CN115090125A - Method and device for preparing polyamide thin-layer composite film by transfer printing and product - Google Patents
Method and device for preparing polyamide thin-layer composite film by transfer printing and product Download PDFInfo
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- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
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Abstract
The invention discloses a method, a device and a product for preparing a polyamide thin-layer composite film by transfer printing, wherein the method comprises the following steps: uniformly coating the polyamine solution on the surface of the conveying mechanism through a coating mechanism to form a polyamine liquid film; immersing a conveying mechanism with a liquid film on the surface into a polyacyl chloride solution, and performing polymerization reaction on polyamine and polyacyl chloride at an interface to generate a polyamide nano film; compounding the polyamide nano film with the porous base film through a compounding mechanism from the upper side of the polyamide nano film to obtain a polyamide thin-layer composite film; the composite strength of the porous base membrane and the polyamide nano-film is enhanced by applying pressure and temperature through a hot-pressing mechanism; and drying and rolling the polyamide thin-layer composite film after the polyamide thin-layer composite film passes through a separation mechanism. The preparation method is simple and convenient to operate, and can continuously and massively compound the polyamide nano film synthesized by the free interface with various porous base films.
Description
Technical Field
The invention relates to the technical field of membrane separation, in particular to a method, a device and a product for preparing a polyamide thin-layer composite membrane by transfer printing.
Background
The polyamide thin-layer composite membrane is widely applied to the fields of separation and purification and the like due to the wide selectable range of the porous base membrane and the selective separation layer and the easy accurate regulation and control of the surface property of the selective separation layer, and has important application in the aspects of seawater desalination, wastewater treatment, drug concentration, food decolorization and the like. The interfacial polymerization method is a main method for preparing the polyamide thin-layer composite membrane due to mild operation conditions, simple process, high synthesis efficiency and low preparation cost. However, because the interfacial polymerization reaction rate is too fast, the difficulty of interfacial polymerization regulation is increased, and the improvement of the performance of the composite membrane becomes a challenge and a difficult problem. Therefore, the controllability of the interfacial polymerization reaction process is increased, which is a sufficient condition for preparing the structure-controllable high-performance composite membrane.
For example, chinese patent publication No. CN111420566B discloses a method for preparing a solvent-resistant nanofiltration membrane of polyamide containing fluorinated organic nanoparticles, in which polyamine, dopamine and fluoroalkyl thiol compounds are used as reactive monomers, and the fluorinated organic nanoparticles are formed by michael addition and schiff base reaction, and then the fluorinated organic nanoparticles are formed on the surface of a porous support membrane by interfacial polymerization with polyacyl chloride. The low surface energy characteristic of the fluorinated organic nanoparticles is utilized to regulate and control the interfacial polymerization process, the chemical composition, the microstructure and the hydrophilicity and hydrophobicity of a polyamide separation layer are optimized, the polyamide solvent-resistant nanofiltration membrane with a unique pore channel structure is obtained, the prepared membrane has high separation selectivity and solvent permeation flux, and the membrane preparation method is simple and convenient, is easy to regulate and control, and has good industrial application prospects. However, this method cannot avoid the influence of the properties of the porous base film on the interfacial polymerization process.
Chinese patent publication No. CN112755813B discloses a method for preparing a thin film composite membrane containing an intermediate layer, which comprises complexing metal ions and organic phosphoric acid on the surface of a supporting layer to obtain a plurality of complex intermediate layers, and then in-situ polymerizing and curing the complex intermediate layers to form a polymer selective layer, thereby obtaining the thin film composite membrane. The invention selects a material with complexation as the intermediate layer to prepare the hollow fiber film composite membrane containing the intermediate layer. The middle layer is introduced by a simple soaking method, so that the influence of a porous base membrane structure on interfacial polymerization reaction is avoided, the uniformity of a selective layer structure is optimized, the dehydration performance of an organic solvent (ethanol) in the polyamide hollow fiber film composite membrane is improved, and compared with a polyamide film composite membrane without the middle layer, the separation factor of the polyamide film composite membrane with the middle layer is greatly improved. However, the introduction of the intermediate layer leads to complicated preparation steps of the composite membrane and also weakens the bonding force between the selective separation layer and the porous base membrane.
Chinese patent publication No. CN112657352B discloses a method for preparing a polyamide film composite reverse osmosis membrane, which comprises preparing an ultrathin metal organic framework CuBDC nanosheet with amphiphilic property, and placing the ultrathin metal organic framework CuBDC nanosheet on a water/oil two-phase interface, wherein the water phase is m-phenylenediamine aqueous solution, the oil phase is n-hexane, after the n-hexane is completely volatilized, an n-hexane solution containing trimesoyl chloride is slowly added to the interface, and the reaction is carried out to form a modified polyamide nano film. Carefully placing the film on an ultrafiltration membrane substrate to prepare the polyamide thin-layer composite reverse osmosis membrane. The inherent thickness of the polyamide film formed on the CuBDC auxiliary free interface is about 5nm, the directivity is provided for the thermal diffusion of the interface polymerization reaction by the ultrathin metal organic framework nanosheets, the intensity of the interface polymerization reaction is enhanced, the diffusion rate of the m-phenylenediamine to the oil phase direction is increased, the surface area and the crosslinking degree of the ultrathin polyamide film are increased while the ultrathin polyamide film is formed, and the flux and the salt rejection rate of the film are greatly increased. The free interface polymerization can effectively avoid the influence of the porous base membrane property on the reaction and improve the reaction controllability, but the method has complex operation, is easy to introduce defects when transferring the polyamide film, and is difficult to realize large-area preparation.
The transfer printing is a printing method that disperse dye or paint is printed on paper according to pattern to make transfer paper, and then the dye or paint on the transfer paper is transferred to the textile under a certain condition.
Disclosure of Invention
The invention provides a method and a device for preparing a polyamide thin-layer composite film by transfer printing, and aims to transfer and attach a polyamide nano film generated by interfacial polymerization to the surface of a porous base film, realize efficient and stable compounding of the polyamide nano film and the porous base film and prepare the polyamide thin-layer composite film. The preparation method is simple to operate, is suitable for various porous base membranes, can improve the acting force and the composite strength between the polyamide nano-film and the porous base membrane through the hot pressing process and the regulation and control of the surface properties of the porous base membrane, avoids the problem that high-viscosity amine solution is not easy to remove when the porous base membrane is compounded with the polyamide nano-film on the upper side of the polyamide nano-film, and can realize the large-area continuous preparation of the structure-controllable high-performance polyamide thin-layer composite membrane.
The technical scheme of the invention is as follows:
a device for preparing a polyamide thin-layer composite film by transfer printing comprises a conveying mechanism, a coating mechanism, a reaction mechanism, a compounding mechanism, a hot-pressing mechanism, a separating mechanism, a drying mechanism and a winding mechanism;
the coating mechanism is arranged above the conveying mechanism and used for coating the first reaction monomer solution on the surface of the conveying mechanism to form a first reaction monomer liquid film;
the reaction mechanism is arranged at the downstream of the coating mechanism and the upstream of the composite mechanism and is used for providing a stable liquid-liquid interface formed by the solution of the second monomer and the liquid film of the first monomer, and when the conveying mechanism bearing the liquid film of the first reaction monomer passes through the reaction mechanism, the first reaction monomer and the second reaction monomer carry out polymerization reaction at the interface to generate the polyamide nano film;
the compounding mechanism is arranged at the downstream of the reaction mechanism and is used for compounding the porous base membrane with the polyamide nano-film to prepare a polyamide thin-layer composite membrane;
the hot-pressing mechanism is arranged at the downstream of the composite mechanism and at the upstream of the separation mechanism and is used for enhancing the composite strength of the polyamide nano film and the porous base film;
the separation mechanism is arranged at the downstream of the hot pressing mechanism and is used for separating the polyamide thin-layer composite film from the conveying mechanism;
the drying mechanism and the winding mechanism are sequentially arranged at the downstream of the separating mechanism and are used for drying and winding the polyamide thin-layer composite film.
Preferably, the porous base film is compounded with the polyamide nano-film on the upper side of the polyamide nano-film.
Preferably, the conveying mechanism is a roller or a conveying belt.
Preferably, the material of the conveying mechanism is an aluminum film, a steel belt, a nylon film, polyurethane or a polyester film; the width of the conveying mechanism is 0.01-20 m.
Preferably, the distance between the scraper of the coating mechanism and the conveying mechanism is adjustable.
Preferably, the composite mechanism consists of a roller.
The hot-pressing mechanism applies pressure and temperature to the polyamide composite membrane and is used for enhancing the composite strength of the polyamide nano-film and the porous base membrane.
The invention also provides a method for preparing the polyamide thin-layer composite film by transfer printing, which comprises the following steps:
(1) uniformly coating the solution of the first reaction monomer polyamine on the surface of the conveying mechanism through a coating mechanism to form a polyamine solution liquid film;
(2) immersing a conveying mechanism with a polyamine solution liquid film on the surface into a solution of second reaction monomer polybasic acyl chloride, and performing polymerization reaction on the polybasic amine and the polybasic acyl chloride at an interface to generate a polyamide nano film;
(3) compounding the porous base membrane with the polyamide nano-film from the upper side of the polyamide nano-film through a compounding mechanism to obtain a polyamide thin-layer composite membrane;
(4) a certain pressure and temperature are applied through a hot-pressing mechanism, so that the composite strength of the porous base membrane and the polyamide nano-film is enhanced;
(5) and (3) immersing the conveying mechanism attached with the polyamide thin-layer composite membrane into a separation mechanism containing constant-temperature water, separating the polyamide thin-layer composite membrane from the conveying mechanism, and then drying and rolling.
In the method, the polyamide nano film prepared by forming a free interface on a compact substrate and polymerizing is compounded with the porous base film in a transfer printing mode, so that the interfacial polymerization process is not influenced by the porous base film, the variety of the applicable porous base film is widened, the binding force between the porous base film and the selective separation layer can be increased by hot pressing operation or optimization of the property of the porous base film, and the separation performance of the polyamide thin-layer composite film in the long-term use process is maintained.
In the step (1):
preferably, the polyamine solution is polyamine glycerol aqueous solution.
More preferably, the viscosity of the polyamine glycerol aqueous solution is in the range of 10 to 300 mPas.
Polyamine solutions in this viscosity range are stable on the conveyor belt surface. The viscosity of the solution is too low, which is not beneficial to forming a stable and uniform liquid film; the solution viscosity is too high, which reduces the amount of amine monomer participating in the reaction, and is not favorable for preparing a polyamide film having a high degree of crosslinking.
The thickness of the polyamine liquid film can be controlled by adjusting the distance between the scraper and the conveying mechanism of the coating mechanism.
Preferably, the thickness of the polyamine liquid film is 1-500 μm.
When the polyamine liquid film is too thin, the total amount of polyamine monomers is insufficient, so that the damage and the defect of the polyamide nano film are easily caused; when the polyamine liquid film is too thick, the liquid film is easy to flow in the transfer process, so that interface disturbance and interface nonuniformity are caused.
More preferably, the thickness of the polyamine liquid film is 20 to 300 μm.
The polyamine is at least one of 1, 3-cyclohexyldimethylamine, diethylenetriamine, p-phenylenediamine, piperazine, o-phenylenediamine and m-phenylenediamine; the concentration of the polyamine solution is 0.01-100 g/L.
The monomer concentration is one of the key factors affecting the polymerization kinetics. When the monomer concentration is low, the prepared polyamide film is loose and is easy to generate defects; when the monomer concentration is moderate, the monomer diffusion capacity is matched with the reaction capacity, and the prepared polyamide film has higher osmotic selectivity; when the monomer concentration is too high, the monomer diffuses too fast, and the prepared polyamide film is thick, resulting in low permeability.
More preferably, the polyamine is m-phenylenediamine; the concentration of the m-phenylenediamine solution is 1-50 g/L.
In the step (2):
the polybasic acyl chloride is at least one of phthaloyl chloride, trimesoyl chloride, terephthaloyl chloride and isophthaloyl chloride; the solvent of the polybasic acyl chloride solution is at least one of heptane, normal hexane, cyclohexane, trichlorotrifluoroethane and isoparaffin; the monomer concentration of the polyacyl chloride solution is 0.1-10 g/L.
More preferably, the polybasic acyl chloride is trimesoyl chloride; the solvent is isoalkane; the monomer concentration of the polyacyl chloride solution is 0.3-5 g/L.
The monomer concentration of the polyacyl chloride solution is also one of the key factors affecting the polymerization kinetics. Both too high and too low concentrations of acid chloride monomer do not form polyamide membranes with high permselectivity.
Preferably, the time of the interfacial polymerization reaction is 5 to 900 seconds.
The reaction time is short and a compact polyamide film cannot be formed; too long results in reduced efficiency and reduced permeability.
More preferably, the interfacial polymerization reaction time is 30-450 s.
In the step (3):
the polyamide nanometer film on the surface of the conveying mechanism is compounded with various porous base films.
Preferably, the porous base membrane is a polypropylene membrane, a polyethylene membrane, a nylon membrane, a polyvinylidene chloride membrane, a polyacrylonitrile membrane or a surface property different asymmetric membrane prepared by biomimetically modifying single-side mussels of various membrane materials.
In the step (4):
the composite strength of the porous base membrane and the polyamide nano-film is enhanced through a hot-pressing mechanism.
Preferably, the hot pressing temperature is 50-100 ℃; the hot pressing pressure is 10-100000 Pa.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention develops a method and a device for preparing a polyamide thin-layer composite film by transfer printing, which can be used for large-scale continuous preparation;
(2) the porous base membrane is compounded with the nano-film on the upper side of the polyamide nano-film, namely the side of the second monomer solution, the solvent of the second monomer solution has low polarity and can infiltrate the porous base membrane with solvent resistance and low surface energy, so that the porous base membrane is favorably attached to the nano-film, and the variety of the porous base membrane is expanded;
(3) the high-viscosity first monomer solution is positioned on the outer surface of the nano film and is easier to clean and remove;
(4) the composite strength of the polyamide nano film and the porous base film can be effectively enhanced by adjusting the pressure and the temperature of the hot-pressing roller;
(5) the bonding force between the selective separation layer and the base membrane can be enhanced by optimizing the property of the porous base membrane, so that the long-term use of the polyamide thin-layer composite membrane is ensured;
(6) the method has universality for various polyamide films and various porous base films, and the prepared polyamide thin-layer composite film can be applied to the fields of organic nanofiltration, organic reverse osmosis, gas separation and the like.
The polyamide nano film can be completely transferred to the surface of the porous base film in a large area by a transfer printing method, and the method for preparing the polyamide composite film is expanded.
Drawings
FIG. 1 is a schematic structural diagram of an apparatus for preparing a polyamide thin-layer composite film by transfer printing.
Detailed Description
The polyamide thin-layer composite organic nanofiltration membrane can be prepared by adopting the structural device shown in FIG. 1.
Firstly, a polyamine solution is coated on the surface of a conveyor belt through a scraper, a polyamine glycerol aqueous solution with a certain thickness is immersed into a solution containing polyacyl chloride under the drive of a motor, and reaction is carried out for a certain time. The polyamide nano film generated on the free interface is compounded with the polypropylene film and then is immersed into a separation tank, the polyamide thin-layer composite film automatically floats on the water surface, enters a drying device and is collected by a winding mechanism. The conveyor belt is then recycled for reuse.
In the examples, the rejection rate and the permeation flux are two important parameters for evaluating the organic nanofiltration membrane. Wherein the retention is defined as:
wherein, C f Represents the concentration of solute in the feed solution before treatment; c p Indicating the concentration of solute in the filtrate after treatment.
The permeate flux is defined as: the volume of the organic solvent per unit membrane area per unit pressure per unit time under a certain operation pressure is L/m 2 H bar, formula:
wherein V represents the volume of the filtrate which penetrates through the organic nanofiltration membrane, and the unit is L; a represents the effective membrane area in m 2 (ii) a t represents time in units of h; p represents the pressure used for the test in bar.
The present invention is described in more detail by the following examples, which are not intended to limit the invention.
Example 1
M-phenylenediamine is selected as a polyamine monomer, the m-phenylenediamine is dissolved in a glycerol aqueous solution, the concentration of the m-phenylenediamine is 30g/L, and the viscosity of an amine monomer solution is controlled to be 200-250 mPa & s. Trimesoyl chloride is selected as a polybasic acyl chloride monomer, and is dissolved in hexane, wherein the concentration of the trimesoyl chloride is 1.5 g/L.
A container filled with m-phenylenediamine solution is coated with a 200-micron thick m-phenylenediamine solution liquid film on the surface of a smooth aluminum conveying belt with the width of 3 m by a scraper. Then the mixture enters a reaction mechanism, a m-phenylenediamine solution liquid membrane is in contact with a trimesoyl chloride solution to trigger interfacial polymerization, after the reaction is carried out for 300s, the reaction product passes through a compounding mechanism, and the generated polyamide nano film is compounded with a polypropylene film. Under the action of the temperature of a hot pressing mechanism of 60 ℃ and the pressure of 100Pa, the composite strength of the polyamide nano film and the porous base film is enhanced. And then the composite membrane and the conveyer belt enter a separation tank together, the polyamide thin-layer composite membrane which automatically falls off is dried and thermally treated for 5min at the temperature of 60 ℃, and the polyamide thin-layer composite membrane is obtained by winding. The organic nanofiltration test results are shown in table 1.
Examples 2 to 6
The polyamine solution is adjusted to have a viscosity of 10 to 50 mPas, 50 to 100 mPas, 100 to 150 mPas, 150 to 200 mPas, 250 to 300 mPas, respectively, and the other conditions are the same as in example 1.
Test example 1
And (3) carrying out the test of the rejection rate and the ethanol flux on the polyamide thin-layer composite organic nanofiltration membrane prepared in the embodiment 1-6. The test method comprises the following steps: and placing the prepared organic nanofiltration membrane in a standard organic nanofiltration testing device, and testing the retention rate and the ethanol flux of the organic nanofiltration membrane on 50ppm rhodamine B ethanol solution under the conditions of 25 ℃ and 6bar of pressure. The results are shown in Table 1.
Table 1 rejection rate and permeation flux of polyamide thin-layer composite organic nanofiltration membrane prepared in examples 1 to 6
Examples 7 to 10
The thicknesses of the polyamine solution liquid films uniformly coated on the conveyer belt were adjusted to 20 μm, 50 μm, 100 μm and 300 μm, respectively, and the other conditions were the same as in example 1.
Test example 2
And (3) testing the rejection rate and the ethanol flux of the polyamide thin-layer composite organic nanofiltration membrane prepared in the embodiment 7-10. The test method comprises the following steps: and placing the prepared organic nanofiltration membrane in a standard organic nanofiltration testing device, and testing the retention rate and the ethanol flux of the organic nanofiltration membrane on 50ppm rhodamine B ethanol solution under the conditions of 25 ℃ and 6bar of pressure. The results are shown in Table 2.
Table 2 rejection rate and permeation flux of the polyamide thin-layer composite organic nanofiltration membrane prepared in examples 7 to 10
Examples 11 to 14
The materials of the adjusting conveyer belt are respectively steel, polyurethane, nylon and polyester films, and the rest conditions are the same as those of the embodiment 1.
Test example 3
And (3) carrying out the test of the rejection rate and the ethanol flux on the polyamide thin-layer composite organic nanofiltration membrane prepared in the embodiment 11-14. The test method comprises the following steps: and placing the prepared organic nanofiltration membrane in a standard organic nanofiltration testing device, and testing the retention rate and the ethanol flux of the organic nanofiltration membrane on 50ppm rhodamine B ethanol solution under the conditions of 25 ℃ and 6bar of pressure. The results are shown in Table 3.
Table 3 rejection rate and permeation flux of polyamide thin-layer composite organic nanofiltration membranes prepared in examples 11 to 14
Examples 15 to 18
The widths of the conveyer belts were adjusted to 0.2 m, 1 m, 5m and 10 m, respectively, and the other conditions were the same as in example 1.
Test example 4
The polyamide thin-layer composite organic nanofiltration membrane prepared in the embodiment 15-18 is subjected to the test of rejection rate and ethanol flux. The test method comprises the following steps: and placing the prepared organic nanofiltration membrane in a standard organic nanofiltration testing device, and testing the retention rate and the ethanol flux of the organic nanofiltration membrane on 50ppm rhodamine B ethanol solution under the conditions of 25 ℃ and 6bar of pressure. The results are shown in Table 4.
Table 4 interception rates and permeation fluxes of polyamide thin-layer composite organic nanofiltration membranes prepared in examples 15 to 18
Examples 19 to 22
The concentrations of m-phenylenediamine solution were adjusted to 5g/L, 10g/L, 20g/L and 50g/L, respectively, and the other conditions were the same as in example 1.
Test example 5
And (3) testing the rejection rate and the ethanol flux of the polyamide thin-layer composite organic nanofiltration membrane prepared in the embodiment 19-22. The test method comprises the following steps: and placing the prepared organic nanofiltration membrane in a standard organic nanofiltration testing device, and testing the retention rate and the ethanol flux of the organic nanofiltration membrane on 50ppm rhodamine B ethanol solution under the conditions of 25 ℃ and 6bar of pressure. The results are shown in Table 5.
TABLE 5 rejection and permeation flux of polyamide thin-layer composite membranes prepared in examples 19-22
Examples 23 to 26
The interfacial polymerization reaction time was adjusted to 30s, 120s, 240s, 450s, respectively, and the other conditions were the same as in example 1.
Test example 6
The polyamide thin-layer composite organic nanofiltration membrane prepared in the embodiment 23-26 is tested for rejection rate and ethanol flux. The test method comprises the following steps: and (3) placing the prepared organic nanofiltration membrane in a standard organic nanofiltration testing device, and testing the retention rate and the ethanol flux of the organic nanofiltration membrane on 50ppm rhodamine B ethanol solution at 25 ℃ under the pressure of 6 bar. The results are shown in Table 6.
TABLE 6 Degrees and permeation fluxes of the polyamide thin-layer composite membranes prepared in examples 23 to 26
Examples 27 to 33
The porous base membrane is adjusted to be polyethylene, nylon, polyvinylidene chloride, polysulfone, polyacrylonitrile, a surface property different asymmetric membrane prepared by biomimetic modification of a single-side mussel of a polypropylene membrane, and a surface property different asymmetric membrane prepared by biomimetic modification of a single-side mussel of a polyethylene membrane, and the other conditions are the same as those in example 1.
Test example 7
The polyamide thin-layer composite organic nanofiltration membrane prepared in the example 27-33 is subjected to the tests of rejection rate and ethanol flux. The test method comprises the following steps: and placing the prepared organic nanofiltration membrane in a standard organic nanofiltration testing device, and testing the retention rate and the ethanol flux of the organic nanofiltration membrane on 50ppm rhodamine B ethanol solution under the conditions of 25 ℃ and 6bar of pressure. The results are shown in Table 7.
TABLE 7 rejection and permeation flux of polyamide thin-layer composite membranes prepared in examples 27-33
Examples 34 to 37
The temperature of the hot press mechanism was adjusted to 70 ℃, 80 ℃, 90 ℃ and 100 ℃ respectively, and the other conditions were the same as in example 1.
Test example 8
The polyamide thin-layer composite organic nanofiltration membrane prepared in the example 34-37 is tested for rejection rate and ethanol flux. The test method comprises the following steps: and placing the prepared organic nanofiltration membrane in a standard organic nanofiltration testing device, and testing the retention rate and the ethanol flux of the organic nanofiltration membrane on 50ppm rhodamine B ethanol solution under the conditions of 25 ℃ and 6bar of pressure. The results are shown in Table 8.
TABLE 8 Degrees and permeation fluxes of the polyamide thin-layer composite membranes prepared in examples 34 to 37
Examples 38 to 41
The pressure of the hot-pressing mechanism is adjusted to be 500Pa, 3000Pa, 6000Pa and 10000Pa respectively, and the rest conditions are the same as the embodiment 1.
Test example 9
The polyamide thin-layer composite organic nanofiltration membrane prepared in the embodiment 38-41 is tested for rejection rate and ethanol flux. The test method comprises the following steps: and placing the prepared organic nanofiltration membrane in a standard organic nanofiltration testing device, and testing the retention rate and the ethanol flux of the organic nanofiltration membrane on 50ppm rhodamine B ethanol solution under the conditions of 25 ℃ and 6bar of pressure. The results are shown in Table 9.
TABLE 9 Degrees and permeation fluxes for Polyamide thin-layer composite membranes prepared in examples 38-41
The above-mentioned embodiments are intended to illustrate the technical solutions and advantages of the present invention, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modifications, additions, equivalents, etc. made within the scope of the principles of the present invention should be included in the scope of the present invention.
Claims (10)
1. A device for preparing a polyamide thin-layer composite film by transfer printing is characterized by comprising a conveying mechanism, a coating mechanism, a reaction mechanism, a compounding mechanism, a hot-pressing mechanism, a separating mechanism, a drying mechanism and a winding mechanism;
the coating mechanism is arranged above the conveying mechanism and used for coating the first reaction monomer solution on the surface of the conveying mechanism to form a first reaction monomer liquid film;
the reaction mechanism is arranged at the downstream of the coating mechanism and the upstream of the composite mechanism and is used for providing a stable liquid-liquid interface formed by the solution of the second monomer and the liquid film of the first monomer, and when the conveying mechanism bearing the liquid film of the first reaction monomer passes through the reaction mechanism, the first reaction monomer and the second reaction monomer carry out polymerization reaction at the interface to generate the polyamide nano film;
the compounding mechanism is arranged at the downstream of the reaction mechanism and is used for finishing the compounding of the porous base membrane and the polyamide nano-film and preparing a polyamide thin-layer composite membrane;
the hot pressing mechanism is arranged at the downstream of the composite mechanism and at the upstream of the separation mechanism and is used for enhancing the composite strength of the polyamide nano film and the porous base film;
the separation mechanism is arranged at the downstream of the hot pressing mechanism and is used for separating the polyamide thin-layer composite film from the conveying mechanism;
the drying mechanism and the winding mechanism are sequentially arranged at the downstream of the separating mechanism and used for drying and winding the polyamide thin-layer composite film.
2. The apparatus for preparing a polyamide thin composite film according to the transfer printing of claim 1, wherein the porous base film is compounded with the polyamide nano film on the upper side of the polyamide nano film.
3. The apparatus for preparing the polyamide thin-layer composite membrane by transfer printing according to claim 1, wherein the hot-pressing mechanism applies pressure and temperature to the polyamide composite membrane for enhancing the composite strength of the polyamide nano-thin membrane and the porous base membrane.
4. A method for preparing a polyamide thin-layer composite film by transfer printing is characterized by comprising the following steps:
(1) uniformly coating the solution of the first reaction monomer polyamine on the surface of the conveying mechanism through the coating mechanism to form a polyamine solution liquid film;
(2) immersing a conveying mechanism with a polyamine solution liquid film on the surface into a solution of second reaction monomer polybasic acyl chloride, and performing polymerization reaction on the polybasic amine and the polybasic acyl chloride at an interface to generate a polyamide nano film;
(3) compounding the porous base membrane with the polyamide nano-film from the upper side of the polyamide nano-film through a compounding mechanism to obtain a polyamide thin-layer composite membrane;
(4) the composite strength of the porous base membrane and the polyamide nano-film is enhanced by applying pressure and temperature through a hot-pressing mechanism;
(5) and (3) immersing the conveying mechanism attached with the polyamide thin-layer composite membrane into a separation mechanism containing constant-temperature water, separating the polyamide thin-layer composite membrane from the conveying mechanism, and then drying and rolling.
5. The method for preparing the polyamide thin-layer composite film by transfer printing according to claim 4, wherein the polyamine solution is a polyamine glycerol aqueous solution; the viscosity range of the polyamine glycerol aqueous solution is 10-300 mPas.
6. The method for preparing the polyamide thin-layer composite film by transfer printing according to claim 4, wherein the thickness of the polyamine liquid film is 1-500 μm.
7. The method for preparing the polyamide thin-layer composite film by transfer printing according to claim 4, wherein the polyamine is at least one of 1, 3-cyclohexyldimethylamine, diethylenetriamine, p-phenylenediamine, piperazine, o-phenylenediamine and m-phenylenediamine; the concentration of the polyamine solution is 0.01-100 g/L.
8. The method for preparing the polyamide thin-layer composite membrane by transfer printing according to claim 4, wherein the poly-acyl chloride is at least one of phthaloyl chloride, trimesoyl chloride, terephthaloyl chloride and isophthaloyl chloride; the solvent of the polybasic acyl chloride solution is at least one of heptane, normal hexane, cyclohexane, trichlorotrifluoroethane and isoparaffin; the monomer concentration of the polyacyl chloride solution is 0.1-10 g/L.
9. The method for preparing the polyamide thin-layer composite film through transfer printing according to claim 4, wherein the hot pressing temperature is 50-100 ℃; the hot pressing pressure is 10-100000 Pa.
10. A polyamide thin-layer composite film prepared by transfer printing is characterized by being prepared by the preparation method of any one of claims 4 to 9.
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| AU2581277A (en) * | 1976-06-24 | 1978-12-07 | Basf Ag | Transfer printing of cellulose fibers and of union fabrics containing cellulose fibers |
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