CN108342902B - Super-hydrophilic polymer microsphere, preparation method thereof and super-hydrophilic fabric prepared from super-hydrophilic polymer microsphere - Google Patents
Super-hydrophilic polymer microsphere, preparation method thereof and super-hydrophilic fabric prepared from super-hydrophilic polymer microsphere Download PDFInfo
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Abstract
The invention discloses a super-hydrophilic polymer microsphere, a preparation method thereof and a super-hydrophilic fabric prepared from the super-hydrophilic polymer microsphere. The micro-morphology of the surface of the microsphere can be controlled by controlling the process conditions such as the concentration of the solvent and the solution selected during the preparation of the spraying solution, the electrostatic spraying voltage and the receiving distance, and the microsphere prepared by the method has a micron-nano composite structure surface, high surface roughness and large specific surface area, so that the microsphere has super-hydrophilicity. The preparation method of the microsphere provided by the invention is simple and convenient in process, strong in controllability and suitable for industrial production, popularization and application.
Description
Technical Field
The invention relates to a super-hydrophilic polymer microsphere, a preparation method thereof and a super-hydrophilic fabric prepared from the super-hydrophilic polymer microsphere.
Background
The polymer microsphere has the characteristics of unique low density and high specific surface area, thereby having strong development potential and good application prospect. Especially polymeric microspheres with biodegradability and biocompatibility, have been receiving continuous attention and research. They are widely used in immobilization, affinity chromatography, drug release, micro-separation, microcarriers, etc.
Currently, many techniques can be used to prepare polymer microspheres, such as interfacial polymerization, emulsion polymerization, suspension polymerization, interfacial deposition, phase separation, spray drying, electrostatic spraying, and the like. Among them, the electrostatic spraying method is a convenient and simple method for preparing polymer nano-and micro-microspheres. It is a method for forming microspheres by means of a high-voltage electrostatic field. The size of the microsphere or particle prepared by the method can reach several micrometers, even can reach a nanometer level. If the polymer liquid is a high-viscosity polymer solution or melt with good fiberizability, the liquid stream does not break into fine polymer droplets in the electric field, but forms continuous fibers, which is called electrospinning, and is currently widely studied. In contrast, the electrostatic spraying method has relatively few reports on the preparation of microspheres and microparticles.
In previous reports, many polymer materials, such as polylactic acid (PLA), polylactic-co-glycolic acid (PLGA), Polystyrene (PS) and Polycaprolactone (PCL), have been prepared into microspheres with solid, hollow, porous, core-shell structures by electrostatic spraying. In recent years, PCL electrostatic spinning and microsphere products are used for biological tissue scaffolds, drug delivery and embedding. PCL and its modified polymers are one of the most common electrostatic spray materials as absorbable polymer materials.
However, as a microcarrier, the wettability of the surface of the microsphere has a great influence on the adhesion performance of the microcarrier to cells, the slow release of the carrier, and the like. The PCL is hydrophobic in nature, and the nano-fiber or microsphere directly prepared from the PCL also has hydrophobicity.
In addition, compared with natural fibers such as cotton, wool, silk and the like, the chemical fiber has the characteristics of low production cost and excellent mechanical property. However, the textile prepared by the method has low equilibrium moisture absorption rate and poor moisture absorption and perspiration performance, and is easy to cause uncomfortable wearing due to the accumulation of static electricity. In this regard, an effective solution is to perform a hydrophilic finish on the textile.
The hydrophilic finishing agents commonly used are both polyacrylates and polyurethanes. The hydrophilic finishing agent of polyurethane provides hydrophilic finishing function with good durability by introducing hydrophilic polyethylene glycol as soft segment into polyurethane system and forming film on fiber surface during finishing.
Currently, polyurethane-based hydrophilic finishing agents have been commercialized abroad, such as elastron w-11 and anicatet M-4 from the first pharmaceutical company of japan, and the finished fabric therefrom has hydrophilicity of less than 10 seconds as measured by the dripping method even after 10 washes, and it is seen that the finish has good wash resistance. However, the hydrophilic performance index provided by the hydrophilic functional auxiliary agent is still up to several seconds, which greatly limits the application of the textile in the field of functional fabrics such as water treatment and the like.
Disclosure of Invention
The invention aims to provide a super-hydrophilic polymer microsphere and a preparation method and application thereof, wherein after PEG with hydrophilicity is segmented in a PCL molecular chain, the hydrophilicity of a copolymer is improved, and different hydrophilicities are shown along with different structures of the PEG chain; the fabric surface is coated with micron-nanometer composite microspheres by an electrostatic spraying method, and the super-hydrophilic fabric is prepared by super-hydrophilicity provided by the composite microspheres.
The technical scheme adopted by the invention is as follows:
a preparation method of super-hydrophilic polymer microspheres comprises the following steps:
(1) adding carboxyl-terminated PCL and N, N' -carbonyldiimidazole into tetrahydrofuran, and dissolving at room temperature; then, under the protection of nitrogen, dripping a tetrahydrofuran solution of PEG; then reacting to obtain a polyethylene glycol-poly (omega-caprolactone) segmented copolymer (PEG-b-PCL);
(2) dissolving a polyethylene glycol-poly (omega-caprolactone) block copolymer into a chloroalkane solvent, stirring and dissolving to prepare a spray stock solution; and finally, preparing the spraying stock solution into the super-hydrophilic polymer microspheres in an electrostatic spraying mode.
In the technical scheme, the mass ratio of the carboxyl-terminated PCL to the N, N' -carbonyl diimidazole to the PEG is 1: 0.1-0.2: 0.03-0.5; the number average molecular weight of the carboxyl-terminated PCL is 2-12 ten thousand, the number average molecular weight of the PEG is 1000-5000, and the reaction is carried out for 8 hours at 35 ℃; the mass concentration of the spraying stock solution is 1.0-9.2%; the processing temperature during electrostatic spraying is 10-35 ℃, the humidity is 45-75%, the applied voltage is 8-25 kV, and the flow rate is 0.6 mL.h-1～3mL· h-1The receiving distance is 10-25 cm, and the rotation speed of the roller is 10-100 rpm.
According to the technical scheme, when the spraying stock solution is prepared into the super-hydrophilic microspheres in an electrostatic spraying mode, the surface of the base material is coated with the adhesive, then the base material is wound and fixed on a roller device of an electrostatic spraying machine, the adhesive layer faces outwards to prepare for receiving the microspheres, the prepared electrostatic spraying stock solution is sucked into an injector and put into a propulsion pump, then the processing temperature and the processing humidity are adjusted, certain external voltage, flow speed and receiving distance are set, and the coating microspheres are electrostatically sprayed on the surface of the base material to obtain the super-hydrophilic microspheres. The base material is metal or plastic, is one of a plate or a sheet, and can also be a fabric; the adhesive is one of polyurethane, polyacrylate or organic silicon adhesive, and is diluted to the mass concentration of 1-5%.
A preparation method of a super-hydrophilic fabric comprises the following steps:
(1) adding carboxyl-terminated PCL and N, N' -carbonyldiimidazole into tetrahydrofuran, and dissolving at room temperature; then, under the protection of nitrogen, dripping a tetrahydrofuran solution of PEG; then reacting to obtain a polyethylene glycol-poly (omega-caprolactone) block copolymer;
(2) dissolving a polyethylene glycol-poly (omega-caprolactone) block copolymer into a chloroalkane solvent, stirring and dissolving to prepare a spray stock solution;
(3) soaking and rolling the fabric in a water-based adhesive for two times to obtain a fabric with liquid;
(4) spraying the spraying stock solution to the surface of the fabric with the liquid by taking the fabric with the liquid as a receiver in an electrostatic spraying manner to obtain a fabric with a microsphere coating;
(5) and drying the coated fabric to obtain the super-hydrophilic fabric.
In the technical scheme, the number average molecular weight of the carboxyl-terminated PCL is 2-12 ten thousand, the number average molecular weight of the PEG is 1000-5000, and the reaction is carried out for 8 hours at 35 ℃.
In the technical scheme, the chlorinated alkane solvent is one of trichloromethane, dichloromethane, carbon tetrachloride and dichloroethane; the mass concentration of the spraying stock solution is 1.0-9.2%.
In the technical scheme, the fabric is one of cotton, terylene, silk and aramid fiber or any blended fabric thereof; the water-based adhesive is one of polyacrylate emulsion or polyurethane emulsion, and the mass concentration of the water-based adhesive is 1-10%; the liquid carrying rate of the liquid carrying fabric is 90-120%.
In the technical scheme, the processing temperature during electrostatic spraying is 10-35 ℃, the humidity is 45-75%, the applied voltage is 8-25 kV, and the flow rate is 0.6 mL.h-1～3 mL· h-1The receiving distance is 10-25 cm, and the rotation speed of the roller is 10-100 revolutions per minute; in the fabric with the microsphere coating, the average particle size of the microspheres is 5.0-10.0 μm.
In the technical scheme, the drying temperature is 40-80 ℃, and the drying time is 1-24 h.
The invention discloses a super-hydrophilic fabric prepared according to the preparation method of the super-hydrophilic fabric; or the super-hydrophilic polymer microsphere prepared according to the preparation method of the super-hydrophilic polymer microsphere. And the application of the super-hydrophilic polymer microspheres in preparing super-hydrophilic fabrics.
The method for preparing the superhydrophilic fabric of the present invention can be represented as follows:
(1) preparing a stock solution for spraying
Weighing 0.1-1 part by weight of polyethylene glycol-poly (omega-caprolactone) block copolymer (PEG-b-PCL), putting into a container, adding 9.9 parts by weight of chloroalkane solvent, stirring and dissolving completely to prepare a spraying stock solution with a certain concentration.
(2) Fabric pre-preg
The fabric is soaked and rolled in the water-based adhesive in advance for two times, the liquid carrying rate is kept at a certain value, and then the fabric is wound and fixed on a roller device of an electrostatic spinning machine to prepare for receiving the microspheres.
(3) Electrostatic spraying
Sucking the prepared electrostatic spraying stock solution into an injector and putting the injector into a propulsion pump. And then, adjusting the processing temperature and humidity, setting a certain external voltage, flow rate and receiving distance, and electrostatically spraying the coating microspheres on the surface of the fabric.
(4) Adhesive treatment
And drying the microsphere coated fabric at a certain temperature to crosslink and solidify the adhesive, and adhering the microspheres on the fabric to obtain the coating finished fabric.
(5) The fabrics were tested for wettability and hydrophilic time.
0.5 μ L of distilled water was dropped onto the finished fabric surface with a micro-syringe and the wetting time was recorded. The test was performed 5 times at different sites, and the average was taken as the hydrophilic time. Testing the water conductivity: 3 pieces of fabric sample were cut to a size of 2.5cm by 30 cm. Preparing 0.5% potassium dichromate water solution, and keeping the liquid temperature at 27 +/-2 ℃. And soaking the lower end of the sample strip in 0.5% potassium dichromate water solution, keeping for 30min, and taking out the sample strip. The penetration height of the sample strips was measured. And (3) averaging the sample strips to obtain the capillary effect value of the fabric.
The mechanism of the invention is as follows: (1) the molecular structure of the block copolymer with amphiphilic property in the electrostatic spraying stock solution is controlled, and the micro-phase separation is generated by utilizing the difference of the amphiphobicity of two blocks in the drying process of liquid drops to generate a rough spherical surface. (2) Polyethylene glycol with the number average molecular weight of 1000-5000 is grafted into the PCL chain segment to form a block polymer, sufficient hydrophilicity can be provided by using a proper PEG chain length, and the esterification reaction of the PEG and the PCL which is a macromolecule can be ensured. (3) And (3) applying higher external voltage by utilizing lower mass concentration of the electrostatic spraying stock solution and lower flow velocity of the spraying solution to enable the sprayed high molecular solution to form secondary liquid drops and secondary liquid drops so as to obtain the sprayed liquid drops. (4) The used chloroalkane solvent has a low boiling point and is easy to evaporate, so that the sprayed liquid drop is completely dried in the falling process, and finally the microsphere particles are obtained.
The invention discloses a preparation method and application of super-hydrophilic polymer microspheres. The process for preparing the microspheres is simple, and the particle size and the surface morphology structure of the obtained microspheres are controllable.
Compared with the prior art, the technical scheme provided by the invention has the beneficial effects that:
(1) in the selected PEG modified PCL molecule, because a PEG chain segment with a certain chain length is embedded, in the process of dropping and drying liquid drops into spheres, the intrinsically hydrophobic PCL chain and the intrinsically hydrophilic PEG chain segment are subjected to microphase separation, wherein the PEG is more prone to gather at an air end, and the PCL chain is more prone to diffuse towards the inside, so that bulges and pits are respectively generated on the surface of the microspheres, and a nano secondary structure with a wrinkle appearance is formed.
(2) The average particle size of the hydrophilic microspheres prepared by the method is 5.0-10.0 microns, the hydrophilic microspheres belong to micron-sized spherical particles, and the hydrophilic microspheres can be used for a substrate coating to obtain a micron-sized primary structure. Meanwhile, the composite material with the micron primary structure and the nanometer secondary structure has high roughness and large specific surface area, so that the composite material has super-hydrophilicity.
(3) When the microspheres are coated on the surface of the fabric, the adopted adhesive is a water-based adhesive, so that a large amount of water dispersant is not evaporated in the rotating process of the roller to cause premature crosslinking and curing. After the electrostatic spray is received, the binder is cross-linked and cured by drying to bond the microspheres to the fiber surface of the fabric and provide durability.
(4) The preparation method of the microsphere provided by the invention is simple and convenient in process, strong in controllability and suitable for industrial production, popularization and application.
Drawings
FIG. 1 is a schematic representation of an electrostatically injected microsphere and coating used in an embodiment of the present invention;
FIG. 2 is a statistical chart of the average particle size of microspheres prepared according to an embodiment of the present invention;
FIG. 3 is a microscopic morphology of microspheres prepared by examples of the present invention and comparative examples;
FIG. 4 is a topographical view of a superhydrophilic fabric prepared in accordance with an embodiment of the present invention.
Detailed Description
The invention is further described below with reference to the figures and examples.
The invention takes a hydrophilic modified block copolymer as a treating agent, utilizes the hydrophilicity of macromolecules, and coats a fabric by an electrostatic spraying method. Controlling the mass concentration of the electrostatic spraying stock solution to be lower, the flow rate of the spraying solution to be lower, and applying higher external voltage to enable the sprayed high molecular solution to form secondary liquid drops and secondary liquid drops, so that microphase separation is generated, and a spherical particle coating with a rough surface is generated on the surface of the fabric. The super-hydrophilicity is provided on the surface of the fabric by using hydrophilic particles with high specific surface area.
Example 1
A250 mL three-necked flask was charged with 10.1 g of carboxyl-terminated PCL having a number average molecular weight of 8 ten thousand, 1.62 g N, N' -Carbonyldiimidazole (CDI) and 100 mL of Tetrahydrofuran (THF), and dissolved at room temperature. Under nitrogen protection, 1.2 g of PEG-1000 was dissolved in 40 g of Tetrahydrofuran (THF), and the solution was added dropwise to a three-necked flask through a constant temperature and pressure funnel over 2 hours. After the addition was complete, the reaction was carried out at 35 ℃ for 8 hours. After the reaction is finished, pouring the reaction liquid into 160g of petroleum ether, precipitating a white solid by an anti-solvent method, filtering to obtain 9.6g of block modified PCL product PEG1000-b-PCL, washing with a mixed solution of ethanol and deionized water (v/v, 1: 1) for 4 times, using 300 g of the mixed solution each time, washing with deionized water for 4 times, using 600 g of the mixed solution each time, putting the obtained product into a vacuum oven, and drying at 37 ℃ for 24 hours for later use.
0.3 g of PEG1000-b-PCL is weighed and transferred to a round-bottom flask, 9.7 g of trichloromethane is added, and the mixture is stirred and dissolved completely to prepare the electrostatic spraying stock solution with the mass concentration of 3%. The prepared electrospray stock solution is sucked into an injector and put into a propelling pump, and then the temperature in the device is adjusted to 18 +/-1 ℃ and the humidity is adjusted to 65%. The applied voltage is adjusted to 12.5kV, and the flow rate is 0.6 mL.h-1And a reception distance of 15 cm.
Diluting the polyacrylate emulsion type adhesive with distilled water until the solid content is 2wt%, then pre-soaking and rolling the dacron in the diluted adhesive for two times, keeping the liquid carrying rate at 115-120%, and then winding and fixing the dacron on a roller device to receive the microspheres for 3 hours. And after receiving, drying the polyester fabric for 24 hours in a drying oven at 50 ℃ to ensure that the adhesive is crosslinked and cured, wherein the average particle size of the microspheres is 5.293 +/-0.623 mu m. It is also possible to use an aluminum plate coated with polyacrylate to receive the microspheres, the resulting microspheres being similar to the fabric.
And (3) wettability testing: 0.5 μ L of distilled water was dropped onto the finished fabric surface with a micro-syringe and the wetting time was recorded. The test was performed 5 times at different sites and the average was taken. The wetting time was measured to be 1s and the fabric exhibited superhydrophilicity.
Testing the water conductivity: 3 pieces of fabric sample were cut to a size of 2.5cm by 30 cm. Preparing 0.5% potassium dichromate water solution, and keeping the liquid temperature at 27 +/-2 ℃. And soaking the lower end of the sample strip in 0.5% potassium dichromate water solution, keeping for 30min, and taking out the sample strip. The penetration height of the sample strips was measured. And taking the average value of the 3 sample strips to obtain the capillary effect value of the fabric, which is 16.7 cm.
And (3) testing air permeability: the air permeability of the coated fabric was measured by a model YG461E-III full-automatic air permeability tester (Ningbo textile instruments Co., Ltd.) under a pressure of 100Pa and a cloth sample area of 20cm2The average was taken 4 times of the test. The air permeability of the coated fabric was measured to be 115.5mm/s and the air permeability of the coated fabric was not reduced compared to the untreated fabric (air permeability of 115.7 mm/s).
Example 2
A250 mL three-necked flask was charged with 11.6 g of carboxyl-terminated PCL having a number average molecular weight of 10 ten thousand, 1.62 g N, N' -Carbonyldiimidazole (CDI) and 110 mL of Tetrahydrofuran (THF), and dissolved at room temperature. 4.1 g of PEG-4000 were dissolved in 40 g of Tetrahydrofuran (THF) under nitrogen protection, and the solution was added dropwise to a three-necked flask through a constant temperature and pressure funnel over 2 hours. After the addition was complete, the reaction was carried out at 35 ℃ for 8 hours. After the reaction is finished, pouring the reaction liquid into 180g of petroleum ether, precipitating white solid by an anti-solvent method, filtering to obtain 13.7g of block modified PCL product PEG4000-b-PCL, washing with a mixed solution of ethanol and deionized water (v/v, 1: 1) for 4 times, using 350 g of the mixed solution each time, washing with deionized water for 4 times, using 700 g of the mixed solution each time, putting the obtained product into a vacuum oven, and drying at 37 ℃ for 24 hours for later use.
0.5 g of PEG1000-b-PCL is weighed and transferred to a round-bottom flask, 10.0 g of dichloromethane is added, and the mixture is stirred and dissolved completely to prepare electrostatic spraying stock solution with the mass concentration of 4.8%. The prepared electrospray stock solution was sucked into a 10mL syringe and placed into a propeller pump, and then the temperature in the device was adjusted to 20. + -. 1 ℃ and the humidity was adjusted to 65%. The applied voltage was adjusted to 12.5kV, and the flow rate was 1.0 mL. h-1And a reception distance of 15 cm.
Diluting the polyurethane emulsion type adhesive with distilled water until the solid content is 2wt%, then pre-soaking and rolling the dacron in the diluted adhesive for two times, keeping the liquid carrying rate at 115-120%, then winding and fixing the dacron on a roller device to receive the sprayed microspheres for 70 min, and after the reception is finished, drying the dacron for 24h in a drying oven at 45 ℃ so as to crosslink and solidify the adhesive, wherein the particle size of the microspheres is 5.9153 +/-0.568 mu m.
According to the wettability test in example 1, the wetting time was measured to be 0.5s, and the fabric was instantly wetted, showing super-hydrophilicity. The capillary value is measured to be 17.6 cm; the air permeability test was carried out according to the method of example 1, and 4 measurements were taken as an average to determine that the air permeability of the coated fabric was 117.8 mm/s.
Example 3
A250 mL three-necked flask was charged with 11.7 g of carboxyl-terminated PCL having a number average molecular weight of 10 ten thousand, 1.62 g N, N' -Carbonyldiimidazole (CDI) and 110 mL of Tetrahydrofuran (THF), and dissolved at room temperature. Under nitrogen protection, 2.4 g of PEG-2000 was dissolved in 35 g of Tetrahydrofuran (THF), and the solution was added dropwise to a three-necked flask through a constant temperature and pressure funnel over 1 hour. After the addition was complete, the reaction was carried out at 35 ℃ for 8 hours. After the reaction is finished, pouring the reaction liquid into 150g of petroleum ether, precipitating white solid by an anti-solvent method, filtering to obtain 11.0g of block modified PCL product PEG3000-b-PCL, washing with a mixed solution of ethanol and deionized water (v/v, 1: 1) for 4 times, using 250 g of the mixed solution each time, washing with deionized water for 4 times, using 500 g of the mixed solution each time, putting the obtained product into a vacuum oven, and drying at 37 ℃ for 24 hours for later use.
0.5 g of PEG2000-b-PCL is weighed and transferred to a round-bottom flask, 9.5 g of trichloromethane is added, and the mixture is stirred and dissolved completely to prepare electrostatic spraying stock solution with the mass concentration of 5.0%. The prepared electrospray stock solution was sucked into a 10mL syringe and placed into a propeller pump, and then the temperature in the device was adjusted to 20. + -. 1 ℃ and the humidity was adjusted to 65%. The applied voltage was adjusted to 12.0kV, and the flow rate was 1.6 mL. h-1And a reception distance of 12 cm.
The polyester fabric is soaked and rolled twice in an adhesive (the solid content of polyacrylate emulsion is 5 wt%) in advance, the liquid carrying rate is kept at 115-mangle 120%, then the polyester fabric is wound and fixed on a roller device to receive the sprayed microspheres for 60min, and after the receiving is finished, the polyester fabric is dried for 24h in a drying oven at the temperature of 45 ℃ so that the adhesive is crosslinked and cured, and the average particle size of the microspheres is 7.252 +/-0.487 mu m.
According to the wettability test in example 1, the wetting time was measured to be 1s, and the fabric was instantly wetted and showed super-hydrophilicity. The hairiness value was found to be 16.9 cm. And (3) testing air permeability: the air permeability of the coated fabric was measured by a model YG461E-III full-automatic air permeability tester (Ningbo textile instruments Co., Ltd.) under a pressure of 100Pa and a cloth sample area of 20cm2The average was taken 4 times of the test. The air permeability of the coated fabric was measured to be 116.9mm/s
Example 4
The preparation process of PEG2000-b-PCL is the same as that of example 3.
0.5 g of PEG2000-b-PCL is weighed and transferred to a round-bottom flask, 9.5 g of trichloromethane is added, and the mixture is stirred and dissolved completely to prepare electrostatic spraying stock solution with the mass concentration of 5.0%. The prepared electrospray stock solution was sucked into a 10mL syringe and placed into a propeller pump, and then the temperature in the device was adjusted to 20. + -. 1 ℃ and the humidity was adjusted to 65%. The applied voltage was adjusted to 10.0kV, and the flow rate was adjusted to 2.0 mL. multidot.h-1And a reception distance of 18 cm.
The polyester fabric is soaked and rolled twice in an adhesive (the solid content of polyacrylate emulsion is 3 wt%) in advance, the liquid carrying rate is kept at 115-mangle 120%, then the polyester fabric is wound and fixed on a roller device to receive the sprayed microspheres for 60min, and after the receiving is finished, the polyester fabric is dried for 24h in a drying oven at the temperature of 45 ℃ so that the adhesive is crosslinked and cured, and the average particle size of the microspheres is 8.439 +/-0.665 mu m.
According to the wettability test in example 1, the wetting time was measured to be 0s, and the fabric was instantaneously wetted and showed super-hydrophilicity. The hairiness value was found to be 18.1 cm. And (3) testing air permeability: the air permeability of the coated fabric was measured by a model YG461E-III full-automatic air permeability tester (Ningbo textile instruments Co., Ltd.) under a pressure of 100Pa and a cloth sample area of 20cm2The average was taken 4 times of the test. The air permeability of the coated fabric was measured to be 114.2 mm/s.
Example 5
The preparation process of PEG2000-b-PCL is the same as that of example 3.
0.3 g of PEG2000-b-PCL is weighed and transferred to a round-bottom flask, 9.7 g of trichloromethane is added, and the mixture is stirred and dissolved completely to prepare electrostatic spraying stock solution with the mass concentration of 3.0%. The prepared electrospray stock solution was sucked into a 10mL syringe and placed into a propeller pump, and then the temperature in the device was adjusted to 20. + -. 1 ℃ and the humidity was adjusted to 65%. The applied voltage was adjusted to 15.0kV, and the flow rate was adjusted to 3.0 mL. h-1And a reception distance of 15 cm.
The polyester fabric is soaked and rolled twice in an adhesive (the solid content of the polyurethane emulsion is 5 wt%) in advance, the liquid carrying rate is kept at 115-120%, then the polyester fabric is wound and fixed on a roller device to receive the sprayed microspheres for 50 min, and after the receiving is finished, the polyester fabric is dried for 24h in a drying oven at the temperature of 45 ℃ so that the adhesive is crosslinked and cured, and the average particle size of the microspheres is 9.672 +/-0.745.
According to the wettability test in example 1, the wetting time was measured to be 0s, and the fabric was instantaneously wetted and showed super-hydrophilicity. The hairiness value was found to be 18.4 cm. And (3) testing air permeability: the air permeability of the coated fabric was measured by a model YG461E-III full-automatic air permeability tester (Ningbo textile instruments Co., Ltd.) under a pressure of 100Pa and a cloth sample area of 20cm2The average was taken 4 times of the test. The air permeability of the coated fabric was measured to be 118.1 mm/s.
Comparative example 1
A250 mL three-necked flask was charged with 11.0g of carboxyl-terminated PCL having a number average molecular weight of 10 ten thousand, 1.62 g N, N' -Carbonyldiimidazole (CDI) and 110 mL of Tetrahydrofuran (THF), and dissolved at room temperature. 0.6 g of PEG-400 was dissolved in 20 g of Tetrahydrofuran (THF) under nitrogen protection, and the solution was added dropwise to a three-necked flask through a constant temperature and pressure funnel for 1 hour. After the addition was complete, the reaction was carried out at 35 ℃ for 8 hours. After the reaction is finished, pouring the reaction liquid into 150g of petroleum ether, precipitating white solid by an anti-solvent method, filtering to obtain 9.1g of block modified PCL product PEG400-b-PCL, washing with a mixed solution of ethanol and deionized water (v/v, 1: 1) for 4 times, using 200 g of the mixed solution each time, washing with deionized water for 4 times, using 400 g of the mixed solution each time, putting the obtained product into a vacuum oven, and drying at 37 ℃ for 24 hours for later use.
0.5 g of PEG1000-b-PCL is weighed and transferred to a round-bottom flask, 9.5 g of trichloromethane is added, and the mixture is stirred and dissolved completely to prepare electrostatic spraying stock solution with the mass concentration of 5.0%. The prepared electrospray stock solution was sucked into a 10mL syringe and placed into a propeller pump, and then the temperature in the device was adjusted to 20. + -. 1 ℃ and the humidity was adjusted to 65%. The applied voltage was adjusted to 12.5kV, and the flow rate was 1.0 mL. h-1And a reception distance of 15 cm.
The dacron fabric is soaked twice and rolled twice in an adhesive (the solid content of polyacrylate emulsion is 2 wt%) in advance, the liquid carrying rate is kept at 115-mangle 120%, and then the dacron fabric is wound and fixed on a roller device to receive the injection microspheres, wherein the particle size of the microspheres is 5.613 +/-0.654 mu m, the surfaces of the microspheres are smooth, and no micro-nano structure is generated. And after receiving, drying the polyester fabric for 24 hours in a drying oven at the temperature of 45 ℃ so as to crosslink and solidify the adhesive. The fabric exhibited poor hydrophilicity as measured by the wettability test in example 1 with a wetting time of 7 s. The root mean square value was found to be 6.2 cm.
FIG. 1 is a schematic representation of an electrostatically-sprayed microsphere and coating used in an embodiment of the present invention. The polymer solution in the injector is pushed by a pump to enter a high-voltage electric field, the stock solution is sprayed under the action of the high-voltage electric field to form liquid drops, the liquid drops are dried when falling to the surface of the fabric pre-coated with the adhesive, and the micro-phase separation is carried out to form microspheres on the surface of the micro-nano composite structure.
FIG. 2 is a statistical graph of the average particle sizes of the microspheres prepared in examples 1 to 5, wherein the average particle size of the microspheres prepared in example 1 is 5.293 + -0.623 μm, the average particle size of the microspheres prepared in example 2 is 5.9153 + -0.568 μm, the average particle size of the microspheres prepared in example 3 is 7.252 + -0.487 μm, the average particle size of the microspheres prepared in example 4 is 8.439 + -0.665 μm, and the average particle size of the microspheres prepared in example 5 is 9.672 + -0.745.
FIG. 3 is a microscopic morphology diagram of microspheres prepared according to examples 1 to 5 and comparative example 1, wherein wrinkles appear on the surfaces of the microspheres prepared according to the examples of the present invention, the microspheres all have a micro-nano composite structure, the average particle size of the microspheres of the comparative example is 5.613 +/-0.654 μm, and the surfaces of the microspheres are smooth.
FIG. 4 is a microscopic topography of a coated fabric prepared according to examples 1-3 of the present invention, wherein abc corresponds to example 1, example 2, and example 3, respectively.
The invention utilizes the amphiphilic property of the polyethylene glycol-poly (omega-caprolactone) block copolymer to form micron-nano composite structure spherical particles with rough surfaces in the forming process; when the microspheres are coated on the surface of the fabric, the adopted adhesive is a water-based adhesive, so that a large amount of water dispersant is not evaporated in the rotating process of the roller to cause premature crosslinking and curing. After the electrostatic spray is received, the binder is cross-linked and cured by drying to bond the microspheres to the fiber surface of the fabric and provide durability.
Claims (3)
1. A preparation method of super-hydrophilic fabric is characterized by comprising the following steps:
(1) adding carboxyl-terminated PCL and N, N' -carbonyldiimidazole into tetrahydrofuran, and dissolving at room temperature; then, under the protection of nitrogen, dripping a tetrahydrofuran solution of PEG; then reacting to obtain a polyethylene glycol-poly (omega-caprolactone) block copolymer;
(2) dissolving a polyethylene glycol-poly (omega-caprolactone) block copolymer into a chloroalkane solvent, stirring and dissolving to prepare a spray stock solution;
(3) soaking and rolling the fabric in a water-based adhesive for two times to obtain a fabric with liquid;
(4) spraying the spraying stock solution to the surface of the fabric with the liquid by taking the fabric with the liquid as a receiver in an electrostatic spraying manner to obtain a fabric with a microsphere coating;
(5) drying the coated fabric to obtain a super-hydrophilic fabric;
the number average molecular weight of the carboxyl-terminated PCL is 2-12 ten thousand, the number average molecular weight of the PEG is 1000-5000, and the reaction is carried out for 8 hours at 35 ℃;
the processing temperature during electrostatic spraying is 10-35 ℃, the humidity is 45-75%, the applied voltage is 8-25 kV, and the flow rate is 0.6 mL.h-1～3 mL· h-1The receiving distance is 10-25 cm, and the rotation speed of the roller is 10-100 revolutions per minute; in the fabric with the microsphere coating, the average particle size of the microspheres is 5.0-10.0 μm.
2. The method of claim 1, wherein the chlorinated alkane solvent is one of chloroform, dichloromethane, carbon tetrachloride and dichloroethane; the mass concentration of the spraying stock solution is 1.0-9.2%.
3. The method for preparing the super-hydrophilic fabric according to claim 1, wherein the fabric is one of cotton, terylene, silk and aramid fiber or any blended fabric thereof; the water-based adhesive is one of polyacrylate emulsion or polyurethane emulsion, and the mass concentration of the water-based adhesive is 1-10%; the liquid carrying rate of the liquid carrying fabric is 90-120%; the drying temperature is 40-80 ℃, and the drying time is 1-24 hours.
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