CN103990385A - Preparation method of novel polyamide composite separation membrane - Google Patents
Preparation method of novel polyamide composite separation membrane Download PDFInfo
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Abstract
The invention discloses a preparation method of a novel polyamide composite separation membrane. The method comprises the following steps: grafting zwitterions onto the surface of inorganic nanoparticles by active/controllable free-radical polymerization to obtain poly-zwitterion-modified inorganic nanoparticles; dissolving acyl chloride monomer in an organic solvent to prepare an oil-phase acyl chloride monomer solution; dispersing the poly-zwitterion-modified inorganic nanoparticles and amine monomer in water to prepare a water-phase amine monomer solution, and immersing a polymer ultrafiltration membrane in the oil-phase acyl chloride monomer solution for 1-10 minutes; immersing in the water-phase amine monomer solution for 1-10 minutes to obtain a nascent state separation membrane; and rinsing, and carrying out heat treatment for 0.5-10 hours to obtain the novel polyamide composite separation membrane. The method is simple and easy to implement, has the advantages of low production cost and obvious, stable and permanent modification effect, and has favorable industrialization application prospects.
Description
Technical field
The present invention relates to diffusion barrier separation field, relate to a kind of preparation method of novel polyamide composite separating film, relate in particular to the preparation method of the novel polyamide composite separating film of the inorganic nano-particle that contains poly-amphion modification in separating layer.
Background technology
Water is Source of life, and still, present many countries and regions are all faced with serious water resource deficiency and the scarcity of with serious pollution problem, especially freshwater resources, the serious production that affects the mankind, life and development.Separative efficiency is high, floor space is little, process is simple owing to having for membrane separation technique, energy consumption low (without phase transformation), the outstanding advantages such as easy to operate, develops into gradually the key technology that solves water resources problems, has obtained the great attention of countries in the world.The kind of membrane process has a lot, mainly contains micro-filtration, ultrafiltration, nanofiltration, counter-infiltration, gas separation and infiltration evaporation etc., although of a great variety, these membrane process have a common feature, realize a certain particular separation process by film.Film is the core of membrane process, and at present, common film mainly comprises micro-filtration membrane, milipore filter, NF membrane, reverse osmosis membrane and infiltrating and vaporizing membrane.The research of micro-filtration membrane and milipore filter in recent years reaches its maturity, more and more to the research of NF membrane and reverse osmosis membrane, especially concentrates on the research of preparing NF membrane and reverse osmosis membrane by interfacial polymerization.
Interfacial polymerization refers to the polymerisation that two kinds of very high monomers (or prepolymer) of reactivity occur two immiscible solvent interfaces.When interfacial polymerization is during for the preparation of NF membrane and reverse osmosis membrane, the most frequently used monomer is the monomer of water miscible amine monomer and oil-soluble acyl chloride, and this two classes monomer, at interface polymerization reaction take place, forms epidermal area, through suitable post processing, generate PA membrane in membrane surface.Although the polyamide-based NF membrane of preparing by interfacial polymerization and reverse osmosis membrane be the marketization,, this class film is still faced with the problems such as water flux is lower, operating pressure is higher, contamination resistance is poor, needs solution badly.
For addressing the above problem, researcher attempts the inorganic nano materials such as inorganic nano-particle, CNT, Graphene, molecular sieve and zeolite to join amine water monomer solution or the amide-type oil phase monomer solution for interfacial polymerization, prepare polyamide-based NF membrane and reverse osmosis membrane (J.Membr.Sci., 428 (2013): 341-348 by interfacial polymerization; Polymer, 53 (2012): 5295-5303; J.Membr.Sci., 423-424 (2012): 238-246), these PA membranes are the in the situation that of basic maintenance rejection, and water flux has obvious increase, and still, the antifouling property of film does not have clear improvement.And easily there is agglomeration owing to having high surface energy and large specific area in inorganic nano material, the performance of involutory film causes adverse effect, and a little less than the polyamide interaction alternate with inorganic nano material two, the inorganic nano-particle that diffusion barrier adds in long-term use procedure easily runs off, and causes secondary pollution.
In order to address the above problem, we are first grafted on inorganic nano-particle sub-surface by the olefin monomer containing amphion group, generate the inorganic nano-particle that poly-amphion is modified, prepare polyamide-based NF membrane and reverse osmosis membrane by interfacial polymerization again, this method not only can suppress the reunion behavior of inorganic nano-particle effectively, increase the interaction of polyamide and inorganic nano-particle two-phase, improve the stability of inorganic nano-particle in film, increase the water flux of polyamide separation film, and can give full play to zwitterionic speciality, the significant hydrophily that improves film, 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 polyamide composite separating film is provided.
The inventive method comprises the steps:
Step (1). by activity/controllable free-radical polymerisation, amphion is grafted on to inorganic nano-particle sub-surface, prepares the inorganic nano-particle that poly-amphion is modified; In the inorganic nano-particle that wherein poly-amphion is modified, the mass ratio of poly-amphion and inorganic nano-particle is 1:10～1:1;
Described activity/controllable free-radical polymerisation is that ATRP (ATRP) or reversible addition-fracture chain shift (RAFT) polymerization;
Described amphion is carboxylic acid type amphion or sulfonic acid type amphion; Carboxylic acid type amphion is 5-(2-methacryloxyethyl dimethylamino) penta carboxylic acid inner salt, 5-(acryloxy ethyl dimethylamino) penta carboxylic acid inner salt, 3-(2-methacryloxyethyl dimethylamino) the third carboxylic acid inner salt, 3-(acryloxy ethyl dimethylamino) the third carboxylic acid inner salt, 2-(2-methacryloxyethyl dimethylamino) second carboxylic acid inner salt or 2-(acryloxy ethyl dimethylamino) second carboxylic acid inner salt; Sulfonic acid type amphion is 3-(2-methacryloxyethyl dimethylamino) propane sulfonic acid inner salt or 3-(acryloxy ethyl dimethylamino) propane sulfonic acid inner salt;
Described inorganic nano-particle is silica, titanium dioxide, alundum (Al2O3), calcium carbonate or silver, and diameter is 20～200 nanometers;
In the inorganic nano-particle that described poly-amphion is modified, poly-zwitterionic number-average molecular weight is 500～400,000 gram/mol;
Step (2). acyl chlorides monomer is dissolved in organic solvent, is mixed with oil phase acyl chlorides monomer solution; In oil phase acyl chlorides monomer solution, the mass content of acyl chlorides monomer is 0.01～10 ﹪;
Described acyl chlorides monomer is m-phthaloyl chloride, paraphthaloyl chloride, o-phthaloyl chloride, pyromellitic trimethylsilyl chloride, 5-oxygen formyl chloride-isophthaloyl chlorine or 5-isocyanates-isophthaloyl chlorine;
Described organic solvent is n-hexane, cyclohexane, normal heptane, normal octane or dodecane.
Step (3). inorganic nano-particle, amine monomer that poly-amphion is modified are dispersed in water, and are mixed with the water amine monomer solution of the inorganic nano-particle that contains poly-amphion modification, and pH value to 7～12 of regulator solution; In water amine monomer solution, the mass content of amine monomer is 0.01～10 ﹪, and the mass content of the inorganic nano-particle that poly-amphion is modified is 0.1～10 ﹪;
Described amine monomer is m-phenylene diamine (MPD), o-phenylenediamine, p-phenylenediamine (PPD), piperazine, ethylenediamine, 1,2-ethylenediamine, Isosorbide-5-Nitrae-cyclohexanediamine, 1,3-hexamethylene dimethylamine or diethyl triamine;
Step (4). polymer milipore filter is immersed in step (2) oil phase phase acyl chlorides monomer solution to 1～10 minute, takes out, wipe the unnecessary oil phase phase acyl chlorides monomer solution in film surface; Be immersed in again in the water amine monomer solution that step (3) regulates the inorganic nano-particle that contains poly-amphion modification after pH value 1～10 minute, take out, wipe the unnecessary water amine monomer solution in film surface, obtain the novel polyamide composite separating film of the inorganic nano-particle of modifying containing poly-amphion of nascent state;
Described polymer milipore filter is polysulphone super-filter membrane, poly (ether-sulfone) ultrafiltration membrane, polyacrylonitrile ultrafiltration film or polyvinylidene fluoride (PVDF) ultrafiltration membrane.
Step (5). step (4) is obtained after the novel polyamide composite separating film rinsed with deionized water 3～10 times of nascent state, heat treatment 0.5～10 hour at 30～100 DEG C, obtains the novel polyamide composite separating film containing the inorganic nano-particle of poly-amphion modification.
Novel polyamide composite separating film prepared by the present invention is polyamide composite nanofiltration membrane or reverse osmosis membrane.
Beneficial effect of the present invention: the olefin monomer containing amphion group is grafted on to inorganic nano-particle sub-surface, generate the inorganic nano-particle that poly-amphion is modified, use it for the preparation of polyamide nanofiltration membrane or reverse osmosis membrane, can effectively suppress the reunion behavior of inorganic nano-particle, promote its dispersiveness in polyamide, increase the interaction of organic and inorganic two-phase, improve the stability of inorganic nano-particle in polyamide.And, by adjusting the chemical constitution of hybridized nanometer particle and the condition of interfacial polymerization, can regulate and control significantly the performance such as hydrophily, permeability, resistance tocrocking and the antibiotic property of water of PA membrane.Film-forming method of the present invention is simple, Yi Hang, is produced into this locality, and modified effect is remarkable, stable, lasting, has good industrial applications prospect.
Brief description of the drawings
Fig. 1 (a) is the transmission electron microscope picture of Nano particles of silicon dioxide;
Fig. 1 (b) is the transmission electron microscope picture of the Nano particles of silicon dioxide of poly-3-(2-methacryloxyethyl dimethylamino) propane sulfonic acid inner salt modification.
Detailed description of the invention
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.
First the inventive method is grafted on amphion inorganic nano-particle sub-surface, generate the hybridized nanometer particle that poly-amphion is modified, be dispersed in again in the water amine monomer solution of synthesizing polyamides diffusion barrier, prepared the novel polyamide composite separating film of the inorganic nano-particle of modifying containing poly-amphion by interfacial polymerization.
Embodiment 1.
By reversible addition-fracture chain transfer polymerization (RAFT), 10g5-(2-methacryloxyethyl dimethylamino) penta carboxylic acid inner salt is grafted on to the Nano particles of silicon dioxide surface that 100g diameter is 70 nanometers, prepare the Nano particles of silicon dioxide that poly-5-(2-methacryloxyethyl dimethylamino) penta carboxylic acid inner salt is modified, the number-average molecular weight of poly-5-(2-methacryloxyethyl dimethylamino) penta carboxylic acid inner salt is 250, 000 gram/mol, the mass ratio of poly-5-(2-methacryloxyethyl dimethylamino) penta carboxylic acid and Nano particles of silicon dioxide is 1:10, poly (ether-sulfone) ultrafiltration membrane is immersed in the oil phase pyromellitic trimethylsilyl chloride hexane solution that mass percent concentration is 10 ﹪, after 1 minute, take out, wipe the unnecessary organic phase solution in film surface, immerse again in water ethylenediamine solution, wherein the mass percent concentration of ethylenediamine is 0.01 ﹪, the mass percent concentration of the Nano particles of silicon dioxide that poly-5-(2-methacryloxyethyl dimethylamino) penta carboxylic acid inner salt is modified is 10 ﹪, the pH value of solution is after 7,10 minutes, film to be taken out, rinsed with deionized water 3 times, heat treatment 10 hours at 30 DEG C, obtains the novel polyamide composite nanometer filtering film of the Nano particles of silicon dioxide of modifying containing poly-5-(2-methacryloxyethyl dimethylamino) penta carboxylic acid inner salt.
Water flux and the rejection of the prepared novel polyamide composite nanometer filtering film of embodiment 1 see attached list 1, and this NEW TYPE OF COMPOSITE NF membrane not only has higher water flux (63.2Lm
-2h
-1), and the rejection of sodium sulphate is greater than to 98 ﹪.
Embodiment 2.
Shift (RAFT) polymerization by reversible addition-fracture chain, 10g3-(acryloxy ethyl dimethylamino) the third carboxylic acid inner salt is grafted on to the titanium dioxide nano-particle surface that 90g diameter is 100 nanometers, prepare the titanium dioxide nano-particle that poly-3-(acryloxy ethyl dimethylamino) the third carboxylic acid inner salt is modified, the number-average molecular weight of poly-3-(acryloxy ethyl dimethylamino) the third carboxylic acid inner salt is 150, 000 gram/mol, the mass ratio of poly-3-(acryloxy ethyl dimethylamino) the third carboxylic acid inner salt and titanium dioxide nano-particle is 1:9, polysulphone super-filter membrane is immersed in the oil phase m-phthaloyl chloride n-heptane solution that mass percent concentration is 0.01 ﹪, after 10 minutes, takes out, wipe the unnecessary oil-phase solution in film surface, immerse again in the water m-phenylene diamine (MPD) aqueous solution 1 minute, wherein the mass percent concentration of m-phenylene diamine (MPD) is 10 ﹪, the mass percent concentration of the titanium dioxide nano-particle that poly-3-(acryloxy ethyl dimethylamino) the third carboxylic acid inner salt is modified is 1 ﹪, the pH value of solution is 12, and film is taken out, rinsed with deionized water 10 times, heat treatment 0.5 hour at 100 DEG C, obtains the novel polyamide complex reverse osmosis membrane containing the titanium dioxide nano-particle of poly-3-(acryloxy ethyl dimethylamino) the third carboxylic acid inner salt modification.
Water flux and the rejection of the prepared novel polyamide complex reverse osmosis membrane of embodiment 2 see attached list 1, and the water flux of this NEW TYPE OF COMPOSITE reverse osmosis membrane is 32.5Lm
-2h
-1, the rejection of sodium sulphate is greater than to 99 ﹪.
Embodiment 3.
By ATRP (ATRP), 10g2-(2-methacryloxyethyl dimethylamino) second carboxylic acid inner salt is grafted on to the calcium carbonate nano particle surface that 80g diameter is 200 nanometers, prepare the calcium carbonate nano particle that poly-2-(2-methacryloxyethyl dimethylamino) second carboxylic acid inner salt is modified, the number-average molecular weight of poly-2-(2-methacryloxyethyl dimethylamino) second carboxylic acid inner salt is 400, 000 gram/mol, the mass ratio of poly-2-(2-methacryloxyethyl dimethylamino) second carboxylic acid inner salt and calcium carbonate nano particle is 1:8, polyacrylonitrile ultrafiltration film is immersed in the oil phase paraphthaloyl chloride cyclohexane solution that mass percent concentration is 4 ﹪, after 5 minutes, takes out, take out and remove the unnecessary organic phase solution in film surface, immerse again in the water o-phenylenediamine aqueous solution 5 minutes, wherein the mass percent concentration of o-phenylenediamine is 2 ﹪, the mass percent concentration of the calcium carbonate nano particle that poly-2-(2-methacryloxyethyl dimethylamino) second carboxylic acid inner salt is modified is 5 ﹪, the pH value of solution is 9, film is taken out, rinsed with deionized water 5 times, heat treatment 3 hours at 80 DEG C, obtains the novel polyamide composite nanometer filtering film containing the calcium carbonate nano particle of poly-2-(2-methacryloxyethyl dimethylamino) second carboxylic acid inner salt modification.
Water flux and the rejection of the prepared novel polyamide composite nanometer filtering film of embodiment 3 see attached list 1, and the water flux of this NEW TYPE OF COMPOSITE NF membrane is 45.9Lm
-2h
-1, sodium sulphate and sodium chloride are all had to higher rejection.
Embodiment 4.
By ATRP (ATRP), 10g3-(2-methacryloxyethyl dimethylamino) propane sulfonic acid inner salt is grafted on to the nano grain of silver sub-surface that 70g diameter is 20 nanometers, prepare the Nano silver grain that poly-3-(2-methacryloxyethyl dimethylamino) propane sulfonic acid inner salt is modified, the number-average molecular weight of poly-3-(2-methacryloxyethyl dimethylamino) propane sulfonic acid inner salt is 500 grams/mol, and the mass ratio of poly-3-(2-methacryloxyethyl dimethylamino) propane sulfonic acid inner salt and Nano silver grain is 1:7; Polyvinylidene fluoride (PVDF) ultrafiltration membrane is immersed in the oil phase o-phthaloyl chloride n-hexane that mass percent concentration is 6 ﹪, after 8 minutes, takes out, remove the unnecessary oil-phase solution in surface; Be immersed in again in the water piperazine aqueous solution 3 minutes, wherein the mass percent concentration of piperazine is 7 ﹪, the mass percent concentration of the Nano silver grain that poly-3-(2-methacryloxyethyl dimethylamino) propane sulfonic acid inner salt is modified is 2 ﹪, the pH value of solution is 9, film is taken out, rinsed with deionized water 8 times, heat treatment 0.5 hour at 100 DEG C, obtains the novel polyamide complex reverse osmosis membrane containing the Nano silver grain of poly-3-(2-methacryloxyethyl dimethylamino) propane sulfonic acid inner salt modification.
Water flux and the rejection of the prepared novel polyamide complex reverse osmosis membrane of embodiment 4 see attached list 1, and the water flux of this NEW TYPE OF COMPOSITE reverse osmosis membrane is 28.6Lm
-2h
-1, to the rejection of sodium chloride up to 93.2 ﹪.
Embodiment 5.
By reversible addition-fracture chain transfer polymerization (RAFT), 10g3-(acryloxy ethyl dimethylamino) propane sulfonic acid inner salt is grafted on to the alundum (Al2O3) nanoparticle surface that 60g diameter is 50 nanometers, prepare the alundum (Al2O3) nano particle that poly-3-(acryloxy ethyl dimethylamino) propane sulfonic acid inner salt is modified, the number-average molecular weight of poly-3-(acryloxy ethyl dimethylamino) propane sulfonic acid inner salt is 100, 000 gram/mol, the mass ratio of poly-3-(acryloxy ethyl dimethylamino) propane sulfonic acid inner salt and alundum (Al2O3) nano particle is 1:6, poly (ether-sulfone) ultrafiltration membrane is immersed in the oil phase pyromellitic trimethylsilyl chloride hexane solution that mass percent concentration is 1 ﹪, after 7 minutes, takes out, remove the unnecessary oil-phase solution in surface, be immersed in again in the water piperazine aqueous solution 8 minutes, wherein the mass percent concentration of piperazine is 3 ﹪, the mass percent concentration of the alundum (Al2O3) nano particle that poly-3-(acryloxy ethyl dimethylamino) propane sulfonic acid inner salt is modified is 8 ﹪, the pH value of solution is 11, film is taken out, rinsed with deionized water 6 times, heat treatment 6 hours at 60 DEG C, obtains the novel polyamide nanofiltration membrane containing the alundum (Al2O3) nano particle of poly-3-(acryloxy ethyl dimethylamino) propane sulfonic acid inner salt modification.
Water flux and the rejection of the prepared novel polyamide composite nanometer filtering film of embodiment 5 see attached list 1, and the water flux of this NEW TYPE OF COMPOSITE NF membrane is 39.4Lm
-2h
-1, the rejection of sodium sulphate and sodium chloride is all greater than to 80 ﹪.
Water flux and the rejection of table 1 novel polyamide composite separating film
Embodiment 6.
By reversible addition-fracture chain transfer polymerization (RAFT), 10g5-(acryloxy ethyl dimethylamino) penta carboxylic acid inner salt is grafted on to the alundum (Al2O3) nanoparticle surface that 50g diameter is 50 nanometers, prepare the alundum (Al2O3) nano particle that poly-5-(acryloxy ethyl dimethylamino) penta carboxylic acid inner salt is modified, the number-average molecular weight of poly-5-(acryloxy ethyl dimethylamino) penta carboxylic acid inner salt is 100, 000 gram/mol, the mass ratio of poly-5-(acryloxy ethyl dimethylamino) penta carboxylic acid inner salt and alundum (Al2O3) nano particle is 1:5, poly (ether-sulfone) ultrafiltration membrane is immersed in oil phase 5-oxygen formyl chloride-isophthaloyl chlorine normal octane solution that mass percent concentration is 5 ﹪, after 5 minutes, takes out, remove the unnecessary oil-phase solution in surface, be immersed in again in the water o-phenylenediamine aqueous solution 8 minutes, wherein the mass percent concentration of o-phenylenediamine is 3 ﹪, the mass percent concentration of the alundum (Al2O3) nano particle that poly-5-(acryloxy ethyl dimethylamino) penta carboxylic acid inner salt is modified is 8 ﹪, the pH value of solution is 11, film is taken out, rinsed with deionized water 6 times, heat treatment 1 hour at 100 DEG C, obtains the novel polyamide nanofiltration membrane containing the alundum (Al2O3) nano particle of poly-5-(acryloxy ethyl dimethylamino) penta carboxylic acid inner salt modification.
Embodiment 7.
By reversible addition-fracture chain transfer polymerization (RAFT), 10g3-(2-methacryloxyethyl dimethylamino) the third carboxylic acid inner salt is grafted on to the Nano particles of silicon dioxide surface that 40g diameter is 50 nanometers, prepare the Nano particles of silicon dioxide that poly-3-(2-methacryloxyethyl dimethylamino) the third carboxylic acid inner salt is modified, the number-average molecular weight of poly-3-(2-methacryloxyethyl dimethylamino) the third carboxylic acid inner salt is 300, 000 gram/mol, the mass ratio of poly-3-(2-methacryloxyethyl dimethylamino) the third carboxylic acid inner salt and Nano particles of silicon dioxide is 1:4, poly (ether-sulfone) ultrafiltration membrane is immersed in oil phase 5-isocyanates-isophthaloyl chlorododecane solution that mass percent concentration is 5 ﹪, after 5 minutes, takes out, remove the unnecessary oil-phase solution in surface, be immersed in again in the water p-phenylenediamine (PPD) aqueous solution 8 minutes, wherein the mass percent concentration of p-phenylenediamine (PPD) is 3 ﹪, the mass percent concentration of the Nano particles of silicon dioxide that poly-3-(2-methacryloxyethyl dimethylamino) the third carboxylic acid inner salt is modified is 0.1 ﹪, the pH value of solution is 11, film is taken out, rinsed with deionized water 6 times, heat treatment 1 hour at 100 DEG C, obtains the novel polyamide nanofiltration membrane containing the Nano particles of silicon dioxide of poly-3-(2-methacryloxyethyl dimethylamino) the third carboxylic acid inner salt modification.
As Fig. 1 (a) transmission electron microscope picture that is Nano particles of silicon dioxide; Fig. 1 (b) is the transmission electron microscope picture of the Nano particles of silicon dioxide of poly-3-(2-methacryloxyethyl dimethylamino) propane sulfonic acid inner salt modification.
Embodiment 8.
By reversible addition-fracture chain transfer polymerization (RAFT), 10g2-(acryloxy ethyl dimethylamino) second carboxylic acid inner salt is grafted on to the titanium dioxide nano-particle surface that 30g diameter is 50 nanometers, prepare the titanium dioxide nano-particle that poly-2-(acryloxy ethyl dimethylamino) second carboxylic acid inner salt is modified, the number-average molecular weight of poly-2-(acryloxy ethyl dimethylamino) second carboxylic acid inner salt is 300,000 gram/mol, the mass ratio of poly-2-(acryloxy ethyl dimethylamino) second carboxylic acid inner salt and titanium dioxide nano-particle is 1:3; Poly (ether-sulfone) ultrafiltration membrane is immersed in oil phase 5-isocyanates-isophthaloyl chlorododecane solution that mass percent concentration is 5 ﹪, after 5 minutes, takes out, remove the unnecessary oil-phase solution in surface; Be immersed in again water 1, in 2-ethylenediamine solution 8 minutes, wherein 1, the mass percent concentration of 2-ethylenediamine is 3 ﹪, the mass percent concentration of the titanium dioxide nano-particle that poly-2-(acryloxy ethyl dimethylamino) second carboxylic acid inner salt is modified is 0.1 ﹪, the pH value of solution is 8, film is taken out, rinsed with deionized water 10 times, heat treatment 1 hour at 100 DEG C, obtains the novel polyamide nanofiltration membrane containing the titanium dioxide nano-particle of poly-2-(acryloxy ethyl dimethylamino) second carboxylic acid inner salt modification.
Embodiment 9.
By ATRP (ATRP), 10g2-(acryloxy ethyl dimethylamino) second carboxylic acid inner salt is grafted on to the titanium dioxide nano-particle surface that 20g diameter is 50 nanometers, prepare the titanium dioxide nano-particle that poly-2-(acryloxy ethyl dimethylamino) second carboxylic acid inner salt is modified, the number-average molecular weight of poly-2-(acryloxy ethyl dimethylamino) second carboxylic acid inner salt is 300,000 gram/mol, the mass ratio of poly-2-(acryloxy ethyl dimethylamino) second carboxylic acid inner salt and titanium dioxide nano-particle is 1:2; Poly (ether-sulfone) ultrafiltration membrane is immersed in oil phase 5-isocyanates-isophthaloyl chlorododecane solution that mass percent concentration is 5 ﹪, after 5 minutes, takes out, remove the unnecessary oil-phase solution in surface; Be immersed in again water 1, in the 4-cyclohexanediamine aqueous solution 8 minutes, wherein 1, the mass percent concentration of 4-cyclohexanediamine is 3 ﹪, the mass percent concentration of the titanium dioxide nano-particle that poly-2-(acryloxy ethyl dimethylamino) second carboxylic acid inner salt is modified is 0.1 ﹪, the pH value of solution is 8, film is taken out, rinsed with deionized water 10 times, heat treatment 1 hour at 100 DEG C, obtains the novel polyamide nanofiltration membrane containing the titanium dioxide nano-particle of poly-2-(acryloxy ethyl dimethylamino) second carboxylic acid inner salt modification.
Embodiment 10.
By ATRP (ATRP), 10g2-(acryloxy ethyl dimethylamino) second carboxylic acid inner salt is grafted on to the Nano particles of silicon dioxide surface that 10g diameter is 100 nanometers, prepare the Nano particles of silicon dioxide that poly-2-(acryloxy ethyl dimethylamino) second carboxylic acid inner salt is modified, the number-average molecular weight of poly-2-(acryloxy ethyl dimethylamino) second carboxylic acid inner salt is 200,000 gram/mol, poly-2-(acryloxy ethyl dimethylamino) second carboxylic acid inner salt and Nano particles of silicon dioxide mass ratio are 1:1; Poly (ether-sulfone) ultrafiltration membrane is immersed in the oil phase m-phthaloyl chloride solution that mass percent concentration is 10 ﹪, after 8 minutes, takes out, remove the unnecessary oil-phase solution in surface; Be immersed in again water 1, in 3-hexamethylene dimethylamine agueous solution 5 minutes, wherein 1, the mass percent concentration of 3-hexamethylene dimethylamine is 0.01 ﹪, the mass percent concentration of the Nano particles of silicon dioxide that poly-2-(acryloxy ethyl dimethylamino) second carboxylic acid inner salt is modified is 0.1 ﹪, the pH value of solution is 8, film is taken out, rinsed with deionized water 10 times, heat treatment 1 hour at 100 DEG C, obtains the novel polyamide nanofiltration membrane containing the Nano particles of silicon dioxide of poly-2-(acryloxy ethyl dimethylamino) second carboxylic acid inner salt modification.
Embodiment 11.
By ATRP (ATRP), 10g2-(acryloxy ethyl dimethylamino) second carboxylic acid inner salt is grafted on to the Nano particles of silicon dioxide surface that 10g diameter is 100 nanometers, prepare the Nano particles of silicon dioxide that poly-2-(acryloxy ethyl dimethylamino) second carboxylic acid inner salt is modified, the number-average molecular weight of poly-2-(acryloxy ethyl dimethylamino) second carboxylic acid inner salt is 200,000 gram/mol, the mass ratio of poly-2-(acryloxy ethyl dimethylamino) second carboxylic acid inner salt and Nano particles of silicon dioxide is 1:1; Poly (ether-sulfone) ultrafiltration membrane is immersed in the oil phase m-phthaloyl chloride solution that mass percent concentration is 10 ﹪, after 8 minutes, takes out, remove the unnecessary oil-phase solution in surface; Be immersed in again in the water diethyl triamine aqueous solution 5 minutes, wherein the mass percent concentration of diethyl triamine is 0.01 ﹪, the mass percent concentration of the Nano particles of silicon dioxide that poly-2-(acryloxy ethyl dimethylamino) second carboxylic acid inner salt is modified is 0.1 ﹪, the pH value of solution is 8, film is taken out, rinsed with deionized water 10 times, heat treatment 1 hour at 100 DEG C, obtains the novel polyamide nanofiltration membrane containing the Nano particles of silicon dioxide of poly-2-(acryloxy ethyl dimethylamino) second carboxylic acid inner salt modification.
The structural formula of 5-(2-methacryloxyethyl dimethylamino) the penta carboxylic acid inner salt described in above-described embodiment is as follows:
The structural formula of 5-(acryloxy ethyl dimethylamino) penta carboxylic acid inner salt is as follows:
The structural formula of 3-(2-methacryloxyethyl dimethylamino) the third carboxylic acid inner salt is as follows:
The structural formula of 3-(acryloxy ethyl dimethylamino) the third carboxylic acid inner salt is as follows:
The structural formula of 2-(2-methacryloxyethyl dimethylamino) second carboxylic acid inner salt is as follows:
The structural formula of 2-(acryloxy ethyl dimethylamino) second carboxylic acid inner salt is as follows:
The structural formula of 3-(2-methacryloxyethyl dimethylamino) propane sulfonic acid inner salt is as follows:
The structural formula of 3-(acryloxy ethyl dimethylamino) propane sulfonic acid inner salt is as follows:
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 (9)
1. a preparation method for novel polyamide composite separating film, is characterized in that the method comprises the following steps:
Step (1). by activity/controllable free-radical polymerisation, amphion is grafted on to inorganic nano-particle sub-surface, prepares the inorganic nano-particle that poly-amphion is modified; In the inorganic nano-particle that wherein poly-amphion is modified, the mass ratio of poly-amphion and inorganic nano-particle is 1:10～1:1;
Step (2). acyl chlorides monomer is dissolved in organic solvent, is mixed with oil phase acyl chlorides monomer solution; In oil phase acyl chlorides monomer solution, the mass content of acyl chlorides monomer is 0.01～10 ﹪;
Step (3). inorganic nano-particle, amine monomer that poly-amphion is modified are dispersed in water, and are mixed with the water amine monomer solution of the inorganic nano-particle that contains poly-amphion modification, pH value to 7～12 of regulator solution; In water amine monomer solution, the mass content of amine monomer is 0.01～10 ﹪, and the mass content of the inorganic nano-particle that poly-amphion is modified is 0.1～10 ﹪;
Step (4). polymer milipore filter is immersed in step (2) oil phase phase acyl chlorides monomer solution to 1～10 minute, takes out, wipe the unnecessary oil phase phase acyl chlorides monomer solution in film surface; Be immersed in again in the water amine monomer solution that step (3) contains the inorganic nano-particle that poly-amphion modifies 1～10 minute, take out, wipe the unnecessary water amine monomer solution in film surface, obtain the novel polyamide composite separating film of the inorganic nano-particle of modifying containing poly-amphion of nascent state;
Step (5). step (4) is obtained after the novel polyamide composite separating film rinsed with deionized water 3～10 times of nascent state, heat treatment 0.5～10 hour at 30～100 DEG C, obtains the novel polyamide composite separating film containing the inorganic nano-particle of poly-amphion modification.
2. the preparation method of a kind of novel polyamide composite separating film as claimed in claim 1, is characterized in that step (1) activity/controllable free-radical polymerisation is ATRP or reversible addition-fracture chain transfer polymerization.
3. the preparation method of a kind of novel polyamide composite separating film as claimed in claim 1, is characterized in that described amphion is carboxylic acid type amphion or sulfonic acid type amphion; Carboxylic acid type amphion is 5-(2-methacryloxyethyl dimethylamino) penta carboxylic acid inner salt, 5-(acryloxy ethyl dimethylamino) penta carboxylic acid inner salt, 3-(2-methacryloxyethyl dimethylamino) the third carboxylic acid inner salt, 3-(acryloxy ethyl dimethylamino) the third carboxylic acid inner salt, 2-(2-methacryloxyethyl dimethylamino) second carboxylic acid inner salt or 2-(acryloxy ethyl dimethylamino) second carboxylic acid inner salt; Sulfonic acid type amphion is 3-(2-methacryloxyethyl dimethylamino) propane sulfonic acid inner salt or 3-(acryloxy ethyl dimethylamino) propane sulfonic acid inner salt.
4. the preparation method of a kind of novel polyamide composite separating film as claimed in claim 1, is characterized in that step (1) inorganic nano-particle is silica, titanium dioxide, alundum (Al2O3), calcium carbonate or silver, and diameter is 20～200 nanometers.
5. the preparation method of a kind of novel polyamide composite separating film as claimed in claim 1, is characterized in that it is 500～400,000 gram/mol that step (1) is gathered poly-zwitterionic number-average molecular weight in the inorganic nano-particle of amphion modification.
6. the preparation method of a kind of novel polyamide composite separating film as claimed in claim 1, is characterized in that step (2) acyl chlorides monomer is m-phthaloyl chloride, paraphthaloyl chloride, o-phthaloyl chloride, pyromellitic trimethylsilyl chloride, 5-oxygen formyl chloride-isophthaloyl chlorine or 5-isocyanates-isophthaloyl chlorine.
7. the preparation method of a kind of novel polyamide composite separating film as claimed in claim 1, is characterized in that step (2) organic solvent is n-hexane, cyclohexane, normal heptane, normal octane or dodecane.
8. the preparation method of a kind of novel polyamide composite separating film as claimed in claim 1, it is characterized in that step (3) amine monomer is m-phenylene diamine (MPD), o-phenylenediamine, p-phenylenediamine (PPD), piperazine, ethylenediamine, 1,2-ethylenediamine, 1,4-cyclohexanediamine, 1,3-hexamethylene dimethylamine or diethyl triamine.
9. the preparation method of a kind of novel polyamide composite separating film as claimed in claim 1, is characterized in that step (4) polymer milipore filter is polysulphone super-filter membrane, poly (ether-sulfone) ultrafiltration membrane, polyacrylonitrile ultrafiltration film or polyvinylidene fluoride (PVDF) ultrafiltration membrane.
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