CN113663539B - Hyperbranched antibacterial polyurethane reverse osmosis membrane and preparation method thereof - Google Patents
Hyperbranched antibacterial polyurethane reverse osmosis membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hyperbranched antibacterial polyurethane reverse osmosis membrane and a preparation method thereof. The preparation method of the reverse osmosis membrane comprises the following steps: firstly, diisocyanate and polyglycol are adopted for prepolymerization, isocyanate group-terminated polyurethane prepolymer is obtained through chain extension and crosslinking, then hydroxyl-terminated or amine-terminated hyperbranched polymer modified polyurethane prepolymer is adopted for preparing isocyanate group-terminated hyperbranched polyurethane, and then the hyperbranched antibacterial polyurethane is obtained through graft reaction by using antibacterial micromolecular biguanide hydrochloride. Diluting the obtained hyperbranched antibacterial polyurethane by an organic solvent, and preparing the hyperbranched antibacterial polyurethane reverse osmosis membrane by adopting an electrostatic spinning technology and vacuum drying. The antibacterial reverse osmosis membrane has the advantages of stable structure, good antibacterial performance and good permeability, and has potential application value in the fields of seawater and brackish water desalination, wastewater reclamation, lithium ion battery diaphragm and substance separation and concentration and the like.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to a hyperbranched antibacterial polyurethane reverse osmosis membrane and a preparation method thereof.
Background
In recent years, global water resource shortage has become an important factor restricting social and economic development. The reverse osmosis membrane separation technology is an advanced membrane separation technology and is widely applied to the fields of seawater and brackish water desalination, wastewater reclamation, substance separation and concentration and the like. The membrane pollution phenomenon causes that the membrane needs to be cleaned chemically frequently in the operation process of the reverse osmosis system, and the frequent cleaning can cause the service life of the reverse osmosis membrane element to be reduced, and the operation cost of the reverse osmosis system is increased. The reverse osmosis membrane with biological pollution resistance is developed, and the biological pollution problem of the reverse osmosis membrane can be effectively solved.
The guanidino polymer is a high-efficiency, broad-spectrum and nontoxic cationic bactericide. The sterilization mechanism is as follows: guanidine polymer antimicrobial agents are generally alkaline, and when a cationic guanidine derivative comes into contact with bacteria, cations carried by the guanidine compound attract negatively charged bacteria, thereby limiting normal activity of the bacteria, damaging the respiratory system of the bacteria and causing 'contact death'. In addition, the negative charges and cations attract each other, so that the negative charges on the surface of the bacteria are unevenly distributed and deformed, and the cell membrane is ruptured, so that substances such as proteins in the cell overflow, and the phenomenon of 'bacterial solution' occurs, and the bacteria die.
At present, many scholars at home and abroad introduce guanidine salt into high polymers to guanidinate and modify the high polymers. Researches on introduction of guanidine groups into the surface of a reverse osmosis membrane for antibiosis are few at present, and the existing reports mainly introduce commercial polymer guanidine materials into the surface of the reverse osmosis membrane through a physical coating method. For example, nikkola et al, coat a mixed solution of polyvinyl alcohol (PVA) and polyhexamethylene guanidine hydrochloride (PHMG) on the surface of a commercial aromatic polyamide reverse osmosis membrane. Zhou Yixuan and the like are used for preparing the PVAmG modified reverse osmosis membrane with the anti-biological pollution performance by guanidinylating modification on polyvinylamine (PVAm) and introducing the synthesized biguanide-glycosylated polyvinylamine (PVAmG) to the surface of the reverse osmosis membrane through secondary interfacial polymerization. In patent CN108786498.7, the surface of the nascent reverse osmosis membrane is immersed in an aqueous solution containing biguanidino chitosan oligosaccharide for reaction, and the residual acyl chloride on the surface of the aromatic polyamide composite reverse osmosis membrane is connected with biguanidino chitosan oligosaccharide to form the anti-adhesion and anti-biological pollution reverse osmosis membrane. In patent CN107303470.6, attapulgite/silica-nano silver composite inorganic powder and hydrophilic polymer material are mixed and then coated on the surface of a functional layer of a reverse osmosis membrane, and the antibacterial reverse osmosis composite membrane with a coating of a cross-linked structure is obtained by heat treatment. Nevertheless, there are problems associated with the above-mentioned studies of anti-fouling reverse osmosis membranes: firstly, when surface grafting modification is carried out on a membrane material, membrane pores are often blocked, and the permeability is reduced; secondly, the stability of the modified material on the surface of the membrane is poor, and the anti-pollution capability is gradually lost after long-term use; thirdly, most of the membrane modification methods have complicated processes and high production cost, and large-scale preparation is difficult to realize.
Disclosure of Invention
Compared with the prior art, the hyperbranched antibacterial polyurethane reverse osmosis membrane and the preparation method thereof provided by the invention can avoid the problems of dispersion and falling off caused by an inorganic antibacterial agent, can avoid the decomposition of a conventional organic antibacterial agent due to poor thermal stability, and can avoid the gradual loss of pollution resistance due to phase separation caused by poor stability of a modified material on the surface of the membrane in long-term use.
In order to solve the technical problems, the invention adopts the following technical scheme:
the hyperbranched antibacterial polyurethane reverse osmosis membrane is a hyperbranched polyurethane nanofiber membrane with controllable porosity, and the tensile strength of the membrane is 5-6 MPa. The elongation at break is 70-85%.
The preparation method of the hyperbranched antibacterial polyurethane reverse osmosis membrane comprises the following steps,
step 1) putting synthetic raw materials of diisocyanate and polyglycol into an electric heating vacuum drying oven for drying;
step 2) reacting diisocyanate and polyglycol obtained after drying treatment in step 1) in N2Stirring and mixing evenly under protection, heating to 80-90 ℃, adding dibutyltin dilaurate (DBTDL) serving as a catalyst for reaction for 0.5-1 h, cooling to 60-70 ℃, adding 1,4-butanediol for chain extension reaction for 0.5-1 h, adding trimethylolpropane for crosslinking reaction for 0.5-1 h, adding a proper amount of organic solvent to reduce the system viscosity, preserving heat and preserving heatReacting for 2-3 h to obtain isocyanate group-terminated polyurethane prepolymer; step 3) heating to 80-90 ℃, slowly dripping the hydroxyl-terminated or amino-terminated hyperbranched polymer dissolved in the organic solvent in advance into the isocyanate-terminated polyurethane prepolymer obtained in the step 2), controlling the dripping speed to be 0.05-0.1 mL/s, and preserving heat for 2-3 h after finishing dripping to obtain isocyanate-terminated hyperbranched polyurethane;
step 4), adopting a dropwise adding mode, controlling the dropping speed to be 0.05-0.1 mL/s, adding antibacterial micromolecule biguanidinyl hydrochloride dissolved in an organic solvent in advance into the isocyanate-terminated hyperbranched polyurethane obtained in the step 3), performing grafting reaction for 2-4 h, and cooling to 30-45 ℃ to obtain a hyperbranched antibacterial polyurethane solution;
diluting the obtained hyperbranched antibacterial polyurethane solution with an organic solvent, magnetically stirring for 4-6 h at room temperature of 25 ℃ to obtain a spinning solution with the mass fraction of 5-8 wt%, injecting the spinning solution into an injection pump, controlling the distance between a receiving plate and a flat-head needle to be 12-15 cm, applying the voltage to be 16-20 kV, the injection rate to be 0.8-1.5 mL/h and the ambient humidity to be 45-60%, performing electrostatic spinning by using the flat-head needle with the inner diameter of 0.25-0.35 mm, and performing vacuum drying on the obtained membrane to prepare the hyperbranched antibacterial polyurethane reverse osmosis membrane.
The polyglycol in the step 1) is one of polyoxypropylene dihydric alcohol, polytetrahydrofuran ether dihydric alcohol, polycaprolactone dihydric alcohol, polycarbonate dihydric alcohol and polybutylene adipate dihydric alcohol, and the relative molecular mass of the polyglycol is 1000.
The diisocyanate in the step 1) is one of isophorone diisocyanate (IPDI), toluene Diisocyanate (TDI), hexamethylene Diisocyanate (HDI) and diphenylmethane diisocyanate (MDI).
The organic solvent in the step 2) is one of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), N-methylpyrrolidone (NMP) and toluene.
The mass ratio of the diisocyanate, the polyglycol, the dibutyltin dilaurate DBTDL, the 1,4-Butanediol (BDO) and the Trimethylolpropane (TMP) in the step 2) is 13-38: 20 to 60 percent: 0.05 to 0.1:0.8 to 1.1: 1.4-2.0, wherein the mass ratio of the organic solvent to the total amount of the reaction monomers is 1-2: 1.
the hydroxyl-terminated or amino-terminated hyperbranched polymer in the step 3) is one of hydroxyl-terminated polyamidoamine zero (CYD-100H), amino-terminated polyamidoamine zero (CYD-100A) and polyetheramine (T403).
The mass ratio of the organic solvent to the hydroxyl-terminated or amino-terminated hyperbranched polymer in the step 3) is 10:1, the mass ratio of the hydroxyl-terminated or amine-terminated hyperbranched polymer to the isocyanate-terminated polyurethane prepolymer is 1.5-3.2: 35 to 105.
The antibacterial micromolecular biguanide-based hydrochloride in the step 4) is one of 1,1-dimethylbiguanide hydrochloride, biguanide hydrochloride, polyhexamethylene biguanide hydrochloride and 1-phenyl biguanide hydrochloride.
The mass ratio of the organic solvent to the antibacterial micromolecular biguanide-based hydrochloride in the step 4) is 5:1, the mass ratio of the antibacterial micromolecular biguanide-based hydrochloride to the isocyanate-terminated hyperbranched polyurethane is 2.0-4.0: 35 to 105.
And step 5), the vacuum drying temperature is 60-80 ℃.
The invention has the beneficial effects that:
compared with the prior art, the invention firstly adopts a hyperbranched mode to improve the polyurethane framework, thereby improving the tensile strength and toughness of the reverse osmosis membrane and improving the impact resistance of the membrane; secondly, the reverse osmosis membrane prepared by the electrostatic spinning method can obtain a fibrous membrane with a uniform microscopic fiber structure and controllable porosity, is beneficial to improving the permeability of the membrane, is not easy to phase separate and has a stable structure; in addition, the reverse osmosis membrane of the invention quantitatively introduces antibacterial active groups, has good antibacterial performance and anti-pollution performance, can effectively control membrane pollution, not only can prolong the service life of the membrane, but also can reduce energy consumption and treatment cost, and has potential application value in the fields of seawater and brackish water desalination, wastewater reclamation, substance separation and concentration and the like.
The hyperbranched antibacterial polyurethane reverse osmosis membrane and the preparation method thereof according to the present invention will be further described by way of illustration and examples in the drawings.
Drawings
FIG. 1 is a schematic diagram of the synthesis of hyperbranched antibacterial polyurethane prepared by the present invention;
FIG. 2 is a microstructure diagram of the hyperbranched antibacterial polyurethane reverse osmosis membrane prepared in example 1 of the present invention;
FIG. 3 is a microstructure diagram of the hyperbranched antibacterial polyurethane reverse osmosis membrane prepared in example 2 of the present invention;
fig. 4 is a microscopic structure view of the hyperbranched antibacterial polyurethane reverse osmosis membrane prepared in example 3 of the present invention.
Detailed Description
Example 1
As shown in FIG. 1, raw materials isophorone diisocyanate (IPDI) and polyoxypropylene glycol were dried in an electric vacuum oven. 25.3g of dried isophorone diisocyanate and 42.8g of polyoxypropylene diol (M)W= 1000) in N2Stirring and mixing uniformly under protection, heating to 80 ℃, adding 0.1g of catalyst dibutyltin dilaurate (DBTDL) for reaction for 0.5h, cooling to 60 ℃, adding 0.82g of 1, 4-Butanediol (BDO) for chain extension reaction for 0.5h, then adding 1.52g of Trimethylolpropane (TMP) for crosslinking reaction for 0.5h, adding 70.5g of N, N-Dimethylformamide (DMF) for reducing the system viscosity, and carrying out heat preservation reaction for 2h to obtain the isocyanate-terminated polyurethane prepolymer.
Heating to 85 ℃, dissolving 2.0g of hydroxyl-terminated polyamidoamine (CYD-100H) in 20g of N, N-Dimethylformamide (DMF) in advance, slowly dripping into the isocyanate-terminated polyurethane prepolymer, controlling the dripping speed to be 0.06mL/s, and preserving heat for 2 hours after dripping is finished to obtain the isocyanate-terminated hyperbranched polyurethane.
2.5g of 1, 1-dimethylbiguanide hydrochloride is dissolved in 12.5g of N, N-Dimethylformamide (DMF) in advance, the dropping speed is controlled to be 0.05mL/s, the solution is dropwise added into the hyperbranched polyurethane solution with the end capped by the isocyanate group, and after grafting reaction for 3 hours, the temperature is reduced to 45 ℃ to obtain the hyperbranched antibacterial polyurethane solution.
Weighing 5g of hyperbranched antibacterial polyurethane solution, diluting the solution to 6wt% by using N, N-Dimethylformamide (DMF), magnetically stirring the solution for 5 hours at room temperature of 25 ℃, taking 5mL of spinning solution, injecting the spinning solution into an injection pump, controlling the distance between a receiving plate and a flat-head needle to be 12cm, controlling the applied voltage to be 16kV, the injection rate to be 0.8mL/h, controlling the ambient humidity to be 45%, carrying out electrostatic spinning by using the flat-head needle with the inner diameter of 0.33mm, carrying out vacuum drying on the obtained membrane at 60 ℃, and preparing the hyperbranched antibacterial polyurethane reverse osmosis membrane, wherein the microscopic morphology structure of the membrane is shown in figure 2, so that the reverse osmosis membrane is a hyperbranched polyurethane nanofiber membrane. The test results of the prepared hyperbranched antibacterial polyurethane reverse osmosis membrane are shown in table 1.
Example 2
As shown in figure 1, the raw materials of Toluene Diisocyanate (TDI) and polycaprolactone diol are dried in an electrothermal vacuum drying oven. 15.4g of dried tolylene diisocyanate and 22.5g of polycaprolactone diol (M)W= 1000) in N2Stirring and mixing uniformly under protection, heating to 85 ℃, adding 0.05g of catalyst dibutyltin dilaurate (DBTDL) for reaction for 0.7h, cooling to 65 ℃, adding 0.83g of 1, 4-Butanediol (BDO) for chain extension reaction for 0.5h, then adding 1.42g of Trimethylolpropane (TMP) for crosslinking reaction for 1.0h, adding 64g N-methyl pyrrolidone (NMP) for reducing the system viscosity, and carrying out heat preservation reaction for 2.5h to obtain the isocyanate-terminated polyurethane prepolymer.
Heating to 85 ℃, slowly dripping 1.6g of amino-terminated polyamidoamine zero (CYD-100A) dissolved in 16.0g N-methyl pyrrolidone (NMP) into the isocyanate group-terminated polyurethane prepolymer, controlling the dripping speed to be 0.06mL/s, and preserving heat for 2.5h after finishing dripping to obtain the isocyanate group-terminated hyperbranched polyurethane.
Pre-dissolving 3.0g of biguanide hydrochloride in 15.0g N-methyl pyrrolidone (NMP), controlling the dropping speed to be 0.08mL/s, dropwise adding the biguanide hydrochloride into the hyperbranched polyurethane solution terminated by isocyanate groups, carrying out grafting reaction for 4 hours, and cooling to 40 ℃ to obtain the hyperbranched antibacterial polyurethane solution.
Weighing 5g of hyperbranched antibacterial polyurethane solution, diluting the solution to 5wt% by using N-methylpyrrolidone (NMP), magnetically stirring the solution for 4 hours at room temperature and 25 ℃, injecting 5mL of spinning solution into an injection pump, controlling the distance between a receiving plate and a flat-head needle to be 13cm, controlling the applied voltage to be 20kV, the injection rate to be 1.2mL/h, controlling the ambient humidity to be 50%, carrying out electrostatic spinning by using the flat-head needle with the inner diameter of 0.25mm, carrying out vacuum drying on the obtained membrane at 70 ℃, and preparing the hyperbranched antibacterial polyurethane reverse osmosis membrane, wherein the microstructure of the membrane is shown in figure 3, so that the reverse osmosis membrane is a hyperbranched polyurethane nanofiber membrane. The test results of the prepared hyperbranched antibacterial polyurethane reverse osmosis membrane are shown in table 1.
Example 3
As shown in FIG. 1, hexamethylene Diisocyanate (HDI) and polytetrahydrofuran ether glycol as raw materials were dried in an electric vacuum oven. 36.8g of dried hexamethylene diisocyanate and 56.4g of polytetrahydrofuran ether diol (M) were weighed outW= 1000) in N2Stirring and mixing uniformly under protection, heating to 90 ℃, adding 0.08g of dibutyltin dilaurate (DBTDL) as a catalyst, reacting for 0.7h, cooling to 70 ℃, adding 1.1g of 1, 4-Butanediol (BDO), extending chain, reacting for 1.0h, adding 1.9g of Trimethylolpropane (TMP), performing cross-linking reaction for 1.0h, adding 190.8g of dimethyl sulfoxide (DMSO), reducing system viscosity, and performing heat preservation reaction for 2.5h to obtain the isocyanate-terminated polyurethane prepolymer.
And (3) heating to 90 ℃, dissolving 3.1g of polyetheramine (T403) in 31.0g of dimethyl sulfoxide (DMSO) in advance, slowly dripping into the polyurethane prepolymer terminated by isocyanate groups, controlling the dripping speed to be 0.1mL/s, and preserving heat for 2.5 hours after dripping is finished to obtain the hyperbranched polyurethane terminated by the isocyanate groups.
Dissolving 4.0g of polyhexamethylene biguanide hydrochloride in 20.0g of dimethyl sulfoxide (DMSO) in advance, controlling the dropping speed to be 0.1mL/s, dropwise adding the solution into the hyperbranched polyurethane solution terminated by the isocyanate group, carrying out grafting reaction for 4 hours, and cooling to 30 ℃ to obtain the hyperbranched antibacterial polyurethane solution.
Weighing 5g of hyperbranched antibacterial polyurethane solution, diluting the solution to 7.5wt% by using dimethyl sulfoxide (DMSO), magnetically stirring the solution for 5 hours at room temperature of 25 ℃, taking 5mL of spinning solution to inject into an injection pump, controlling the distance between a receiving plate and a flat-head needle to be 15cm, controlling the applied voltage to be 18kV, the injection rate to be 1.5mL/h, controlling the ambient humidity to be 60%, carrying out electrostatic spinning by using a flat-head needle with the inner diameter of 0.35mm, carrying out vacuum drying on the obtained membrane at 80 ℃, and preparing the hyperbranched antibacterial polyurethane reverse osmosis membrane, wherein the microstructure of the membrane is shown in figure 4, so that the reverse osmosis membrane is a hyperbranched polyurethane nanofiber membrane. The test results of the prepared hyperbranched antibacterial polyurethane reverse osmosis membrane are shown in table 1.
Comparative example 1
Putting raw materials isophorone diisocyanate (IPDI) and polyoxypropylene glycol into an electrothermal vacuum drying oven for drying. 25.3g of dried isophorone diisocyanate and 42.8g of polyoxypropylene diol (M)W= 1000) in N2Stirring and mixing uniformly under protection, heating to 80 ℃, adding 0.1g of catalyst dibutyltin dilaurate (DBTDL) for reaction for 0.5h, cooling to 60 ℃, adding 0.82g of 1, 4-Butanediol (BDO) for chain extension reaction for 0.5h, then adding 1.52g of Trimethylolpropane (TMP) for crosslinking reaction for 0.5h, adding 70.5g of N, N-Dimethylformamide (DMF) for reducing the system viscosity, and carrying out heat preservation reaction for 2h to obtain the isocyanate-terminated polyurethane prepolymer.
3.2g of 1, 1-dimethylbiguanide hydrochloride is dissolved in 16.0g of N, N-Dimethylformamide (DMF) in advance, the dropping speed is controlled to be 0.1mL/s, the mixture is dropwise added into polyurethane solution with end capped by isocyanate groups, and after grafting reaction for 3 hours, the temperature is reduced to 45 ℃ to obtain the antibacterial polyurethane solution.
Weighing 5g of antibacterial polyurethane solution, diluting the antibacterial polyurethane solution to 6wt% by using N, N-Dimethylformamide (DMF), magnetically stirring the antibacterial polyurethane solution for 5 hours at room temperature of 25 ℃, injecting 5mL of spinning solution into an injection pump, controlling the distance between a receiving plate and a flat-head needle to be 12cm, controlling the applied voltage to be 17kV, controlling the injection rate to be 1.0mL/h and the ambient humidity to be 45%, carrying out electrostatic spinning by using the flat-head needle with the inner diameter of 0.33mm, and carrying out vacuum drying on the obtained membrane at 60 ℃ to prepare the antibacterial polyurethane reverse osmosis membrane. The test results of the prepared antibacterial polyurethane reverse osmosis membrane are shown in table 1.
Comparative example 2
Putting raw materials isophorone diisocyanate (IPDI) and polyoxypropylene glycol into an electrothermal vacuum drying oven for drying. 25.3g of dried isophorone diisocyanate and 42.8g of polyoxypropylene diol (M)W= 1000) inN2Stirring and mixing uniformly under protection, heating to 80 ℃, adding 0.1g of catalyst dibutyltin dilaurate (DBTDL) for reaction for 0.5h, cooling to 60 ℃, adding 0.82g of 1, 4-Butanediol (BDO) for chain extension reaction for 0.5h, then adding 1.52g of Trimethylolpropane (TMP) for crosslinking reaction for 0.5h, adding 70.5g of N, N-Dimethylformamide (DMF) for reducing the system viscosity, and carrying out heat preservation reaction for 2h to obtain the isocyanate-terminated polyurethane prepolymer.
Heating to 85 ℃, slowly dripping 2.0g of hydroxyl-terminated polyamidoamine (CYD-100H) dissolved in 20g of N, N-Dimethylformamide (DMF) into the isocyanate-terminated polyurethane prepolymer, controlling the dripping speed to be 0.2mL/s, and preserving heat for 2 hours after dripping is finished to obtain the hyperbranched polyurethane solution.
Weighing 5g of hyperbranched polyurethane solution, diluting the hyperbranched polyurethane solution to 6wt% by using N, N-Dimethylformamide (DMF), magnetically stirring the solution for 5 hours at room temperature of 25 ℃, injecting 5mL of spinning solution into an injection pump, controlling the distance between a receiving plate and a flat-head needle to be 12cm, controlling the applied voltage to be 17kV, the perfusion rate to be 1.0mL/h and the ambient humidity to be 45%, carrying out electrostatic spinning by using the flat-head needle with the inner diameter of 0.33mm, and carrying out vacuum drying on the obtained membrane at 60 ℃ to prepare the hyperbranched polyurethane reverse osmosis membrane. The test results of the prepared hyperbranched polyurethane reverse osmosis membrane are listed in table 1.
The items tested in the examples of the invention and the comparative examples are: mechanical property test, permeability test and antibacterial property test. (1) mechanical property testing was performed with reference to GB/T1040-1992; (2) permeability test: a. the initial permeate flux and salt rejection of the nascent reverse osmosis membrane were tested at 2.0MPa, 25 ℃ cross-flow rate of 1.5L/min using 2500mg/L aqueous sodium chloride. b. The reverse osmosis membrane was placed in 1000 μ g/L bovine serum albumin and lysozyme solution (pH = 7.0) and run continuously for 24h, and then the water flux and salt rejection of the membrane after fouling were tested. c. Keeping the reverse osmosis membrane diaphragm not taken out, discharging the polluted liquid in the test system completely, flushing the reverse osmosis membrane for 1h by using a 2500mg/L sodium chloride aqueous solution under the conditions of 0.7MPa and 25 ℃ cross flow of 4.0L/min, testing the water flux and the salt rejection rate of the cleaned membrane under the conditions of 2.0MPa and 25 ℃ cross flow of 1.5L/min, and calculating the water flux attenuation rate and the recovery rate according to the obtained data. (3) Will be provided with500. Mu.L of mixed suspension of Escherichia coli and Staphylococcus aureus (cell concentration ca.2X 10)6cfu/mL)) is uniformly coated on the surface of a reverse osmosis membrane of 5cm multiplied by 5cm, and the antibacterial rate is detected according to the current GB/T31402 detection standard.
Tensile stress, elongation at break, permeation flux, salt rejection and antibacterial properties obtained after the test of the reverse osmosis membranes prepared in examples 1 to 3 and the reverse osmosis membranes prepared in comparative examples 1 to 2 are shown in table 1.
Table 1 test results of examples and comparative examples:
as can be seen from the performance test results of examples 1 to 3, the reverse osmosis membranes prepared in examples 1 to 3 have good mechanical properties, initial permeation flux and salt rejection rate, and have excellent antibacterial properties and anti-pollution properties. As can be seen from examples 1 to 3 and comparative example 1, the introduction of the hydroxyl-terminated or amino-terminated hyperbranched polymer into the reverse osmosis membrane can effectively improve the mechanical strength and flexibility of the reverse osmosis membrane, and as can be seen from examples 1 to 3 and comparative example 2, the introduction of the guanidyl can effectively improve the antibacterial property and the anti-pollution property of the reverse osmosis membrane.
In summary, although the present invention has been described in detail with reference to the specific embodiments, the description is illustrative, and those skilled in the art can make various modifications and changes based on the principle without departing from the invention, and the scope of the invention is defined by the appended claims.
Claims (9)
1. A preparation method of a hyperbranched antibacterial polyurethane reverse osmosis membrane is provided, wherein the reverse osmosis membrane is a hyperbranched polyurethane nanofiber membrane with controllable porosity, the tensile strength of the hyperbranched polyurethane nanofiber membrane is 5 to 6MPa, and the elongation at break of the hyperbranched antibacterial polyurethane nanofiber membrane is 70 to 85 percent; the method is characterized by comprising the following steps:
step 1) putting synthetic raw materials of diisocyanate and polyglycol into an electric heating vacuum drying oven for drying;
step 2) reacting diisocyanate and polyglycol obtained after drying treatment in step 1) in N2Stirring and mixing uniformly under protection, heating to 80-90 ℃, adding a catalyst dibutyltin dilaurate DBTDL (dibutyl tin dilaurate) for reaction for 0.5-1 h, cooling to 60-70 ℃, adding 1,4-butanediol for chain extension reaction for 0.5-1 h, adding trimethylolpropane for crosslinking reaction for 0.5-1 h, adding an organic solvent for reducing system viscosity, and carrying out heat preservation reaction for 2-3 h to obtain an isocyanate-terminated polyurethane prepolymer;
step 3) heating to 80-90 ℃, slowly dripping the hydroxyl-terminated or amino-terminated hyperbranched polymer dissolved in the organic solvent in advance into the isocyanate-terminated polyurethane prepolymer obtained in the step 2), controlling the dripping speed to be 0.05-0.1 mL/s, and preserving heat for 2-3 h after finishing dripping to obtain isocyanate-terminated hyperbranched polyurethane;
step 4), adopting a dropwise adding mode, controlling the dropping speed to be 0.05-0.1 mL/s, adding antibacterial micromolecule biguanidinyl hydrochloride dissolved in an organic solvent in advance into the isocyanate-terminated hyperbranched polyurethane obtained in the step 3), performing grafting reaction for 2-4 h, and cooling to 30-45 ℃ to obtain a hyperbranched antibacterial polyurethane solution;
step 5) diluting the hyperbranched antibacterial polyurethane solution obtained in the step 4) with an organic solvent, magnetically stirring for 4 to 6 hours at the room temperature of 25 ℃ to obtain a spinning solution with the mass fraction of 5 to 8wt%, injecting the spinning solution into an injection pump, controlling the distance between a receiving plate and a flat-headed needle to be 12 to 15cm, controlling the external voltage to be 16 to 20kV, the perfusion rate to be 0.8 to 1.5mL/h, controlling the environmental humidity to be 45 to 60%, performing electrostatic spinning by using the flat-headed needle with the inner diameter of 0.25 to 0.35mm, and performing vacuum drying on the obtained membrane to prepare the hyperbranched antibacterial polyurethane reverse osmosis membrane;
the polyglycol in the step 1) is one of polyoxypropylene dihydric alcohol, polytetrahydrofuran ether dihydric alcohol, polycaprolactone dihydric alcohol, polycarbonate dihydric alcohol and polybutylene adipate dihydric alcohol, and the relative molecular mass of the polyglycol is 1000.
2. The method for preparing a hyperbranched antibacterial polyurethane reverse osmosis membrane according to claim 1, wherein the diisocyanate in step 1) is one of isophorone diisocyanate (IPDI), toluene Diisocyanate (TDI), hexamethylene Diisocyanate (HDI) and diphenylmethane diisocyanate (MDI).
3. The method for preparing a hyperbranched antibacterial polyurethane reverse osmosis membrane according to claim 1, wherein the organic solvent in step 2) is one of N, N-dimethylformamide DMF, dimethyl sulfoxide DMSO, tetrahydrofuran THF, N-methylpyrrolidone NMP and toluene.
4. The method for preparing a hyperbranched antibacterial polyurethane reverse osmosis membrane according to claim 1, wherein the mass ratio of the diisocyanate, the polyglycol, the dibutyltin dilaurate DBTDL, the 1,4-butanediol BDO and the trimethylolpropane TMP in the step 2) is 13 to 38:20 to 60:0.05 to 0.1:0.8 to 1.1:1.4 to 2.0, wherein the mass ratio of the organic solvent to the total amount of the reaction monomers is 1~2:1.
5. the method for preparing the hyperbranched antibacterial polyurethane reverse osmosis membrane according to claim 1, wherein the hydroxyl-terminated or amine-terminated hyperbranched polymer in step 3) is one of hydroxyl-terminated polyamidoamine zero-substituted CYD-100H, amino-terminated polyamidoamine zero-substituted CYD-100A and polyetheramine T403.
6. The preparation method of the hyperbranched antibacterial polyurethane reverse osmosis membrane according to claim 1, wherein the mass ratio of the organic solvent in the step 3) to the hydroxyl-terminated or amine-terminated hyperbranched polymer is 10:1, the mass ratio of the hydroxyl-terminated or amino-terminated hyperbranched polymer to the isocyanate-terminated polyurethane prepolymer is 1.5 to 3.2:35 to 105.
7. The method of preparing a hyperbranched antibacterial polyurethane reverse osmosis membrane according to claim 1, wherein the antibacterial small molecule biguanide hydrochloride of step 4) is one of 1,1-dimethylbiguanide hydrochloride, biguanide hydrochloride, polyhexamethylene biguanide hydrochloride and 1-phenyl biguanide hydrochloride.
8. The preparation method of the hyperbranched antibacterial polyurethane reverse osmosis membrane according to claim 1, wherein the mass ratio of the organic solvent in the step 4) to the antibacterial small molecule biguanide-based hydrochloride is 5:1, the mass ratio of the antibacterial micromolecular biguanide base hydrochloride to the isocyanate-terminated hyperbranched polyurethane is 2.0 to 4.0:35 to 105.
9. The method for preparing the hyperbranched antibacterial polyurethane reverse osmosis membrane according to claim 1, wherein the vacuum drying temperature in the step 5) is 60 to 80 ℃.
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