In the present invention, masking and membrane modifying synchronously carry out, and production efficiency is high, cost is low, is beneficial to large-scale Development and Production, has the prospect of wide industrial applications.
Detailed description of the invention
The present invention is with the quaternised hybrid inorganic-organic Nano particles of silicon dioxide in surface for decentralized photo, take polymeric film material as principal phase, prepares novel inorganic, realize its functionalization simultaneously by non-solvent induction phase separation method.
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 derive all distortion, all think protection scope of the present invention.
Embodiment 1.
60g poly-(dimethylaminoethyl methacrylate) is grafted on by reversible addion-fragmentation chain transfer polymerization (RAFT) the Nano particles of silicon dioxide surface that 40g diameter is 100 nanometers, 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 gram/mol; By poly-for 0.5g (dimethylaminoethyl methacrylate)-grafting-silica inorganic-organic hybridization nano particle dispersion 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 99.5g5-bromine valeric acid, stir 24 hours at 10 DEG C, 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, 50gN, N '-dimethyl acetamide, 30g polysulfones, 10g pore-foaming agent (in pore-foaming agent, the mass ratio of polyethylene glycol and water is 10:1), stir 24 hours at 10 DEG C, vacuum defoamation 30 minutes, leave standstill 12 hours at 10 DEG C, obtain casting solution; By non-solvent induction phase separation method masking, to be immersed by film in the deionized water of 10 DEG C 72 hours, take out, obtaining with quaternized inorganic-organic hybridization nano particle for decentralized photo, take polysulfones as the novel organic-inorganic hybrid microfiltration membranes of principal phase.
The water contact angle of the novel organic-inorganic hybrid microfiltration membranes prepared by embodiment 1, 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 459Lm
-2h
-1, be 71 ﹪ to bovine serum albumin(BSA) rejection.
Embodiment 2.
5g poly-(diethyl aminoethyl methacrylate) is grafted on by reversible addion-fragmentation chain transfer polymerization (RAFT) the Nano particles of silicon dioxide surface that 95g diameter is 30 nanometers, 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 gram/mol; By poly-for 10g (diethyl aminoethyl methacrylate)-grafting-silica inorganic-organic hybridization nano particle dispersion 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 90g3-bromo-propionic acid, stir 0.5 hour at 80 DEG C, centrifugation 3 times, obtains the quaternized inorganic-organic hybridization nano particle of purifying; By quaternized for 0.5g inorganic-organic hybridization nano particle, 85gN, N '-dimethyl acetamide, 12g Kynoar, 2.5g pore-foaming agent (in pore-foaming agent, polyethylene glycol is 1:10 with the mass ratio of water) mix, stir 4 hours at 80 DEG C, vacuum defoamation 5 minutes, leave standstill 0.5 hour at 80 DEG C, obtain casting solution; By non-solvent induction phase separation method masking, to be immersed by film in the deionized water of 60 DEG C 6 hours, take out, obtaining with quaternized inorganic-organic hybridization nano particle for decentralized photo, take Kynoar as the novel organic-inorganic hybrid microfiltration membranes of principal phase.
Embodiment 3.
45g poly-(acrylic acid diethylamino ethyl ester) is grafted on by reversible addion-fragmentation chain transfer polymerization (RAFT) the Nano particles of silicon dioxide surface that 55g diameter is 50 nanometers, 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 gram/mol; By poly-for 5g (first acrylic acid diethylamino ethyl ester)-grafting-silica inorganic-organic hybridization nano particle dispersion at 95g1, 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 DEG C, realize the quaternized of poly-(acrylic acid lignocaine ethyl ester), centrifugation 5 times, obtains the quaternized inorganic-organic hybridization nano particle of purifying; By quaternized for 2g inorganic-organic hybridization nano particle, 79.5gN, N '-dimethyl acetamide, 18g polyether sulfone, 0.5g pore-foaming agent (in pore-foaming agent, polyethylene glycol is 1:1 with the mass ratio of water) mix, stir 12 hours at 60 DEG C, vacuum defoamation 10 minutes, leave standstill 2 hours at 60 DEG C, obtain casting solution; By non-solvent induction phase separation method masking, to be immersed by film in the deionized water of 30 DEG C 48 hours, take out, obtaining with amphoteric ion type inorganic-organic hybridization nano particle for decentralized photo, take polyether sulfone as the novel organic-inorganic hybrid milipore filter of principal phase.
The water contact angle of the novel organic-inorganic hybrid milipore filter prepared by embodiment 3, 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, be 88 ﹪ to bovine serum albumin(BSA) rejection.
Embodiment 4.
17g P4VP is grafted on by reversible addion-fragmentation chain transfer polymerization (RAFT) the Nano particles of silicon dioxide surface that 83g diameter is 70 nanometers, centrifugation 8 times, obtain the P4VP-grafting-silica inorganic-organic hybridization nano particle of purifying, the weight average molecular weight of graft polymers is 25,000 gram/mol; By 8g P4VP-grafting-silica inorganic-organic hybridization nano particle dispersion in the methanol solution (in the methanol solution of iodomethane, the mass percent concentration of iodomethane is 4 ﹪) of 92g iodomethane, stir 10 hours at 30 DEG C, realize the quaternized of P4VP, centrifugation 7 times, obtains the quaternized inorganic-organic hybridization nano particle of purifying; By quaternized for 4g inorganic-organic hybridization nano particle, 64gN, N '-dimethyl acetamide, 24g polysulfones, 8g pore-foaming agent (in pore-foaming agent, polyethylene glycol is 3:7 with the mass ratio of water) mix, stir 8 hours at 40 DEG C, vacuum defoamation 15 minutes, leave standstill 10 hours at 40 DEG C, obtain casting solution; By non-solvent induction phase separation method masking, to be immersed by film in the deionized water of 40 DEG C 24 hours, take out, obtaining with quaternized inorganic-organic hybridization nano particle for decentralized photo, take polysulfones as the novel organic-inorganic hybrid milipore filter of principal phase.
Embodiment 5.
45g poly-(dimethylaminoethyl acrylate) is grafted on by reversible addion-fragmentation chain transfer polymerization (RAFT) the Nano particles of silicon dioxide surface that 55g diameter is 80 nanometers, 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 gram/mol; By poly-for 3g (dimethylaminoethyl acrylate)-grafting-silica inorganic-organic hybridization nano particle dispersion in the methanol solution (in the methanol solution of iodomethane, the mass percent concentration of iodomethane is 4 ﹪) of 97g iodomethane, stir 16 hours at 35 DEG C, realize the quaternized of poly-(dimethylaminoethyl acrylate), centrifugation 4 times, obtains the quaternized inorganic-organic hybridization nano particle of purifying; By quaternised for 7g inorganic-organic hybridization nano particle, 73gN, N '-dimethyl acetamide, 16g Kynoar, 4g pore-foaming agent (in pore-foaming agent, polyethylene glycol is 3:2 with the mass ratio of water) mix, stir 10 hours at 50 DEG C, vacuum defoamation 20 minutes, leave standstill 3 hours at 50 DEG C, obtain casting solution; By non-solvent induction phase separation method masking, to be immersed by film in the deionized water of 50 DEG C 60 hours, take out, obtaining with quaternized inorganic-organic hybridization nano particle for decentralized photo, take Kynoar as the novel organic-inorganic hybrid milipore filter of principal phase.
The water contact angle of the novel organic-inorganic hybrid milipore filter prepared by embodiment 5, 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 183Lm
-2h
-1, be 57 ﹪ to bovine serum albumin(BSA) rejection.
Embodiment 6.
58g poly-(2-vinylpyridine) is grafted on by reversible addion-fragmentation chain transfer polymerization (RAFT) the Nano particles of silicon dioxide surface that 42g diameter is 90 nanometers, centrifugation 8 times, obtain poly-(the 2-vinylpyridine)-grafting-silica inorganic-organic hybridization nano particle of purifying, the weight average molecular weight of graft polymers is 550,000 gram/mol; By poly-for 3g (2-vinylpyridine)-grafting-silica inorganic-organic hybridization nano particle dispersion in the methanol solution (in the methanol solution of iodomethane, the mass percent concentration of iodomethane is 4 ﹪) of 97g iodomethane, stir 16 hours at 35 DEG C, realize the quaternized of poly-(2-vinylpyridine), centrifugation 4 times, obtains the quaternized inorganic-organic hybridization nano particle of purifying; By quaternized for 7g inorganic-organic hybridization nano particle, 63gN, N '-dimethyl acetamide, 10g Kynoar, 20g pore-foaming agent (in pore-foaming agent, polyethylene glycol is 3:2 with the mass ratio of water) mix, stir 10 hours at 50 DEG C, vacuum defoamation 20 minutes, leave standstill 3 hours at 50 DEG C, obtain casting solution; By non-solvent induction phase separation method masking, to be immersed by film in the deionized water of 50 DEG C 60 hours, take out, obtaining with quaternized inorganic-organic hybridization nano particle for decentralized photo, take Kynoar as the novel organic-inorganic hybrid microfiltration membranes of principal phase.
Embodiment 7.
20g poly-(methyl methacrylate)-poly-(dimethylaminoethyl methacrylate) block copolymer is grafted on by reversible addion-fragmentation chain transfer polymerization (RAFT) the Nano particles of silicon dioxide surface that 80g diameter is 70 nanometers, centrifugation 4 times, obtain poly-(methyl methacrylate)-poly-(dimethylaminoethyl methacrylate) block copolymer-grafting-silica inorganic-organic hybridization nano particle of purifying, the weight average molecular weight of graft polymers is 150,000 gram/mol; By 2g poly-(methyl methacrylate)-poly-(dimethylaminoethyl methacrylate) block copolymer-grafting-silica inorganic-organic hybridization nano particle dispersion 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 98g5-bromine valeric acid, stir 12 hours at 30 DEG C, realize poly-(methyl methacrylate)-gather the quaternized of (dimethylaminoethyl methacrylate) block copolymer, centrifugation 3 times, obtains the quaternized inorganic-organic hybridization nano particle of purifying; By quaternized for 4g inorganic-organic hybridization nano particle, 65gN, N '-dimethyl acetamide, 13g Kynoar, 18g pore-foaming agent (in pore-foaming agent, polyethylene glycol is 3:2 with the mass ratio of water) mix, stir 10 hours at 50 DEG C, vacuum defoamation 20 minutes, leave standstill 3 hours at 50 DEG C, obtain casting solution; By non-solvent induction phase separation method masking, to be immersed by film in the deionized water of 50 DEG C 60 hours, take out, obtaining with quaternized inorganic-organic hybridization nano particle for decentralized photo, take Kynoar as the novel organic-inorganic hybrid microfiltration membranes of principal phase.
The water contact angle of the novel organic-inorganic hybrid microfiltration membranes prepared by embodiment 7, 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 4512Lm
-2h
-1, be 38 ﹪ to bovine serum albumin(BSA) rejection.
Embodiment 8.
50g poly-(methyl methacrylate)-poly-(diethyl aminoethyl methacrylate) block copolymer is grafted on by reversible addion-fragmentation chain transfer polymerization (RAFT) the Nano particles of silicon dioxide surface that 50g diameter is 30 nanometers, centrifugation 3 times, obtain poly-(methyl methacrylate)-poly-(diethyl aminoethyl methacrylate) block copolymer-grafting-silica inorganic-organic hybridization nano particle of purifying, the weight average molecular weight of graft polymers is 12,000 gram/mol; By 10g poly-(methyl methacrylate)-poly-(diethyl aminoethyl methacrylate) block copolymer-grafting-silica inorganic-organic hybridization nano particle dispersion 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 90g3-bromo-propionic acid, stir 0.5 hour at 80 DEG C, realize poly-(methyl methacrylate)-gather the quaternized of (diethyl aminoethyl methacrylate) block copolymer, centrifugation 3 times, obtains the quaternized inorganic-organic hybridization nano particle of purifying; By quaternized for 0.5g inorganic-organic hybridization nano particle, 85gN, N '-dimethyl acetamide, 12g Kynoar, 2.5g pore-foaming agent (in pore-foaming agent, polyethylene glycol is 1:10 with the mass ratio of water) mix, stir 4 hours at 80 DEG C, vacuum defoamation 5 minutes, leave standstill 0.5 hour at 80 DEG C, obtain casting solution; By non-solvent induction phase separation method masking, to be immersed by film in the deionized water of 60 DEG C 6 hours, take out, obtaining with quaternized inorganic-organic hybridization nano particle for decentralized photo, take Kynoar as the novel organic-inorganic hybrid milipore filter of principal phase.
Embodiment 9.
25g poly-(methyl methacrylate)-poly-(acrylic acid diethylamino ethyl ester) block copolymer is grafted on by reversible addion-fragmentation chain transfer polymerization (RAFT) the Nano particles of silicon dioxide surface that 75g diameter is 50 nanometers, centrifugation 6 times, obtain poly-(methyl methacrylate)-poly-(acrylic acid diethylamino ethyl ester) block copolymer-grafting-silica inorganic-organic hybridization nano particle of purifying, the weight average molecular weight of graft polymers is 400,000 gram/mol; By 5g poly-(methyl methacrylate)-poly-(acrylic acid diethylamino ethyl ester) block copolymer-grafting-silica inorganic-organic hybridization nano particle dispersion at 95g1, 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 DEG C, realize poly-(methyl methacrylate)-gather the quaternized of (acrylic acid diethylamino ethyl ester) block copolymer, centrifugation 5 times, obtains the quaternized inorganic-organic hybridization nano particle of purifying; By quaternized for 2g inorganic-organic hybridization nano particle, 79.5gN, N '-dimethyl acetamide, 18g polyether sulfone, 0.5g pore-foaming agent (in pore-foaming agent, polyethylene glycol is 1:1 with the mass ratio of water) mix, stir 12 hours at 60 DEG C, vacuum defoamation 10 minutes, leave standstill 2 hours at 60 DEG C, obtain casting solution; By non-solvent induction phase separation method masking, to be immersed by film in the deionized water of 30 DEG C 48 hours, take out, obtaining with amphoteric ion type inorganic-organic hybridization nano particle for decentralized photo, take polyether sulfone as the novel organic-inorganic hybrid milipore filter of principal phase.
The water contact angle of the novel organic-inorganic hybrid milipore filter prepared by embodiment 9, 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 79Lm
-2h
-1, be 91 ﹪ to bovine serum albumin(BSA) rejection.
Embodiment 10.
Poly-for 15g (methyl methacrylate-) P4VP block copolymer is grafted on by reversible addion-fragmentation chain transfer polymerization (RAFT) the Nano particles of silicon dioxide surface that 85g diameter is 70 nanometers, centrifugation 8 times, obtain poly-(methyl methacrylate-) P4VP block copolymer-grafting-silica inorganic-organic hybridization nano particle of purifying, the weight average molecular weight of graft polymers is 25,000 gram/mol; By poly-for 8g (methyl methacrylate-) P4VP block copolymer-grafting-silica inorganic-organic hybridization nano particle dispersion in the methanol solution (in the methanol solution of iodomethane, the mass percent concentration of iodomethane is 4 ﹪) of 92g iodomethane, stir 10 hours at 30 DEG C, realize the quaternized of poly-(methyl methacrylate)-P4VP block copolymer, centrifugation 7 times, obtains the quaternized inorganic-organic hybridization nano particle of purifying; By quaternized for 4g inorganic-organic hybridization nano particle, 64gN, N '-dimethyl acetamide, 24g polysulfones, 8g pore-foaming agent (in pore-foaming agent, polyethylene glycol is 3:7 with the mass ratio of water) mix, stir 8 hours at 40 DEG C, vacuum defoamation 15 minutes, leave standstill 10 hours at 40 DEG C, obtain casting solution; By non-solvent induction phase separation method masking, to be immersed by film in the deionized water of 40 DEG C 24 hours, take out, obtaining with quaternized inorganic-organic hybridization nano particle for decentralized photo, take polysulfones as the novel organic-inorganic hybrid microfiltration membranes of principal phase.
Embodiment 11.
30g poly-(methyl methacrylate)-poly-(dimethylaminoethyl acrylate) block copolymer is grafted on by reversible addion-fragmentation chain transfer polymerization (RAFT) the Nano particles of silicon dioxide surface that 70g diameter is 80 nanometers, 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 gram/mol; By 3g poly-(methyl methacrylate)-poly-(dimethylaminoethyl acrylate) block copolymer-grafting-silica inorganic-organic hybridization nano particle dispersion in the methanol solution (in the methanol solution of bromoethane, the mass percent concentration of bromoethane is 4 ﹪) of 97g bromoethane, stir 16 hours at 35 DEG C, realize poly-(methyl methacrylate)-gather the quaternized of (dimethylaminoethyl acrylate) block copolymer, centrifugation 4 times, obtains the quaternized inorganic-organic hybridization nano particle of purifying; By quaternised for 7g inorganic-organic hybridization nano particle, 73gN, N '-dimethyl acetamide, 16g Kynoar, 4g pore-foaming agent (in pore-foaming agent, polyethylene glycol is 3:2 with the mass ratio of water) mix, stir 10 hours at 50 DEG C, vacuum defoamation 20 minutes, leave standstill 3 hours at 50 DEG C, obtain casting solution; By non-solvent induction phase separation method masking, to be immersed by film in the deionized water of 50 DEG C 60 hours, take out, obtaining with quaternized inorganic-organic hybridization nano particle for decentralized photo, take Kynoar as the novel organic-inorganic hybrid milipore filter of principal phase.
The water contact angle of the novel organic-inorganic hybrid milipore filter prepared by embodiment 11, 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 143Lm
-2h
-1, be 64 ﹪ to bovine serum albumin(BSA) rejection.
Embodiment 12.
55g poly-(methyl methacrylate)-poly-(2-vinylpyridine) block copolymer is grafted on by reversible addion-fragmentation chain transfer polymerization (RAFT) the Nano particles of silicon dioxide surface that 45g diameter is 90 nanometers, 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 gram/mol; By 3g poly-(methyl methacrylate)-poly-(2-vinylpyridine) block copolymer-grafting-silica inorganic-organic hybridization nano particle dispersion 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, stir 16 hours at 35 DEG C, realize poly-(methyl methacrylate)-gather the quaternized of (2-vinylpyridine) block copolymer, centrifugation 4 times, obtains the quaternized inorganic-organic hybridization nano particle of purifying; By quaternized for 7g inorganic-organic hybridization nano particle, 63gN, N '-dimethyl acetamide, 10g Kynoar, 20g pore-foaming agent (in pore-foaming agent, polyethylene glycol is 3:2 with the mass ratio of water) mix, stir 10 hours at 50 DEG C, vacuum defoamation 20 minutes, leave standstill 3 hours at 50 DEG C, obtain casting solution; By non-solvent induction phase separation method masking, to be immersed by film in the deionized water of 50 DEG C 60 hours, take out, obtaining with quaternized inorganic-organic hybridization nano particle for decentralized photo, take Kynoar as the novel organic-inorganic hybrid microfiltration membranes of principal phase.
The water contact angle of table 1 novel organic-inorganic hybrid diffusion barrier, water flux and rejection
Note: probe temperature 25 DEG C, 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 application claims, all belongs to protection scope of the present invention.
Claims (6)
1. a preparation method for hybrid inorganic-organic microporous separation membrane, is characterized in that the method comprises the following steps:
Step (1). at nano-silica surface by reversible addion-fragmentation chain transfer graft polymerization polymer, 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). inorganic-organic hybridization nano particle dispersion step (1) obtained is in quaternizing agent solution, wherein the mass content of inorganic-organic hybridization nano particle is 0.5 ~ 10 ﹪, stir 0.5 ~ 24 hour at 10 ~ 80 DEG C, realize the quaternized of graft polymers, eccentric cleaning 3 ~ 10 times, obtains the quaternized hybridized nanometer particle of purifying;
Step (3). by quaternized for step (2) hybridized nanometer particle, N, N '-dimethyl acetamide, polymeric film material, pore-foaming agent mix, stir 4 ~ 24 hours at 10 ~ 80 DEG C, vacuum defoamation 5 ~ 30 minutes, leave standstill 0.5 ~ 12 hour at 10 ~ 80 DEG C, obtain casting solution; Wherein in casting solution, the mass content of polymeric film material is 12 ~ 30 ﹪, N, and the mass content of N '-dimethyl acetamide is 50 ~ 85 ﹪, and the mass content of pore-foaming agent is 0.5 ~ 20 ﹪; By non-solvent induction phase separation method, casting solution is made film, then film to be immersed in the deionized water of 10 ~ 60 DEG C 6 ~ 72 hours, take out, obtain hybrid inorganic-organic microporous separation membrane.
2. the preparation method of a kind of hybrid inorganic-organic 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 hybrid inorganic-organic 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), poly-(methyl methacrylate)-poly-(dimethylaminoethyl methacrylate) block copolymer, poly-(methyl methacrylate)-poly-(diethylaminoethyl methacrylate) block copolymer, poly-(methyl methacrylate)-poly-(dimethylaminoethyl acrylate) block copolymer, poly-(methyl methacrylate)-poly-(acrylic acid diethylamino ethyl ester) block copolymer, poly-(methyl methacrylate)-P4VP block copolymer or poly-(methyl methacrylate)-poly-(2-vinylpyridine) block copolymer, weight average molecular weight is 2, 000 ~ 600, 000 gram/mol.
4. the preparation method of a kind of hybrid inorganic-organic microporous separation membrane as claimed in claim 1, is characterized in that step (2) quaternizing agent solution is the acetone soln of the methanol solution of quaternizing agent, the aqueous solution of quaternizing agent or 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 hybrid inorganic-organic 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 hybrid inorganic-organic 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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| CN106474946A (en) * | 2016-10-17 | 2017-03-08 | 东华大学 | A kind of preparation method of the polymeric film with hydrophilic antifouling property |
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