CN104069749A - Hyperbranched polymer polyamide composite reverse osmosis membrane and preparation method thereof - Google Patents
Hyperbranched polymer polyamide composite reverse osmosis membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hyperbranched polymer polyamide composite reverse osmosis membrane and a preparation method thereof. The composite reverse osmosis membrane is prepared by conducting interfacial polymerization on amine terminated hyperbranched polymer, linear polyamine mixed solution and an aromatic acyl chloride organic solution. The hyperbranched polymer polyamide composite reverse osmosis membrane is stable in chemical property, excellent in mechanical property, large in flux, high in desalinization rate, and can be widely applied to the fields such as environmental protection and food.
Description
Technical field
The invention belongs to membrane separation technique field, be specifically related to a kind of Hyperbranched Polymer with Terminal Amido complex reverse osmosis membrane and preparation method thereof.
Background technology
Reverse osmosis membrane is a kind of pressure drive membrane, the organic matter that its energy all dissolving salts of effectively catching and molecular weight are greater than 100, allow hydrone to pass through simultaneously, be widely used in the fields such as pure water and preparation of high-purity water, drinking water preparation, middle water reuse, percolate processing, desalinization.At present, commercialization reverse osmosis membrane is composite membrane mostly, generally adopts interfacial polymerization technology to obtain at the ultra-thin compacted zone of porous support layer surface recombination.Porous support layer claims again basement membrane, works to increase mechanical strength; Compacted zone also claims epidermal area, plays desalination, therefore claim again desalination layer.Known disclosed have aromatic polyamide composite membrane, fatty polyamide composite membrane etc. at present.But but current the studied relatively low problem of the higher flux of reverse osmosis membrane ubiquity salt rejection rate.
Dissaving polymer (hyperbranched polymer) is a kind of polymer with special macromolecular structure, there is novel three dimensions pore passage structure, the performance of uniqueness and potential application prospect, make this base polymer be subject to numerous researchers' attention and favor, be regarded as the important directions of 21 century polymer science development.Hyperbranched polymer molecule chain not easy entanglement, contain a large amount of active function groups, have advantages of that viscosity is low, dissolubility is good etc. unique, be widely used in the fields such as agricultural, medicine, liquid crystal, functional material, life science, cosmetics, coatings industry, paint industry.Dissaving polymer has special space structure, can be used for preparing the reverse osmosis composite membrane of high flux, equipment with high desalinization, but currently available technology does not openly utilize dissaving polymer to prepare technique and the method for complex reverse osmosis membrane.
Summary of the invention
The present invention will overcome the deficiencies in the prior art exactly, utilizes dissaving polymer to have the characteristic of special space structure, and dissaving polymer polyamide composite reverse osmosis membrane that a kind of flux is large and salt rejection rate is high and preparation method thereof is provided.
First, the invention provides a kind of technical scheme of dissaving polymer polyamide composite reverse osmosis membrane: its by porous support layer with and the polyamide desalination layer that forms by interfacial polymerization of surface, described polyamide desalination layer is dissaving polymer aramid layer, and described dissaving polymer aramid layer is formed by interfacial polymerization by Hyperbranched Polymer with Terminal Amido, polyamine and aromatic series acyl chlorides.
Such scheme can be more preferably:
Described dissaving polymer is that molecular weight is 2000 ~ 5000 Hyperbranched Polymer with Terminal Amidos; Described dissaving polymer aramid layer thickness is 30nm ~ 200nm.
Described porous support layer is any one in polyacrylonitrile, polyether sulfone, modified polyvinilidene fluoride and polysulfones micro-filtration membrane or milipore filter, and described porous support layer thickness is 60 μ m ~ 120 μ m.Porous support layer can oneself prepare or market is buied.
Described complex reverse osmosis membrane is flat sheet membrane, hollow-fibre membrane or tubular membrane; The pore-size distribution of described complex reverse osmosis membrane is 0.5 ~ 10nm.
Then, provide a kind of preparation method of above-mentioned dissaving polymer polyamide composite reverse osmosis membrane, it comprises the following steps:
(1), at the hygrometric state porous support layer surface dip-coating dissaving polymer having cleaned up and the mixed aqueous solution of linear polyamine, then remove surface liquid, the time of described dip-coating is 3 s ~ 300 s; The total mass fraction of described dissaving polymer and linear polyamine mixed aqueous solution is 2% ~ 10%; Described dissaving polymer is that molecular weight is 2000 ~ 5000 Hyperbranched Polymer with Terminal Amidos; Described linear polyamine is at least one in diethylamine, triethylamine, propane diamine, butanediamine, pentanediamine, hexamethylene diamine, piperazine, 4-amino methyl piperazine, m-phenylene diamine (MPD), o-phenylenediamine and p-phenylenediamine (PPD);
(2), contact with the organic solution of aromatic series acyl chlorides with the porous support layer surface of linear polyamine mixed aqueous solution scribbling Hyperbranched Polymer with Terminal Amido, carry out obtaining aramid layer on the surface of porous support layer after interfacial polymerization, the time of described interfacial polymerization is 3s ~ 120s; The mass fraction of described aromatic series acyl chlorides organic solution is 0.05% ~ 2%, described aromatic series acyl chlorides is pyromellitic trimethylsilyl chloride, m-phthaloyl chloride, face at least one in phthalyl chloride, paraphthaloyl chloride and benzene-disulfo-chloride, and the solvent of described organic solution is at least one in the aliphatic hydrocarbon that contains 4 ~ 10 carbon atoms; Then drop is except surperficial residual reaction solution, and at room temperature dries in the shade, described in time of drying in the shade be 4s ~ 300s;
(3), the following four kinds of solution of porous support layer employing with aramid layer desalination layer prepared step (2) the successively last oven dry of rinsing are obtained to complex reverse osmosis membrane; Described solution is followed successively by: a solution that mass fraction is 3% ~ 15%, and described a is any one in maleic acid, maleic anhydride, citric acid, oxalic acid, lactic acid; Mass fraction is 3% ~ 15% b solution, and described b is methyl alcohol or ethanol; Mass fraction is 0.05% ~ 5% c solution, and described c is any one in nano TiO 2 carrying silver, nano zine oxide, Nano Silver, nano titanium oxide; Mass fraction is 5% ~ 10% d solution, and described d is at least one in glycerine, camphorsulfonic acid, sodium hydrogensulfite.
Such scheme can be more preferably:
The total mass fraction of described Hyperbranched Polymer with Terminal Amido and linear polyamine mixed aqueous solution is 3% ~ 5%; The mass fraction of described aromatic series acyl chlorides organic solution is 0.1% ~ 0.3%; Described aromatic series acyl chlorides is preferably pyromellitic trimethylsilyl chloride; The solvent of described organic solution is preferably n-hexane.
Described a is preferably lactic acid, and the mass fraction of lactic acid solution is 5% ~ 7%; Described b is preferably ethanol, and the mass fraction of ethanolic solution is 5% ~ 7%; Described c is preferably nano TiO 2 carrying silver, and the mass fraction of nano TiO 2 carrying silver solution is 0.6% ~ 1%.
In described mixed aqueous solution, also include mass fraction and be 0.05% ~ 0.8% surfactant, described surfactant is at least one in neopelex, sodium glycocholate, dioctyl sodium sulfosuccinate, lauryl sodium sulfate, sldium lauryl sulfate; More preferably neopelex of described surfactant, and its mass fraction is preferably 0.15%.
The temperature of described oven dry is that 75 ~ 100 DEG C, time are 2min ~ 40min; More preferably 85 DEG C of the temperature of described oven dry, more preferably 3min of time.
The rinsing time of four kinds of described solution is 60 s.
Compared with prior art, the stable chemical performance of dissaving polymer complex reverse osmosis membrane, mechanical performance excellence in the present invention, flux is large, salt rejection rate is high, can be widely used in the field such as environmental protection, food.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described further, but not as a limitation of the invention.
A kind of preparation method that first dissaving polymer polyamide composite reverse osmosis membrane is provided, comprises the following steps:
(1) one side of the porous support layer of hygrometric state is immersed in Hyperbranched Polymer with Terminal Amido and linear polyamine mixed aqueous solution, continues to use rubber roll-in except surperficial liquid after 20s;
(2) continue this surface to be immersed in the organic solution that contains aromatic series acyl chlorides, the 30s that dries in the shade under room temperature after lasting 20 s, forms dissaving polymer aramid layer;
(3) then carrying out substep rinsing, is to soak a solution 1min that mass fraction is 3% ~ 15% successively, 3% ~ 15% b solution 1min, and 0.05% ~ 5% c solution 1min, 5% ~ 10% d solution 1min, finally dries and obtains reverse osmosis membrane.
The layoutprocedure of several solns in said method is then provided:
1, the process for preparation of Hyperbranched Polymer with Terminal Amido and linear polyamine mixed aqueous solution is: by Hyperbranched Polymer with Terminal Amido (HBP ~ NH
2) add in 18 DEG C ~ 65 DEG C aqueous solution that contain surfactant with linear polyamine mixture, stir 20min ~ 90min and form the required aqueous solution to solution complete miscibility.
Wherein polyamine is at least one in diethylamine, triethylamine, propane diamine, butanediamine, pentanediamine, hexamethylene diamine, piperazine, 4 ~ amino methyl piperazine, m-phenylene diamine (MPD), o-phenylenediamine, p-phenylenediamine (PPD).
Wherein Hyperbranched Polymer with Terminal Amido molecular weight is 2000 to 5000, and polymer ends is amino group; The total mass fraction of Hyperbranched Polymer with Terminal Amido and linear polyamine mixed aqueous solution is 2% ~ 10%, preferably 3% ~ 5%, and wherein the ratio of Hyperbranched Polymer with Terminal Amido and linear polyamine can regulate and control voluntarily.
Wherein at least one in surfactant neopelex, sodium glycocholate, dioctyl sodium sulfosuccinate, lauryl sodium sulfate, sldium lauryl sulfate, preferably neopelex, mass fraction is 0.05% ~ 0.8%, preferably 0.15%.
,the process for preparation of aromatic series acyl chlorides organic solution is: aromatic series acyl chlorides is added in organic solvent, at 18 DEG C ~ 65 DEG C, stir 20min ~ 90min to solution complete miscibility, form required organic solution.
Wherein aromatic series acyl chlorides is pyromellitic trimethylsilyl chloride, m-phthaloyl chloride, faces at least one in phthalyl chloride, paraphthaloyl chloride, benzene-disulfo-chloride, preferably pyromellitic trimethylsilyl chloride.
Wherein organic solution solvent is at least one in the aliphatic hydrocarbon that contains 4 ~ 10 carbon atoms, preferably n-hexane.
Wherein the mass fraction of aromatic series acyl chlorides organic solution is 0.05% ~ 2%, preferably 0.1% ~ 0.3%.
,the preparation of the required solution of four step rinse step: prepare respectively mass fraction and be 3% ~ 15% a solution, 3% ~ 15% b solution, 0.05% ~ 5% c solution, 5% ~ 10% d solution.
Wherein a solution be in maleic acid, maleic anhydride, citric acid, oxalic acid, lactic acid any one, preferably lactic acid, mass fraction preferably 5% ~ 7%.
Wherein b solution is at least one in methyl alcohol, ethanolic solution, preferred alcohol, mass fraction preferably 5% ~ 7%.
Wherein c solution be in nano TiO 2 carrying silver, nano zine oxide, sodium dehydroacetate, sodium hydrogensulfite, Nano Silver, nanometer titanium dioxide titanium solution any one, preferably nano TiO 2 carrying silver solution, mass fraction preferably 0.6% ~ 1%.
Wherein d solution is at least one in glycerite, camphorsulfonic acid solution, solution of sodium bisulfite, and mass fraction is 5% ~ 15%.
Drying steps after rinsing is: the polymer film after rinsing is dried and obtained reverse osmosis membrane in baking oven.Bake out temperature is 75 ~ 100 DEG C, and preferably 85 DEG C, be 2min ~ 40min drying time, preferably 3min, blower fan wind speed 2m/s ~ 20m/s, preferably 4m/s.
The composite membrane pore-size distribution finally making is 0.5nm ~ 10nm, and aramid layer thickness is 30nm ~ 200nm.
Adopt the complex reverse osmosis membrane performance that following method is prepared said method to test:
Flux and salt rejection rate to complex reverse osmosis membrane on diaphragm monitor station are tested, and test condition is: the self-control 250ppmNaCl aqueous solution, probe temperature are that 25 DEG C, monitor station operating pressure are 0.45Mpa, 5.2 square feet of monitor station Validity Test areas.Open detection platform, under test pressure, move 12min, start to measure (the product water collection that every sample film is made, collect altogether 8min, at least 3 of sample film test quantity prepared by every kind of preparation method, test result is averaged), record strong brine electrical conductivity (being NaCl aqueous solution electrical conductivity), produce water volume (ml) and produce water conductivity (μ s/cm), calculate permeant flux (gfd, i.e. gallon/square feet day), calculate salt rejection rate (%), salt rejection rate computing formula is 1 ~ (producing water conductivity/strong brine electrical conductivity) × 100%.
On above-mentioned disclosed preparation method's basis, according to being chosen as below example, the present invention is described further respectively for various raw materials; Be that to be chosen as molecular weight be 2000,3000 and 5000 Hyperbranched Polymer with Terminal Amido to Hyperbranched Polymer with Terminal Amido, polyamine is chosen as m-phenylene diamine (MPD), aromatic series acyl chlorides is chosen as pyromellitic trimethylsilyl chloride, organic solvent is chosen as n-hexane, a solution is chosen as lactic acid solution, b solution is chosen as ethanolic solution, and c solution is chosen as nano TiO 2 carrying silver solution, and d solution is chosen as glycerite.
Embodiment 1
A preparation method for dissaving polymer polyamide composite reverse osmosis membrane, comprises the following steps:
(1) one side of the porous support layer of hygrometric state being immersed into molecular weight is in 2000 Hyperbranched Polymer with Terminal Amido and linear polyamine mixed aqueous solution (gross mass mark 3.5%), continue to use rubber roll-in except surface liquid after 20s, wherein the mass fraction of Hyperbranched Polymer with Terminal Amido in solution is 1%, m-phenylene diamine (MPD) mass fraction 2.5%, neopelex mass fraction is 0.15%;
(2) continuation one side is immersed in and contains in the hexane solution that mass fraction is 0.1% pyromellitic trimethylsilyl chloride, continues 20s, and 30s wherein dries in the shade under rear room temperature;
(3) then carry out four step rinsings, to soak the lactic acid solution 1min that mass fraction is 5% successively, 5% ethanolic solution 1min, 0.6% nano TiO 2 carrying silver solution 1min, 12% glycerite 1min, finally at 85 DEG C, dry 3min is dried and is obtained reverse osmosis membrane.
Embodiment 2
A preparation method for dissaving polymer polyamide composite reverse osmosis membrane, comprises the following steps:
(1) one side of the porous support layer of hygrometric state being immersed into molecular weight is in 2000 Hyperbranched Polymer with Terminal Amidos and linear polyamine mixed aqueous solution (mass fraction 3.5%), continue to use rubber roll-in except surface liquid after 20s, wherein the mass fraction of Hyperbranched Polymer with Terminal Amido in solution is 1.5%, m-phenylene diamine (MPD) mass fraction 2%, neopelex mass fraction is 0.15%;
(2) continuation one side is immersed in and contains in the hexane solution that mass fraction is 0.1% pyromellitic trimethylsilyl chloride, continues 20s, and 30s wherein dries in the shade under rear room temperature;
(3) then carry out four step rinsings, to soak the lactic acid solution 1min that mass fraction is 5% successively, 5% ethanolic solution 1min, 0.6% nano TiO 2 carrying silver solution 1min, 12% glycerite 1min, finally at 85 DEG C, dry 3min is dried and is obtained reverse osmosis membrane.
Embodiment 3
A preparation method for dissaving polymer polyamide composite reverse osmosis membrane, comprises the following steps:
(1) the one side face of the porous support layer of hygrometric state being immersed into molecular weight is in 2000 Hyperbranched Polymer with Terminal Amidos and linear polyamine mixed aqueous solution (mass fraction 3.5%), continue to use rubber roll-in except surface liquid after 20s, wherein the mass fraction of Hyperbranched Polymer with Terminal Amido in solution is 2%, m-phenylene diamine (MPD) mass fraction 1.5%, neopelex mass fraction is 0.15%;
(2) continuation one side is immersed in and contains in the hexane solution that mass fraction is 0.1% pyromellitic trimethylsilyl chloride, continues 20s, and 30s wherein dries in the shade under rear room temperature;
(3) then carry out four step rinsings, to soak the lactic acid solution 1min that mass fraction is 5% successively, 5% ethanolic solution 1min, 0.6% nano TiO 2 carrying silver solution 1min, 12% glycerite 1min, finally at 85 DEG C, dry 3min is dried and is obtained reverse osmosis membrane.
Embodiment 4
A preparation method for dissaving polymer polyamide composite reverse osmosis membrane, comprises the following steps:
(1) one side of the porous support layer of hygrometric state being immersed into molecular weight is in 2000 Hyperbranched Polymer with Terminal Amidos and linear polyamine mixed aqueous solution (mass fraction 3.5%), continue to use rubber roll-in except surface liquid after 20s, wherein the mass fraction of Hyperbranched Polymer with Terminal Amido in solution is 2.5%, m-phenylene diamine (MPD) mass fraction 1%, neopelex mass fraction is 0.15%;
(2) continuation one side is immersed in and contains in the hexane solution that mass fraction is 0.1% pyromellitic trimethylsilyl chloride, continues 20s, and 30s wherein dries in the shade under rear room temperature;
(3) then carry out four step rinsings, to soak the lactic acid solution 1min that mass fraction is 5% successively, 5% ethanolic solution 1min, 0.6% nano TiO 2 carrying silver solution 1min, 12% glycerite 1min, finally at 85 DEG C, dry 3min is dried and is obtained reverse osmosis membrane.
Embodiment 5
A preparation method for dissaving polymer polyamide composite reverse osmosis membrane, comprises the following steps:
(1) one side of the porous support layer of hygrometric state being immersed into molecular weight is in 2000 Hyperbranched Polymer with Terminal Amidos and linear polyamine mixed aqueous solution (mass fraction 3.5%), continue to use rubber roll-in except surface liquid after 20s, wherein the mass fraction of Hyperbranched Polymer with Terminal Amido in solution is 3%, m-phenylene diamine (MPD) mass fraction 0.5%, neopelex mass fraction is 0.15%;
(2) continuation one side is immersed in and contains in the hexane solution that mass fraction is 0.1% pyromellitic trimethylsilyl chloride, continues 20s, and 30s wherein dries in the shade under rear room temperature;
(3) then carry out four step rinsings, to soak the lactic acid solution 1min that mass fraction is 5% successively, 5% ethanolic solution 1min, 0.6% nano TiO 2 carrying silver solution 1min, 12% glycerite 1min, finally at 85 DEG C, dry 3min is dried and is obtained reverse osmosis membrane.
Embodiment 6
A preparation method for dissaving polymer polyamide composite reverse osmosis membrane, comprises the following steps:
(1) the one side face of the porous support layer of hygrometric state being immersed into molecular weight is in 2000 Hyperbranched Polymer with Terminal Amidos and linear polyamine mixed aqueous solution (mass fraction 4%), continue to use rubber roll-in except surface liquid after 20s, wherein the mass fraction of Hyperbranched Polymer with Terminal Amido in solution is 1%, m-phenylene diamine (MPD) mass fraction 3%, neopelex mass fraction is 0.15%;
(2) continuation one side is immersed in and contains in the hexane solution that mass fraction is 0.1% pyromellitic trimethylsilyl chloride, continues 20s, and 30s wherein dries in the shade under rear room temperature;
(3) then carry out four step rinsings, to soak the lactic acid solution 1min that mass fraction is 5% successively, 5% ethanolic solution 1min, 0.6% nano TiO 2 carrying silver solution 1min, 12% glycerite 1min, finally at 85 DEG C, dry 3min is dried and is obtained reverse osmosis membrane.
Comparative example 1
A preparation method for complex reverse osmosis membrane, comprises the following steps:
(1) one side of the porous support layer of hygrometric state is immersed in the linear polyamine aqueous solution, continues to use rubber roll-in except surface liquid after 20s, wherein m-phenylene diamine (MPD) mass fraction 3.5%, neopelex mass fraction is 0.15%;
(2) continuation one side is immersed in and contains in the hexane solution that mass fraction is 0.1% pyromellitic trimethylsilyl chloride, continues 20s, and 30s wherein dries in the shade under rear room temperature;
(3) then carry out four step rinsings, to soak the lactic acid solution 1min that mass fraction is 5% successively, 5% ethanolic solution 1min, 0.6% nano TiO 2 carrying silver solution 1min, 12% glycerite 1min, finally at 85 DEG C, dry 3min is dried and is obtained reverse osmosis membrane.
Embodiment 7
A preparation method for dissaving polymer polyamide composite reverse osmosis membrane, comprises the following steps:
(1) one side of the porous support layer of hygrometric state being immersed into molecular weight is in 2000 Hyperbranched Polymer with Terminal Amidos and linear polyamine mixed aqueous solution (mass fraction 3.5%), continue to use rubber roll-in except surface liquid after 20s, wherein the mass fraction of Hyperbranched Polymer with Terminal Amido in solution is 1.5%, m-phenylene diamine (MPD) mass fraction 2%, neopelex mass fraction is 0.15%;
(2) continuation one side is immersed in and contains in the hexane solution that mass fraction is 0.1% pyromellitic trimethylsilyl chloride, continues 20s, and 30s wherein dries in the shade under rear room temperature;
(3) then carry out four step rinsings, to soak the lactic acid solution 1min that mass fraction is 6% successively, 5% ethanolic solution 1min, 0.6% nano TiO 2 carrying silver solution 1min, 12% glycerite 1min, finally at 85 DEG C, dry 3min is dried and is obtained reverse osmosis membrane.
Embodiment 8
A preparation method for dissaving polymer polyamide composite reverse osmosis membrane, comprises the following steps:
(1) one side of the porous support layer of hygrometric state being immersed into molecular weight is in 2000 Hyperbranched Polymer with Terminal Amidos and linear polyamine mixed aqueous solution (mass fraction 3.5%), continue to use rubber roll-in except surface liquid after 20s, wherein the mass fraction of Hyperbranched Polymer with Terminal Amido in solution is 1.5%, m-phenylene diamine (MPD) mass fraction 2%, neopelex mass fraction is 0.15%;
(2) continuation one side is immersed in and contains in the hexane solution that mass fraction is 0.1% pyromellitic trimethylsilyl chloride, continues 20s, and 30s wherein dries in the shade under rear room temperature;
(3) then carry out four step rinsings, to soak the lactic acid solution 1min that mass fraction is 7% successively, 5% ethanolic solution 1min, 0.6% nano TiO 2 carrying silver solution 1min, 12% glycerite 1min, finally at 85 DEG C, dry 3min is dried and is obtained reverse osmosis membrane.
Embodiment 9
A preparation method for dissaving polymer polyamide composite reverse osmosis membrane, comprises the following steps:
(1) one side of the porous support layer of hygrometric state being immersed into molecular weight is in 2000 Hyperbranched Polymer with Terminal Amidos and linear polyamine mixed aqueous solution (mass fraction 3.5%), continue to use rubber roll-in except surface liquid after 20s, wherein the mass fraction of Hyperbranched Polymer with Terminal Amido in solution is 1.5%, m-phenylene diamine (MPD) mass fraction 2%, neopelex mass fraction is 0.15%;
(2) continuation one side is immersed in and contains in the hexane solution that mass fraction is 0.3% pyromellitic trimethylsilyl chloride, continues 20s, and 30s wherein dries in the shade under rear room temperature;
(3) then carry out four step rinsings, to soak the lactic acid solution 1min that mass fraction is 5% successively, 6% ethanolic solution 1min, 0.6% nano TiO 2 carrying silver solution 1min, 12% glycerite 1min, finally at 85 DEG C, dry 3min is dried and is obtained reverse osmosis membrane.
Comparative example 2
A preparation method for complex reverse osmosis membrane, comprises the following steps:
(1) the porous support layer one side of hygrometric state is immersed in the linear polyamine aqueous solution, continues to use rubber roll-in except surface liquid after 20s, wherein m-phenylene diamine (MPD) mass fraction 3.5%, neopelex mass fraction is 0.15%;
(2) continuation one side is immersed in and contains in the hexane solution that mass fraction is 0.1% pyromellitic trimethylsilyl chloride, continues 20s, and 30s wherein dries in the shade under rear room temperature;
(3) then carry out four step rinsings, to soak the lactic acid solution 1min that mass fraction is 6% successively, 5% ethanolic solution 1min, 0.6% nano TiO 2 carrying silver solution 1min, 12% glycerite 1min, finally at 85 DEG C, dry 3min is dried and is obtained reverse osmosis membrane.
Embodiment 10
A preparation method for dissaving polymer polyamide composite reverse osmosis membrane, comprises the following steps:
(1) one side of the porous support layer of hygrometric state being immersed into molecular weight is in 3000 Hyperbranched Polymer with Terminal Amido and linear polyamine mixed aqueous solution (gross mass mark 3.5%), continue to use rubber roll-in except surface liquid after 20s, wherein the mass fraction of Hyperbranched Polymer with Terminal Amido in solution is 1%, m-phenylene diamine (MPD) mass fraction 2.5%, neopelex mass fraction is 0.15%;
(2) continuation one side is immersed in and contains in the hexane solution that mass fraction is 0.1% pyromellitic trimethylsilyl chloride, continues 20s, and 30s wherein dries in the shade under rear room temperature;
(3) then carry out four step rinsings, to soak the lactic acid solution 1min that mass fraction is 5% successively, 5% ethanolic solution 1min, 0.6% nano TiO 2 carrying silver solution 1min, 12% glycerite 1min, finally at 85 DEG C, dry 3min is dried and is obtained reverse osmosis membrane.
Embodiment 11
A preparation method for dissaving polymer polyamide composite reverse osmosis membrane, comprises the following steps:
(1) one side of the porous support layer of hygrometric state being immersed into molecular weight is in 5000 Hyperbranched Polymer with Terminal Amido and linear polyamine mixed aqueous solution (gross mass mark 3.5%), continue to use rubber roll-in except surface liquid after 20s, wherein the mass fraction of Hyperbranched Polymer with Terminal Amido in solution is 1%, m-phenylene diamine (MPD) mass fraction 2.5%, neopelex mass fraction is 0.15%;
(2) continuation one side is immersed in and contains in the hexane solution that mass fraction is 0.1% pyromellitic trimethylsilyl chloride, continues 20s, and 30s wherein dries in the shade under rear room temperature;
(3) then carry out four step rinsings, to soak the lactic acid solution 1min that mass fraction is 5% successively, 5% ethanolic solution 1min, 0.6% nano TiO 2 carrying silver solution 1min, 12% glycerite 1min, finally at 85 DEG C, dry 3min is dried and is obtained reverse osmosis membrane.
The performance test results of the prepared sample film of above-described embodiment and reference examples is as shown in the table:
| Classification | Flux (GFD) | Salt rejection rate (%) |
| Embodiment 1 | 30.5 | 97.6 |
| Embodiment 2 | 34.8 | 97.4 |
| Embodiment 3 | 39.4 | 96.8 |
| Embodiment 4 | 42.3 | 95.3 |
| Embodiment 5 | 47.4 | 94.0 |
| Embodiment 6 | 28.3 | 97.2 |
| Comparative example 1 | 20.1 | 97.4 |
| Embodiment 7 | 36 | 96.2 |
| Embodiment 8 | 37.2 | 95.3 |
| Embodiment 9 | 36.2 | 95.8 |
| Comparative example 2 | 24.8 | 95.6 |
| Embodiment 10 | 30.4 | 96.8 |
| Embodiment 11 | 27.8 | 97.1 |
By the contrast of above embodiment and technical indicator, the present invention (embodiment 1-11) is keeping under the substantially constant prerequisite of salt rejection rate and prior art (comparative example 1 and 2), by introduce Hyperbranched Polymer with Terminal Amido in desalination layer, utilize its three dimensions pore passage structure can increase substantially flux, thereby improve the efficiency of counter-infiltration; And those skilled in the art are to be understood that; above embodiment is only several exemplary embodiments of the present invention; in the situation that not exceeding or do not depart from protection domain of the present invention; technical solutions and their implementation methods of the present invention have multiple modification, improvement or equivalent variations, and these all should fall within the scope of protection of the present invention.
Claims (10)
1. a dissaving polymer polyamide composite reverse osmosis membrane, by porous support layer with and the polyamide desalination layer that forms by interfacial polymerization of surface, it is characterized in that: described polyamide desalination layer is dissaving polymer aramid layer, and described dissaving polymer aramid layer is formed by interfacial polymerization by Hyperbranched Polymer with Terminal Amido, polyamine and aromatic series acyl chlorides.
2. dissaving polymer polyamide composite reverse osmosis membrane according to claim 1, is characterized in that, described dissaving polymer is that molecular weight is 2000 ~ 5000 Hyperbranched Polymer with Terminal Amidos; Described dissaving polymer aramid layer thickness is 30nm ~ 200nm.
3. dissaving polymer polyamide composite reverse osmosis membrane according to claim 1, it is characterized in that, described porous support layer is any one in polyacrylonitrile, polyether sulfone, modified polyvinilidene fluoride and polysulfones micro-filtration membrane or milipore filter, and described porous support layer thickness is 60 μ m ~ 120 μ m; Described complex reverse osmosis membrane is flat sheet membrane, hollow-fibre membrane or tubular membrane; The pore-size distribution of described complex reverse osmosis membrane is 0.5 ~ 10nm.
4. the preparation method of the arbitrary described dissaving polymer polyamide composite reverse osmosis membrane of claim 1-3, is characterized in that, comprises the following steps:
(1), at the hygrometric state porous support layer surface dip-coating dissaving polymer having cleaned up and the mixed aqueous solution of linear polyamine, then remove surface liquid, the time of described dip-coating is 3 s ~ 300 s; The total mass fraction of described dissaving polymer and linear polyamine mixed aqueous solution is 2% ~ 10%; Described dissaving polymer is that molecular weight is 2000 ~ 5000 Hyperbranched Polymer with Terminal Amidos; Described linear polyamine is at least one in diethylamine, triethylamine, propane diamine, butanediamine, pentanediamine, hexamethylene diamine, piperazine, 4-amino methyl piperazine, m-phenylene diamine (MPD), o-phenylenediamine and p-phenylenediamine (PPD);
(2), contact with the organic solution of aromatic series acyl chlorides with the porous support layer surface of linear polyamine mixed aqueous solution scribbling Hyperbranched Polymer with Terminal Amido, carry out obtaining aramid layer on the surface of porous support layer after interfacial polymerization, the time of described interfacial polymerization is 3s ~ 120s; The mass fraction of described aromatic series acyl chlorides organic solution is 0.05% ~ 2%, described aromatic series acyl chlorides is pyromellitic trimethylsilyl chloride, m-phthaloyl chloride, face at least one in phthalyl chloride, paraphthaloyl chloride and benzene-disulfo-chloride, and the solvent of described organic solution is at least one in the aliphatic hydrocarbon that contains 4 ~ 10 carbon atoms; Then drop is except surperficial residual reaction solution, and at room temperature dries in the shade, described in time of drying in the shade be 4s ~ 300s;
(3), the following four kinds of aqueous solution of porous support layer employing with aramid layer desalination layer prepared step (2) the successively last oven dry of rinsing are obtained to complex reverse osmosis membrane; Described solution is followed successively by: a solution that mass fraction is 3% ~ 15%, and described a is any one in maleic acid, maleic anhydride, citric acid, oxalic acid, lactic acid; Mass fraction is 3% ~ 15% b solution, and described b is methyl alcohol or ethanol; Mass fraction is 0.05% ~ 5% c solution, and described c is any one in nano TiO 2 carrying silver, nano zine oxide, Nano Silver, nano titanium oxide; Mass fraction is 5% ~ 10% d solution, and described d is at least one in glycerine, camphorsulfonic acid, sodium hydrogensulfite.
5. the preparation method of dissaving polymer polyamide composite reverse osmosis membrane according to claim 4, is characterized in that, the total mass fraction of described Hyperbranched Polymer with Terminal Amido and linear polyamine mixed aqueous solution is 3% ~ 5%; The mass fraction of described aromatic series acyl chlorides organic solution is 0.1% ~ 0.3%; Described aromatic series acyl chlorides is preferably pyromellitic trimethylsilyl chloride; The solvent of described organic solution is preferably n-hexane.
6. the preparation method of dissaving polymer polyamide composite reverse osmosis membrane according to claim 4, is characterized in that, described a is preferably lactic acid, and the mass fraction of lactic acid solution is 5% ~ 7%; Described b is preferably ethanol, and the mass fraction of ethanolic solution is 5% ~ 7%; Described c is preferably nano TiO 2 carrying silver, and the mass fraction of nano TiO 2 carrying silver solution is 0.6% ~ 1%.
7. the preparation method of dissaving polymer polyamide composite reverse osmosis membrane according to claim 4, it is characterized in that, in described mixed aqueous solution, also include mass fraction and be 0.05% ~ 0.8% surfactant, described surfactant is at least one in neopelex, sodium glycocholate, dioctyl sodium sulfosuccinate, lauryl sodium sulfate, sldium lauryl sulfate.
8. the preparation method of dissaving polymer polyamide composite reverse osmosis membrane according to claim 7, is characterized in that, described surfactant is preferably neopelex, and its mass fraction is 0.15%.
9. the preparation method of dissaving polymer polyamide composite reverse osmosis membrane according to claim 5, is characterized in that, the temperature of described oven dry is that 75 ~ 100 DEG C, time are 2min ~ 40min; The rinsing time of four kinds of described solution is 60 s.
10. the preparation method of dissaving polymer polyamide composite reverse osmosis membrane according to claim 9, is characterized in that, the temperature of described oven dry is that 85 DEG C, time are 3min.
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