CN115138347B - Preparation method of strong-acid hollow nanospheres and application of strong-acid hollow nanospheres in urea adsorption - Google Patents
Preparation method of strong-acid hollow nanospheres and application of strong-acid hollow nanospheres in urea adsorption Download PDFInfo
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Abstract
The invention discloses a preparation method of a strong acid hollow nanosphere and application thereof in urea adsorption. The method of the invention firstly uses a modified emulsion polymerization method, uses styrene as a monomer and divinylbenzene as a cross-linking agent, and obtains the polystyrene core-shell nanospheres with linear cores and cross-linked shells through delayed dripping of the cross-linking agent. Then the polystyrene hollow nanospheres can be obtained by etching the polystyrene hollow nanospheres with good solvents, and after etching, the linear cores are dissolved while the crosslinked shells remain. Finally, the hollow nanospheres are subjected to sulfonic acid treatment to modify sulfonic acid groups on the hollow nanospheres, so that the strongly acidic hollow nanospheres are finally obtained. The method is simple to operate, and the obtained hollow sphere has a good hollow structure and uniform particle size. The synthesized strong acid hollow nanospheres can be used as an adsorption material for adsorbing urea in an aqueous solution. The invention does not relate to heavy metal ions, has no worry of metal leakage, and has faster adsorption speed and stronger adsorption capacity.
Description
Technical Field
The invention belongs to the technical field of biomedical materials and the technical field of polymer nano materials, and particularly relates to a synthesis method of a strong acid hollow nanosphere and application of the strong acid hollow nanosphere in urea adsorption.
Background
In recent years, chronic kidney disease has become a global public health problem that severely jeopardizes human health. At present, more than 90% of patients with End-stage renal disease (End-Stage Renal Disease, ESRD) in China use hemodialysis methods. The frequent dialysis and the limited physical activity during dialysis make the daily life of the patient very inconvenient. In addition, the dialysis process consumes a large amount of expensive dialysate and related consumables, bringing economic pressure to the patient. To solve the above problems, researchers have proposed the concept of a wearable artificial kidney (Wearable Artificial Kidney, WAK). By regenerating the dialysate, the dosage of the dialysate is reduced, so that the miniaturized dialysis machine is possible to be used by patients so as to realize dialysis anytime and anywhere, thereby reducing the treatment cost and improving the life quality and compliance of the patients.
Currently, the biggest bottleneck in developing WAK is to prepare a highly efficient urea adsorbent material to remove urea that diffuses into the dialysate through dialysis. Adults produce about 400mmol of urea per day, far more than other metabolites. However, due to the low chemical activity of urea, it is difficult to react with other compounds under physiological conditions, so that there is a lack of a good method for effectively scavenging urea. It was found that when urea is adsorbed by non-covalent bonding using materials such as activated carbon, silicon, zeolite, and two-dimensional titanium carbide (MXenes), the urea adsorption capacity of these materials is low due to the competing effects of water, resulting in the need to use more adsorbent material to adsorb urea, thus making it difficult to miniaturize artificial kidneys. For example, in 2018, yury go tsi et al used MXenes as an adsorbent, and developed a urea adsorbent having a maximum adsorption capacity of only 0.36mmol/g at 37 ℃ by utilizing hydroxyl groups, oxygen atoms and fluorine atoms which are rich in the surface and which can be non-covalently bonded to urea. Therefore, in order to overcome the problem of low urea adsorption capacity of materials due to the competitive adsorption of water, researchers have introduced metal coordination bonds, namely, the metal ion-loaded polymeric urea adsorption materials with high adsorption capacity are prepared by the principle that the bonding capacity of metal ions and urea is greater than that of water. For example, the teaching of the university of double denier Zhouping that the macroporous Chitosan film (Chitosan) is added into the aqueous solution of copper sulfate to prepare the macromolecular metal ion compound urea adsorption material Chitosan-Cu 2 +. Although Chitosan-Cu was prepared 2 + has a high urea adsorption capacity (about 1.3 mmol/g) at room temperature, but potential heavy metal leakage is a concern.
In addition, some researchers have proposed covalent processes for preparing multi-carbonyl compounds (e.g., aldehyde groups, glycolaldehyde groups, keto esters, ninhydrin, etc.) containing covalent bonds with urea, to produce urea-adsorbing materials with high adsorption capacity and without metal leakage problems. For example, in 2019, by chemical modification, benzoyl formaldehyde (phenylglyoxylaldehydes) capable of covalently binding urea is modified on polystyrene microspheres with a size of about hundreds of micrometers, and the maximum urea adsorption capacity of the obtained material reaches 2.2mmol/g. Although the maximum urea adsorption capacity of this material is higher than that reported previously, its kinetic adsorption rate on urea is slow (urea adsorption capacity of only about 0.5mmol/g for 8 hours at 37 ℃) and is difficult to be truly applied in WAK. Therefore, finding a urea adsorbent material with high adsorption capacity and rapid adsorption kinetics remains a critical issue in WAK.
The search of the literature and patent results related to urea adsorption materials at home and abroad shows that: at present, no report on a preparation method of the strong acid hollow nanospheres and application of the strong acid hollow nanospheres in the field of urea adsorption is found.
Disclosure of Invention
The invention aims to provide a preparation method of a strong acid hollow nanosphere.
The method of the invention firstly uses a modified emulsion polymerization method, uses styrene as a monomer and divinylbenzene as a cross-linking agent, and obtains the polystyrene core-shell nanospheres with linear cores and cross-linked shells through delayed dripping of the cross-linking agent. Then the polystyrene hollow nanospheres can be obtained by etching the polystyrene hollow nanospheres with good solvents, and after etching, the linear cores are dissolved while the crosslinked shells remain. Finally, the hollow nanospheres are subjected to sulfonic acid treatment to modify sulfonic acid groups on the hollow nanospheres, so that the strongly acidic hollow nanospheres are finally obtained. The method of the invention is as follows:
step (1), adding styrene, a surfactant and an initiator into water, and stirring to obtain emulsion; styrene 35-140 ml, surfactant 0.2-1.0 g and initiator 0.5-5.0 g are added into each liter of water.
The surfactant is an ionic surfactant, and is specifically sodium dodecyl sulfate, sodium cetyl sulfate, sodium stearyl sulfate, cetyltrimethylammonium bromide or cetyltrimethylammonium chloride.
The initiator is potassium persulfate, sodium persulfate, ammonium persulfate, azodiisobutyronitrile, azodiisoheptonitrile or azodicyanovaleric acid.
Step (2) deoxidizing by nitrogen, heating to 60-80 ℃ in water bath, and reacting for 1-6 hours; too short a reaction time may result in difficulty in forming a hollow structure, while too long may result in a final shell that is too thin and is easily broken or collapsed.
And (3) adding a mixed solution of divinylbenzene and styrene, and continuing the reaction for 18-24 hours.
The volume ratio of the divinylbenzene to the styrene added into the mixed solution is 0.15-0.6: 1, a step of; the volume ratio of the emulsion in the step (1) to the mixed solution in the step (3) is 1:0.01 to 0.02.
The mixed solution finally causes the crosslinking degree of the hollow sphere to be 0.5% -3%, otherwise, insufficient crosslinking can be caused by too low crosslinking degree, and the hollow sphere can be completely dissolved during etching; and too high crosslinking degree can cause excessive crosslinking, so that the interior cannot be etched and dissolved, and the hollow nanospheres cannot be obtained.
And (4) centrifuging and washing the reaction product to obtain the polystyrene core-shell nanospheres.
And (5) dispersing the prepared polystyrene core-shell nanospheres in an organic solvent, and stirring and reacting for 12-48 hours at the temperature of 20-80 ℃ in a water bath.
The organic solvent is a good solvent of polystyrene, and is specifically one or more mixed solvents of DMF, THF, dimethylbenzene and cyclohexane; each gram of polystyrene core-shell nanospheres are dispersed in 0.01 to 0.1 liter of organic solvent.
Step (6), centrifuging and washing the reaction product to obtain polystyrene hollow nanospheres;
step (7), adding the prepared polystyrene hollow nanospheres into a strong acid solution, and reacting for 3-8 hours at the temperature of 60-80 ℃ in a water bath;
the strong acid solvent is concentrated sulfuric acid, fuming sulfuric acid or chlorosulfonic acid, and 0.01-0.05 liter of strong acid solution is added into each gram of polystyrene hollow nanospheres;
and (8) centrifuging and washing the reaction product to obtain the strong acid hollow nanospheres.
Compared with the existing preparation method of the strong acid hollow nanospheres, the preparation method has the following beneficial effects:
1. compared with the prior conventional method for preparing the hollow spheres by using a template method, namely, firstly preparing the template, then wrapping a layer of required material outside to prepare the core-shell spheres, and finally etching the template to obtain the hollow spheres;
2. compared with the modified dispersion polymerization method of the prior invention, the modified emulsion polymerization method provided by the invention can obtain hollow spheres with smaller size, namely, the specific surface area of the hollow spheres can be better increased, so that the adsorption capacity is improved;
3. the method for preparing the hollow sphere is simple, and the size, the shell thickness and the porosity of the hollow sphere can be conveniently adjusted by adjusting the dropping time and the concentration of the cross-linking agent.
Another object of the present invention is to provide the use of strongly acidic hollow nanospheres in urea adsorption. The strong acid hollow nanospheres ionize hydrogen ions in water, the hydrogen ions and urea are combined to form protonated urea, and the positively charged protonated urea and negatively charged sulfonate ions on the hollow nanospheres are combined through electrostatic interaction, so that the material can adsorb urea in water.
In the application environment, the concentration of urea in the urea aqueous solution to be adsorbed is less than or equal to 30mM, and the concentration is similar to the concentration of urea in the body of a patient suffering from uremia; the pH value of the urea aqueous solution to be adsorbed is 3-6, and the ionic strength is less than or equal to 500mM. The strong acid hollow nanospheres are used as adsorption materials, 1-20 g of strong acid hollow nanospheres are added into each liter of urea aqueous solution to be adsorbed, and the adsorption time is 1-8 hours.
Compared with the existing adsorption material, the invention has the following beneficial effects:
1. compared with the material which adsorbs urea by hydrogen bond interaction, the invention uses electrostatic interaction, thus avoiding the interference of water and being capable of adsorbing urea in water solution;
2. compared with the adsorption material containing heavy metal ions, the adsorption material does not involve heavy metal ions and has no worry about metal leakage;
3. compared with the method for adsorbing urea by covalent interaction, the material obtained by the invention has higher adsorption speed and stronger adsorption capacity;
4. the invention can realize the controllable adjustment of the size, shell thickness, porosity, sulfonic acid group content and other properties of the hollow sphere by adjusting and controlling the concentration of the cross-linking agent, the dripping time, various reactant ratios, the sulfonic acid degree and other experimental parameters.
Drawings
FIG. 1 is a transmission electron microscope picture of a strongly acidic hollow nanosphere according to one embodiment of the invention;
FIG. 2 shows a hollow nanosphere before sulfonation (H-CPS) and a strongly acidic hollow nanosphere after sulfonation (H-CPS-SO) according to an embodiment of the present invention 3 H) Is an infrared spectrum of (2);
FIG. 3 is a transmission electron microscope picture of a strongly acidic hollow nanosphere according to another embodiment of the present invention;
FIG. 4 is a transmission electron microscope image of a strongly acidic hollow nanosphere according to yet another embodiment of the invention;
FIG. 5 is a graph showing the urea adsorption capacity of the strong acid hollow nanospheres over time in one embodiment of the present invention.
Detailed Description
Example 1.
Step (1), adding 35ml of styrene, 0.2g of sodium dodecyl sulfate and 0.5g of potassium persulfate into 1 liter of water, and uniformly stirring to obtain emulsion;
step (2) deoxidizing by nitrogen, heating to 80 ℃ in a water bath, and reacting for 1 hour;
step (3) according to the volume ratio of 0.15:1, preparing divinylbenzene and styrene into a mixed solution; then adding the mixed solution into the dairy industry according to the volume ratio of 1:0.02, and continuing to react for 18 hours;
step (4), centrifuging and washing the reaction product to obtain polystyrene core-shell nanospheres;
step (5), dispersing the prepared polystyrene core-shell nanospheres in an organic solvent DMF according to the proportion of dispersing in 0.01 liter of the organic solvent per gram, and stirring in a water bath at 20 ℃ for reaction for 48 hours;
step (6), centrifuging and washing the reaction product to obtain polystyrene hollow nanospheres;
step (7), adding the prepared polystyrene hollow nanospheres into concentrated sulfuric acid, and reacting in a water bath at 60 ℃ for 8 hours; adding 0.02 liter of concentrated sulfuric acid into each gram of polystyrene hollow nanospheres;
and (8) centrifuging and washing the reaction product to obtain the strong acid hollow nanospheres.
Example 2.
Step (1), adding 50ml of styrene, 0.4g of sodium hexadecyl sulfate and 1.0g of sodium persulfate into 1 liter of water, and uniformly stirring to obtain emulsion;
step (2) deoxidizing by nitrogen, heating to 70 ℃ in a water bath, and reacting for 2 hours;
step (3) according to the volume ratio of 0.3:1, preparing divinylbenzene and styrene into a mixed solution; then adding the mixed solution into the dairy industry according to the volume ratio of 1:0.015, and continuing to react for 20 hours;
step (4), centrifuging and washing the reaction product to obtain polystyrene core-shell nanospheres;
step (5), dispersing the prepared polystyrene core-shell nanospheres in an organic solvent THF according to the proportion of dispersing in 0.02 liter of the organic solvent per gram, and stirring in a water bath at 30 ℃ for reaction for 36 hours;
step (6), centrifuging and washing the reaction product to obtain polystyrene hollow nanospheres;
step (7), adding the prepared polystyrene hollow nanospheres into fuming sulfuric acid, and reacting for 5 hours at 70 ℃ in water bath; 0.01 liter of fuming sulfuric acid is added into each gram of polystyrene hollow nanospheres;
and (8) centrifuging and washing the reaction product to obtain the strong acid hollow nanospheres.
Example 3.
Step (1), adding 80ml of styrene, 0.5g of sodium octadecyl sulfate and 2.0g of ammonium persulfate into 1 liter of water, and uniformly stirring to obtain emulsion;
step (2) deoxidizing by nitrogen, heating to 65 ℃ in a water bath, and reacting for 3 hours;
step (3) according to the volume ratio of 0.4:1, preparing divinylbenzene and styrene into a mixed solution; then adding the mixed solution into the dairy industry according to the volume ratio of 1:0.012, and continuing to react for 24 hours;
step (4), centrifuging and washing the reaction product to obtain polystyrene core-shell nanospheres;
step (5), dispersing the prepared polystyrene core-shell nanospheres in xylene as an organic solvent according to the proportion of dispersing in 0.05 liter of the organic solvent per gram, and stirring and reacting for 24 hours at the water bath temperature of 50 ℃;
step (6), centrifuging and washing the reaction product to obtain polystyrene hollow nanospheres;
step (7), adding the prepared polystyrene hollow nanospheres into chlorosulfonic acid, and reacting in a water bath at 80 ℃ for 3 hours; 0.05 liter of chlorosulfonic acid is added into each gram of polystyrene hollow nanospheres;
and (8) centrifuging and washing the reaction product to obtain the strong acid hollow nanospheres.
Example 4.
Step (1), adding 100ml of styrene, 0.6g of hexadecyl trimethyl ammonium bromide and 3.0g of azodiisobutyronitrile into 1 liter of water, and uniformly stirring to obtain emulsion;
step (2) deoxidizing by nitrogen, heating to 60 ℃ in a water bath, and reacting for 4 hours;
step (3) according to the volume ratio of 0.5:1, preparing divinylbenzene and styrene into a mixed solution; then adding the mixed solution into the dairy industry according to the volume ratio of 1:0.01, and continuing to react for 20 hours;
step (4), centrifuging and washing the reaction product to obtain polystyrene core-shell nanospheres;
step (5), dispersing the prepared polystyrene core-shell nanospheres in cyclohexane serving as an organic solvent according to the proportion of dispersing in 0.1 liter of the organic solvent per gram, and stirring and reacting for 12 hours at the water bath temperature of 80 ℃;
step (6), centrifuging and washing the reaction product to obtain polystyrene hollow nanospheres;
step (7), adding the prepared polystyrene hollow nanospheres into chlorosulfonic acid, and reacting in a water bath at 70 ℃ for 6 hours; 0.04 liter of chlorosulfonic acid is added into each gram of polystyrene hollow nanospheres;
and (8) centrifuging and washing the reaction product to obtain the strong acid hollow nanospheres.
Example 5.
Step (1), adding 120ml of styrene, 0.8g of hexadecyl trimethyl ammonium chloride and 4.0g of azodiisoheptanenitrile into 1 liter of water, and uniformly stirring to obtain emulsion;
step (2) deoxidizing by nitrogen, heating to 75 ℃ in a water bath, and reacting for 5 hours;
step (3) according to the volume ratio of 0.6:1, preparing divinylbenzene and styrene into a mixed solution; then adding the mixed solution into the dairy industry according to the volume ratio of 1:0.01, and continuing to react for 22 hours;
step (4), centrifuging and washing the reaction product to obtain polystyrene core-shell nanospheres;
step (5), dispersing the prepared polystyrene core-shell nanospheres in an organic solvent according to the proportion of dispersing in 0.08 liter of the organic solvent per gram, and stirring and reacting for 48 hours at the water bath temperature of 30 ℃; the organic solvent adopts a mixed organic solvent of dimethylbenzene and cyclohexane in any proportion;
step (6), centrifuging and washing the reaction product to obtain polystyrene hollow nanospheres;
step (7), adding the prepared polystyrene hollow nanospheres into fuming sulfuric acid, and reacting for 5 hours at the water bath temperature of 60 ℃; 0.03 liter of fuming sulfuric acid is added into each gram of polystyrene hollow nanospheres;
and (8) centrifuging and washing the reaction product to obtain the strong acid hollow nanospheres.
Example 6.
Step (1), adding 140ml of styrene, 1.0g of sodium dodecyl sulfate and 5.0g of azodicarbonyl valeric acid into 1 liter of water, and uniformly stirring to obtain emulsion;
step (2) deoxidizing by nitrogen, heating to 80 ℃ in a water bath, and reacting for 6 hours;
step (3) according to the volume ratio of 0.35:1, preparing divinylbenzene and styrene into a mixed solution; then adding the mixed solution into the dairy industry according to the volume ratio of 1:0.018, and continuing to react for 18 hours;
step (4), centrifuging and washing the reaction product to obtain polystyrene core-shell nanospheres;
step (5), dispersing the prepared polystyrene core-shell nanospheres in an organic solvent according to the proportion of dispersing in 0.08 liter of the organic solvent per gram, and stirring in a water bath at 60 ℃ for reaction for 24 hours; the organic solvent adopts a mixed organic solvent of DMF and THF in any proportion;
step (6), centrifuging and washing the reaction product to obtain polystyrene hollow nanospheres;
step (7), adding the prepared polystyrene hollow nanospheres into concentrated sulfuric acid, and reacting in a water bath at 75 ℃ for 4 hours; adding 0.04 liter of concentrated sulfuric acid into each gram of polystyrene hollow nanospheres;
and (8) centrifuging and washing the reaction product to obtain the strong acid hollow nanospheres.
Example 7.
Step (1) 70ml of water, 0.16ml of 20% strength aqueous solution of sodium dodecyl sulfate, 5ml of styrene and 194mg of potassium persulfate were added to a 100ml three-necked round-bottomed flask, and nitrogen was deoxygenated for 15min. The round bottom flask was then placed in a 70 ℃ water bath and heated. After 4 hours of reaction, a mixture containing 214. Mu.L of divinylbenzene and 0.75ml of styrene was slowly injected into the round-bottomed flask, and the reaction was continued for 21 hours. Finally stopping the reaction, centrifuging, and washing the product with ethanol for 3 times.
Step (2) the core-shell spheres obtained in step (1) were dispersed in 100ml of DMF and reacted at 70 ℃ for 24 hours. The reaction was then stopped and centrifuged, and washed 3 times with DMF, ethanol and water in sequence. And finally, freeze-drying and vacuum-drying.
Step (3) the hollow spheres (1 g) obtained in step (2) were added to 10ml of concentrated sulfuric acid, reacted at 80℃for 5 hours, and then centrifuged and washed three times with water. And finally, freeze-drying and vacuum-drying.
Characterization of morphology and chemical composition of the strongly acidic hollow nanospheres was performed using Transmission Electron Microscopy (TEM), fourier transform infrared spectrometer (FT-IR). The specific test results are as follows:
(1) Transmission Electron Microscope (TEM):
the transmission electron microscope photograph shows the appearance and nano-size of the strong acid hollow nanospheres, and the result is shown by referring to fig. 1, the strong acid hollow nanospheres prepared by the method have good hollow structure and good dispersibility, the diameter is about 280+/-9 nm, and the shell thickness is about 83+/-7 nm.
(2) Fourier transform infrared spectrometer (FT-IR):
the Fourier transform infrared spectrometer (FT-IR) shows the characteristic spectrum of the strong acid hollow nanospheres synthesized by the method. As a result, referring to FIG. 2, after sulfonation, the infrared spectra were obtained at 1650, 1412 and 1389cm- 1 A new peak appears, which can be attributed to the related vibration of the sulfonated benzene ring. In addition, at 1000 and 1250cm- 1 There appear a number of strong infrared peaks which can be attributed to symmetrical and asymmetrical vibrations of the s=o double bond on the sulfonic acid group introduced. As can be seen from the infrared spectrogram, the strongly acidic hollow nanospheres have been successfully prepared.
Example 8.
Step (1) 70ml of water, 0.16ml of 20% strength aqueous solution of sodium dodecyl sulfate, 5ml of styrene and 194mg of potassium persulfate were added to a 100ml three-necked round-bottomed flask, and nitrogen was deoxygenated for 15min. The round bottom flask was then placed in a 70 ℃ water bath and heated. After 2 hours of reaction, a mixture containing 107. Mu.L of divinylbenzene and 0.75ml of styrene was slowly injected into the round-bottomed flask, and the reaction was continued for 21 hours. Finally stopping the reaction, centrifuging, and washing the product with ethanol for 3 times.
Step (2) the core-shell spheres obtained in step (1) were dispersed in 100ml of DMF and reacted at 70 ℃ for 24 hours. The reaction was then stopped and centrifuged, and washed 3 times with DMF, ethanol and water in sequence. And finally, freeze-drying and vacuum-drying.
Step (3) the hollow spheres (1 g) obtained in step (2) were added to 10ml of concentrated sulfuric acid, reacted at 80℃for 5 hours, and then centrifuged and washed three times with water. And finally, freeze-drying and vacuum-drying.
TEM characterization is carried out on the strong acid hollow nanospheres prepared in the embodiment, and the obtained nanoparticles have good hollow structure and good dispersibility as shown in a figure 3. The diameter is about 310+/-15 nm, and the thickness of the shell layer is about 59+/-4 nm.
Example 9.
Step (1) 70ml of water, 0.16ml of 20% strength aqueous solution of sodium dodecyl sulfate, 5ml of styrene and 194mg of potassium persulfate were added to a 100ml three-necked round-bottomed flask, and nitrogen was deoxygenated for 15min. The round bottom flask was then placed in a 70 ℃ water bath and heated. After 3 hours of reaction, a mixture containing 107. Mu.L of divinylbenzene and 0.75ml of styrene was slowly injected into the round-bottomed flask, and the reaction was continued for 21 hours. Finally stopping the reaction, centrifuging, and washing the product with ethanol for 3 times.
Step (2) the core-shell spheres obtained in step (1) were dispersed in 100ml of DMF and reacted at 70 ℃ for 24 hours. The reaction was then stopped and centrifuged, and washed 3 times with DMF, ethanol and water in sequence. And finally, freeze-drying and vacuum-drying.
Step (3) the hollow spheres (1 g) obtained in step (2) were added to 10ml of concentrated sulfuric acid, reacted at 80℃for 5 hours, and then centrifuged and washed three times with water. And finally, freeze-drying and vacuum-drying.
TEM characterization is carried out on the strong acid hollow nanospheres prepared in the embodiment, and as shown in figure 4, the obtained nanoparticles have good dispersibility, are mostly hollow, and are rarely hollow. The diameter is about 290+ -10 nm, and the thickness of the shell layer is about 84+ -8 nm.
The strong acid hollow nanospheres prepared in any one of examples 1 to 9 are used as an adsorption material in urea adsorption.
Example 10.
1g of the strongly acidic hollow nanospheres was added to 1 liter of an aqueous urea solution having a urea concentration of 25mM, pH=3, an ionic strength of 500mM and an adsorption time of 8 hours.
Example 11.
5g of the strongly acidic hollow nanospheres were added to 1 liter of an aqueous urea solution having a urea concentration of 27mM, pH=4, an ionic strength of 450mM and an adsorption time of 6 hours.
Example 12.
10 g of the strongly acidic hollow nanospheres were added to 1 liter of an aqueous urea solution having a urea concentration of 28mM, pH=5, an ionic strength of 480mM, and an adsorption time of 3 hours.
Example 13.
15 g of the strongly acidic hollow nanospheres were added to 1 liter of an aqueous urea solution with a urea concentration of 30mM, pH=6, an ionic strength of 450mM and an adsorption time of 1 hour.
Example 14.
20 g of the strongly acidic hollow nanospheres were added to 1 liter of an aqueous urea solution having a urea concentration of 26mM, pH=4, an ionic strength of 400mM and an adsorption time of 2 hours.
Example 15.
Typically, 50mg of strongly acidic hollow nanospheres are added to 5ml of an aqueous urea solution having a urea concentration of 30mM, and then placed on a shaker and shaken at 37℃to sample at various time points, the reaction solution is subjected to membrane filtration (0.22 μm filter), the filtrate is collected, and the urea concentration in the filtrate is determined. Adsorption capacityWherein c 0 And c 1 The initial concentration of urea and the concentration of urea in the filtrate after reaction are respectively, V is the volume of the reaction solution, and m is the mass of the added strong acid hollow nanospheres.
As shown in FIG. 5, the strong acid hollow nanospheres adsorb urea very fast for the first 10min, and the adsorption capacity and adsorption time almost show a linear relationship. The adsorption rate then becomes slow and reaches an adsorption equilibrium at about 30min, at which time the maximum urea adsorption capacity reaches about 0.9mmol/g. The kinetics experiment result shows that the speed of the strong acid hollow nanospheres for absorbing urea is extremely high, and the urea reaches equilibrium about 30 minutes and remains basically unchanged in the later time. These results show that the strong acid nanometer hollow sphere prepared by the research has good urea adsorption performance, and is expected to be applied to the fields of wearable artificial kidneys and the like as a urea purification component.
The above description of the invention is intended to be illustrative, and not restrictive, and it will be appreciated by those skilled in the art that many modifications, changes, or equivalents may be made thereto without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (9)
1. The preparation method of the strong acid hollow nanospheres is characterized by comprising the following steps:
step (1), adding styrene, a surfactant and an initiator into water, and stirring to obtain emulsion; adding 35-140 ml of styrene, 0.2-1.0 g of surfactant and 0.5-5.0 g of initiator into each liter of water;
step (2) deoxidizing by nitrogen, heating to 60-80 ℃ in water bath, and reacting for 1-6 hours;
step (3), adding a mixed solution of divinylbenzene and styrene, and continuing the reaction for 18-24 hours; the volume ratio of the divinylbenzene to the styrene added into the mixed solution is 0.15-0.6: 1, a step of;
step (4), centrifuging and washing the reaction product to obtain polystyrene core-shell nanospheres;
dispersing the prepared polystyrene core-shell nanospheres in an organic solvent, and stirring and reacting for 12-48 hours at the temperature of 20-80 ℃ in a water bath;
step (6), centrifuging and washing the reaction product to obtain polystyrene hollow nanospheres;
step (7), adding the prepared polystyrene hollow nanospheres into a strong acid solution, and reacting for 3-8 hours at the temperature of 60-80 ℃ in a water bath;
and (8) centrifuging and washing the reaction product to obtain the strong acid hollow nanospheres.
2. The method for preparing the strongly acidic hollow nanospheres according to claim 1, wherein: the surfactant is sodium dodecyl sulfate, sodium hexadecyl sulfate, sodium octadecyl sulfate, cetyltrimethylammonium bromide or cetyltrimethylammonium chloride.
3. The method for preparing the strongly acidic hollow nanospheres according to claim 1, wherein: the initiator is potassium persulfate, sodium persulfate, ammonium persulfate, azodiisobutyronitrile, azodiisoheptonitrile or azodicyanovaleric acid.
4. The method for preparing the strongly acidic hollow nanospheres according to claim 1, wherein: in the reaction system, the volume ratio of the emulsion in the step (1) to the mixed solution in the step (3) is 1:0.01 to 0.02.
5. The method for preparing the strongly acidic hollow nanospheres according to claim 1, wherein: the organic solvent is one or more mixed solvents of DMF, THF, dimethylbenzene and cyclohexane; each gram of polystyrene core-shell nanospheres are dispersed in 0.01 to 0.1 liter of organic solvent.
6. The method for preparing the strongly acidic hollow nanospheres according to claim 1, wherein: the strong acid solution is concentrated sulfuric acid, fuming sulfuric acid or chlorosulfonic acid, and 0.01-0.05 liter of the strong acid solution is added into each gram of polystyrene hollow nanospheres.
7. Use of the strongly acidic hollow nanospheres prepared by the method of any one of claims 1-6 in urea adsorption.
8. The use of the strongly acidic hollow nanospheres as claimed in claim 7 in urea adsorption, characterized in that: in the application environment, the concentration of urea in the urea aqueous solution to be adsorbed is less than or equal to 30mM, the pH value is 3-6, and the ionic strength is less than or equal to 500mM.
9. The use of the strongly acidic hollow nanospheres as claimed in claim 7 in urea adsorption, characterized in that: the strong acid hollow nanospheres are used as adsorption materials, 1-20 g of strong acid hollow nanospheres are added into each liter of urea aqueous solution to be adsorbed, and the adsorption time is 1-8 hours.
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| CN1618824A (en) * | 2004-01-16 | 2005-05-25 | 清华大学 | Crosslinked core-shell structure nano-polymer microsphere and its preparation method |
| CN101323444A (en) * | 2007-06-15 | 2008-12-17 | 中国科学院化学研究所 | Carbon or carbon composite hollow ball and preparation thereof |
| CN103554325A (en) * | 2013-10-28 | 2014-02-05 | 北京化工大学 | Preparation method of functional hollow polymer microspheres |
| CN113801258A (en) * | 2021-09-03 | 2021-12-17 | 江苏月旭新材料科技有限公司 | Preparation method of monodisperse crosslinked polystyrene-divinylbenzene microspheres |
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|---|---|---|---|---|
| CN1618824A (en) * | 2004-01-16 | 2005-05-25 | 清华大学 | Crosslinked core-shell structure nano-polymer microsphere and its preparation method |
| CN101323444A (en) * | 2007-06-15 | 2008-12-17 | 中国科学院化学研究所 | Carbon or carbon composite hollow ball and preparation thereof |
| CN103554325A (en) * | 2013-10-28 | 2014-02-05 | 北京化工大学 | Preparation method of functional hollow polymer microspheres |
| CN113801258A (en) * | 2021-09-03 | 2021-12-17 | 江苏月旭新材料科技有限公司 | Preparation method of monodisperse crosslinked polystyrene-divinylbenzene microspheres |
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