CN118240267A - Blended active carbon polyether sulfone porous material prepared by freeze-induced phase separation method, and preparation method and application thereof - Google Patents
Blended active carbon polyether sulfone porous material prepared by freeze-induced phase separation method, and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000004695 Polyether sulfone Substances 0.000 title claims abstract description 88
- 229920006393 polyether sulfone Polymers 0.000 title claims abstract description 88
- 239000011148 porous material Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000005191 phase separation Methods 0.000 title claims abstract description 18
- 238000001179 sorption measurement Methods 0.000 claims abstract description 97
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- 210000004369 blood Anatomy 0.000 claims abstract description 27
- 239000008280 blood Substances 0.000 claims abstract description 27
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- 238000000926 separation method Methods 0.000 claims abstract description 17
- 238000000746 purification Methods 0.000 claims abstract description 11
- 239000011521 glass Substances 0.000 claims description 40
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 229920001577 copolymer Polymers 0.000 claims description 35
- 238000005266 casting Methods 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 10
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 10
- 238000011049 filling Methods 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 238000010526 radical polymerization reaction Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 230000008081 blood perfusion Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 229920001480 hydrophilic copolymer Polymers 0.000 abstract description 9
- 239000003053 toxin Substances 0.000 abstract description 7
- 231100000765 toxin Toxicity 0.000 abstract description 7
- 108700012359 toxins Proteins 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 5
- 238000007710 freezing Methods 0.000 abstract description 3
- 230000008014 freezing Effects 0.000 abstract description 3
- 239000012620 biological material Substances 0.000 abstract description 2
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- 238000009827 uniform distribution Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 50
- DDRJAANPRJIHGJ-UHFFFAOYSA-N creatinine Chemical compound CN1CC(=O)NC1=N DDRJAANPRJIHGJ-UHFFFAOYSA-N 0.000 description 28
- 229940109239 creatinine Drugs 0.000 description 15
- 206010018910 Haemolysis Diseases 0.000 description 11
- 230000008588 hemolysis Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 230000004907 flux Effects 0.000 description 9
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- 108090000623 proteins and genes Proteins 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229940098773 bovine serum albumin Drugs 0.000 description 3
- 210000003743 erythrocyte Anatomy 0.000 description 3
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- 239000002953 phosphate buffered saline Substances 0.000 description 2
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- 238000009020 BCA Protein Assay Kit Methods 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
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- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 1
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
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Abstract
The invention discloses a blending active carbon polyether sulfone porous material prepared by a freeze-induced phase separation method, a preparation method and application thereof, and belongs to the technical field of biological materials; adding a proper amount of non-solvent into a homogeneous phase polyethersulfone solution until microphase separation is generated, and then forming through freezing treatment, wherein the prepared adsorption column has a micron-sized pore diameter and a continuous pore structure with uniform distribution; the activated carbon and the hydrophilic copolymer are introduced by a blending method, so that the adsorption column has good blood toxin adsorption performance and blood compatibility, can efficiently adsorb blood toxins, has good mechanical properties, cannot be damaged due to pressure in the blood purification treatment process, can be used in the field of blood purification, is simple and easy to obtain in raw materials, and is easy to realize industrialization.
Description
Technical Field
The invention relates to the technical field of biological materials, in particular to a blending active carbon polyether sulfone porous material prepared by a freeze-induced phase separation method, a preparation method and application thereof.
Background
Blood purification therapies have been widely used in the treatment of acute poisoning, organ damage or failure. Polyethersulfone (PES) has received increasing attention in the development of blood purification materials due to stable physical and chemical properties, excellent mechanical properties, and relatively good blood compatibility. At present, however, the preparation of polyethersulfone porous materials is based on the principle of liquid-solid phase conversion, and is generally designed as hollow fiber membranes, flat membranes for dialysis and separation, and microspheres, hollow microspheres for adsorption and perfusion.
The principle of the forming mode adopted by the materials in different forms is that the liquid-solid phase conversion capability of polyethersulfone is utilized, namely, polyethersulfone dissolved in good solvent is added into a large amount of non-solvent, the polyethersulfone is rapidly separated out at the solvent interface at first, and solidified into a dense layer with the aperture in nano scale; and then solidified under the dense layer into an incompletely interconnected porous layer with solvent exchange. The whole curing process is very rapid, and finally the polyether sulfone material with an asymmetric porous structure is formed. Thus, polyethersulfone porous materials prepared by liquid-solid phase conversion, whose permeation and separation can be controlled primarily by the dense layer, sometimes exhibit lower permeabilities. The polyethersulfone material can meet the requirement of hemodialysis, namely, the separation and removal of small molecular toxins can be realized, and meanwhile, beneficial proteins and other components can be intercepted. However, the lower permeability in terms of blood perfusion has limited the use of polyethersulfone materials. For PES microsphere adsorbents, for example, the dense layer and the non-interconnected pore structure allow insufficient time for toxin molecules to diffuse into the interior of the microsphere, but are only adsorbed by the microsphere surface, which greatly reduces the amount of adsorption by the cartridge and the efficiency of material use.
Therefore, for improving the pore uniformity and adsorption performance of the polyethersulfone porous adsorbent material for blood purification, a new material preparation method is still needed to solve the above problems.
Disclosure of Invention
One of the purposes of the invention is to develop a preparation method of a blending active carbon polyethersulfone porous material with high-efficiency adsorption performance aiming at the defects of the prior art so as to solve the problems. The preparation method of the blending active carbon polyether sulfone porous material prepared by the freeze-induced phase separation method comprises the following components in parts by weight:
1) Polyether sulfone solution:
16 to 20 parts of polyether sulfone
80-84 Parts of organic solvent
2) Activated carbon;
3) Copolymer:
10 to 15 parts of methyl methacrylate
10 To 15 parts of N-vinyl pyrrolidone
0.1 To 1 part of oil-soluble azo initiator
4) Non-solvent
The weight ratio of the polyethersulfone solution to the activated carbon to the copolymer is (88-100): (0-6): (0-10);
The preparation method comprises the following steps:
1) Preparation of polyethersulfone solution
Quantitatively weighing 16-20 parts of polyethersulfone, dissolving in 84-80 parts of organic solvent, stirring and dissolving for 12-24 hours to obtain polyethersulfone solution;
2) Preparation of the copolymer
Weighing 10-15 parts of methyl methacrylate, 10-15 parts of N-vinyl pyrrolidone, 0.1-1 part of oil-soluble azo initiator and 80-84 parts of organic solvent quantitatively, adding the prepared polyether sulfone solution, stirring and heating at 70-100 ℃ for 12-24 hours, performing free radical polymerization reaction to obtain copolymer solution, washing the copolymer solution to remove micromolecules and unreacted monomers, and finally drying;
The washing and drying method can be as follows: the copolymer solution was poured into deionized water and stirred for 3 days, water was changed every 24 hours to remove small molecules and unreacted monomers, and finally dried in an oven at 60 ℃ for 12 hours.
3) Preparation of microphase separation casting solution
According to the polyethersulfone solution: activated carbon: the weight ratio of the copolymer is (88-100): (0-6): (0-10), weighing active carbon and copolymer, adding the prepared polyether sulfone solution, and stirring for 2-6 hours at room temperature; adding a non-solvent until the solution becomes suspended so as to obtain microphase separated casting solution;
4) Forming of porous adsorption column by blending activated carbon and polyether sulfone
And (3) filling the microphase separation casting solution into a glass bottle, placing the glass bottle into a refrigerator at the temperature of minus 40 ℃ to minus 20 ℃ for standing, enabling the glass bottle to be further subjected to phase separation and simultaneously forming a uniform porous structure, taking out the glass bottle, placing the glass bottle into deionized water, and replacing a solvent to obtain the blending active carbon polyether sulfone porous adsorption column.
The method for replacing the solvent can be, for example: and taking out, putting into deionized water, replacing the solvent, and changing water every 12 hours for at least three times to obtain the blended active carbon polyether sulfone porous adsorption column.
As a preferable technical scheme, the organic solvent is at least one of dimethylformamide, dimethylacetamide or dimethyl sulfoxide.
As a preferable technical scheme, the activated carbon is spherical granular activated carbon with the diameter of 5-8 mm.
As a preferable technical scheme, the initiator is at least one of an oil-soluble azo initiator such as azodiisobutyronitrile, azodiisoheptonitrile and the like.
As a preferable technical scheme, the non-solvent is at least one of water, ethanol, methanol, glycol, glycerol or mixed non-solvent.
As a preferable technical scheme, the pore diameter of the porous adsorption column is 50-50000 nm by controlling the concentration of polyethersulfone and the mixing amount of copolymer.
The second purpose of the invention is to provide the blended active carbon polyether sulfone porous material prepared by the method.
The invention further provides an application of the blended active carbon polyethersulfone porous material prepared by the method in preparation of blood purification devices.
As a preferred technical scheme, the blended activated carbon polyethersulfone porous adsorption column is used for blood purification, including blood perfusion, blood filtration and plasma separation.
The principle of the invention is as follows: firstly, adding a proper amount of non-solvent into a homogeneous phase polyethersulfone solution until microphase separation is generated, and then forming through freezing treatment, wherein the prepared adsorption column has a micron-sized pore diameter and a continuous pore structure with uniform distribution; and the activated carbon and the hydrophilic copolymer are introduced by a blending method, so that the adsorption column has good blood toxin adsorption performance and blood compatibility, can efficiently adsorb blood toxins, has good mechanical properties, and cannot be damaged due to pressure in the blood purification treatment process.
Firstly, synthesizing a hydrophilic copolymer through free radical polymerization, then preparing a polyethersulfone solution, adding the copolymer into the polyethersulfone solution according to a proper proportion, dripping a proper amount of non-solvent after uniformly mixing until the solution becomes turbid, transferring the solution into a mould, and freeze-forming to obtain the blended active carbon polyethersulfone porous adsorption column.
The preparation method is simple and convenient, the operation is convenient, the monomer sources are wide, and no further chemical modification is needed. The ion adsorption material in the prior art often has no good blood compatibility and cannot be directly used for blood purification. The method of the invention prepares the blending active carbon polyether sulfone porous adsorption column by utilizing simple free radical polymerization to prepare hydrophilic copolymer and combining with freeze-induced phase separation. The hydrophilic copolymer is used for realizing ideal blood compatibility, and the activated carbon is used for improving the adsorption effect.
The hydrophilic copolymer is synthesized by free radical polymerization, and the mechanism is that an oil-soluble azo initiator such as azodiisobutyronitrile initiates the free radical polymerization of methyl methacrylate monomer and N-vinyl pyrrolidone monomer under the heating condition to generate the linear hydrophilic copolymer. The polymer solution generated in the microphase separation process has certain viscosity, so that the activated carbon can be uniformly dispersed in the polymer solution, and then the polymer solution is formed by the freeze phase separation, so that the activated carbon particles are uniformly dispersed and fixed in the porous polymer matrix, and the strong adsorption capacity is provided for the porous adsorption column.
Compared with the prior art, the invention has the advantages that:
1. The invention provides a simpler and more stable forming method of a polyethersulfone porous material, and a blended active carbon polyethersulfone porous adsorption column with uniform aperture and high adsorption performance is prepared only through solution microphase separation and freezing without a complex device;
2. the pore size and the porosity can be effectively controlled by adjusting the mixing amount of the modified copolymer and the activated carbon, and the modified copolymer is suitable for removing different blood toxins, and the specific formula and pore parameters are shown in the following table;
3. Compared with polyether sulfone microspheres, the blended active carbon polyether sulfone porous adsorption column has larger holes and more uniform hole distribution, so that the adsorption capacity and the adsorption speed are higher;
4. The continuous pore structure and the regular skeleton structure enable the blending active carbon polyethersulfone porous adsorption column to have good mechanical properties, and can bear larger pressure when being applied to high-flux plasma perfusion along with the further improvement of the mixing of the active carbon and the copolymer;
5. the surface of the blended active carbon polyethersulfone porous adsorption column has a pore structure similar to a polyethersulfone flat membrane, can be regarded as a plasma separation membrane with a thickness, and can realize synchronous plasma separation and blood endotoxin adsorption and removal processes;
6. The monomer used for preparing the material and the solvent are all common chemical raw materials, can be prepared in large quantity by chemical industry, has rich resources and low cost, and is favorable for industrialization.
Drawings
FIG. 1 is a scanning electron microscope image of a cross section of a porous adsorption column of the blended activated carbon polyethersulfone;
FIG. 2 shows the mechanical properties of the different materials of the examples and comparative examples;
FIG. 3 shows the water flux of the different materials in the examples and comparative examples;
FIG. 4 shows the adsorption amount of creatinine by different materials in each example and comparative example;
FIG. 5 shows the static adsorption of bovine serum albumin by various materials in each example and comparative example;
FIG. 6 shows the hemolysis ratio of the different materials in each of the examples and comparative examples.
Detailed Description
The invention is further illustrated below with reference to examples. It should be noted that: parts in the present invention, unless otherwise specified, refer to parts by weight.
The performance test method of the blended active carbon polyethersulfone porous adsorption column prepared by the invention comprises the following steps:
For the water flux test, an adsorption column is fixed in a self-made perfusion device by using a raw rubber belt, so that the filtration is stable, then water continuously passes through the adsorption column under constant pressure, and the flux is calculated by the following formula:
Flux = volume of water passing/(effective filtration area of material pressure time)
For the adsorption test of creatinine, it was obtained from a static adsorption test. Creatinine (1 mg) was first dissolved by sonication in 20mL of phosphate buffered saline (PBS and ph=7.4, respectively). Then, 20mg of the blended activated carbon polyethersulfone porous adsorption column slice was weighed into a different solution (20 mL) and incubated at room temperature with shaking for 12h. After 12 hours of adsorption, the concentration of creatinine was monitored at 232nm and 293nm, respectively. The adsorption amount is calculated from the following formula:
adsorption amount = (initial creatinine concentration-creatinine concentration after adsorption)/sample mass creatinine solution volume
For the anti-protein adhesion performance test, a static adsorption test of bovine serum albumin is taken as an example. A1X 1cm 2 sample was immersed in phosphate buffer of bovine serum albumin at a concentration of 1mg/mL and treated at 37℃for 1 hour. The sample was washed sequentially with phosphate buffer and deionized water, placed in a wash solution containing 2% sodium dialkylsulfate and 0.05mol/L sodium hydroxide, and vibrated at 37℃for 2h to desorb the adsorbed protein. Protein concentration in the wash was determined using BCA protein assay kit (Thermo Scientific, pierce) and protein adsorption was calculated.
For the blood compatibility test of the porous adsorption column of the blended activated carbon polyethersulfone, a hemolysis rate test is taken as an example. Samples of 1X 1cm 2 were pretreated by soaking in phosphate buffer for 12 hours and incubated for 1 hour at 37 ℃. Phosphate buffer solution is mixed with whole blood according to the volume ratio of 1:1, and separating with a centrifuge for 15 minutes at a centrifugation rate of 2000rpm to obtain red blood cells. The procedure for obtaining erythrocytes by the upper separation was repeated 5 times. 0.2mL of red blood cells and 0.8mL of phosphate buffer were added to the above pretreated samples, and the mixture was shaken in an incubator at 37℃for 2 hours. The suspension was obtained by centrifugation using a centrifuge at 8000rpm for 5 minutes. The absorbance of the suspension was measured using an ultraviolet-visible spectrometer. Deionized water and phosphate buffer were provided as positive and negative controls, respectively. The calculation formula of the hemolysis rate is as follows:
Hemolysis ratio (%) = (absorbance of suspension-absorbance of negative control)/(absorbance of positive control-absorbance of negative control) ×100%.
The "parts" in the following examples and comparative examples, unless otherwise specified, refer to "parts by weight".
Example 1
The embodiment aims at describing a formula and a process of a pure polyethersulfone porous adsorption column, and mainly aims at proving that a freeze-induced phase separation method can be compatible with a method for blending inorganic filler and hydrophilic copolymer, so that the adsorption performance and blood compatibility of the polyethersulfone porous adsorption column are improved.
The polyethersulfone solution (18 parts polyethersulfone, 82 parts dimethylformamide) was slowly added dropwise with vigorous stirring with non-solvent until the solution started to become a white turbid liquid, to give a microphase separated casting solution. And (3) filling the casting solution into a glass bottle, placing the glass bottle in a refrigerator at the temperature of minus 20 ℃ for standing for 24 hours to enable the glass bottle to be subjected to phase separation and form a uniform porous structure, taking out the glass bottle, placing the glass bottle in deionized water to replace a solvent, changing water every 12 hours for at least three times, and obtaining the pure polyether sulfone porous adsorption column. The scanning electron microscope image of the freeze-dried and cut-in-half type polyether sulfone porous adsorption column is shown in fig. 1, and as can be seen from fig. 1, the pure polyether sulfone porous adsorption column has a uniform honeycomb porous structure. And the water contact angle of the porous adsorption column is 138 degrees, and the porous adsorption column shows extremely high hydrophobicity.
The test of creatinine adsorption ability, protein adhesion resistance and hemolysis rate was performed according to the above method, and the results are shown in fig. 4, 5 and 6, and it can be seen from the figures that the microsphere of the present example has poor creatinine adsorption ability, protein adhesion resistance and high hemolysis rate.
Example 2
This example is intended to illustrate the effect of introducing copolymer and activated carbon by blending on a porous adsorption column, and differs from example 1 in that a minimum amount of copolymer and activated carbon is added:
95.5 parts of a polyethersulfone solution (18 parts of polyethersulfone, 82 parts of dimethylformamide) was added to 2.5 parts of a copolymer (15 parts of methyl methacrylate, 15 parts of N-vinylpyrrolidone, 1 part of azobisisobutyronitrile, 70 parts of dimethylformamide), 2 parts of activated carbon, and stirred at room temperature for 6 hours; the non-solvent (ethanol) was slowly added dropwise with vigorous stirring until the solution started to become a white turbid liquid, to obtain a microphase separated casting solution. And (3) filling the casting solution into a glass bottle, placing the glass bottle in a refrigerator at the temperature of minus 20 ℃ for standing for 24 hours to enable the glass bottle to be subjected to phase separation and form a uniform porous structure, taking out the glass bottle, placing the glass bottle in deionized water to replace a solvent, changing water every 12 hours for at least three times, and obtaining the pure polyether sulfone porous adsorption column. The mixing of the hydrophilic copolymer and the activated carbon promotes the separation process of the frozen phase, and a uniform cellular porous structure is formed, so that the appearance is good. The water contact angle of the porous adsorption column is 106 degrees, and the porous adsorption column still has hydrophobicity.
In terms of performance, it can be seen from fig. 2 and 3 that the addition of the copolymer and activated carbon increases the mechanical properties of the adsorption column and decreases the porosity and results in a reduced water flux. The porous adsorption column prepared in this example has a certain creatinine adsorption capacity, and the anti-protein adhesion performance is improved compared with that of example 1, and the hemolysis rate is reduced compared with that of example 1.
Example 3
This example is intended to illustrate the effect of introducing copolymer by blending on a porous adsorption column, and differs from example 2 in that the dosage of copolymer is increased:
93 parts of a polyethersulfone solution (18 parts of polyethersulfone, 82 parts of dimethylformamide) was added to 5 parts of a copolymer (15 parts of methyl methacrylate, 15 parts of N-vinylpyrrolidone, 1 part of azobisisobutyronitrile, 70 parts of dimethylformamide), 2 parts of activated carbon, and stirred at room temperature for 6 hours. The non-solvent (ethanol) was slowly added dropwise with vigorous stirring until the solution started to become a white turbid liquid, to obtain a microphase separated casting solution. And (3) filling the casting solution into a glass bottle, placing the glass bottle in a refrigerator at the temperature of minus 20 ℃ for standing for 24 hours to enable the glass bottle to be subjected to phase separation and form a uniform porous structure, taking out the glass bottle, placing the glass bottle in deionized water to replace a solvent, changing water every 12 hours for at least three times, and obtaining the pure polyether sulfone porous adsorption column. The porous adsorption column was observed to have a uniform cellular porous structure from a scanning electron microscope, and the pore diameter and porosity were smaller than those of example 2. The water contact angle of the porous adsorption column is 94 degrees, and the porous adsorption column has certain hydrophobicity.
In terms of properties, it can be seen from the graph that as the amount of the copolymer blended increases, the mechanical properties are improved and the porosity is reduced, further resulting in a decrease in water flux. Compared with example 2, the creatinine adsorption capacity was increased, the anti-protein adhesion performance was increased compared with example 2, and the hemolysis rate was decreased compared with example 2.
Example 4
This example is intended to illustrate the effect of introducing copolymer by blending on a porous adsorption column, and differs from example 3 in that the maximum amount of copolymer is added:
88 parts of a polyethersulfone solution (18 parts of polyethersulfone, 82 parts of dimethylformamide) was added to 10 parts of a copolymer (15 parts of methyl methacrylate, 15 parts of N-vinylpyrrolidone, 1 part of azobisisobutyronitrile, 70 parts of dimethylformamide), 2 parts of activated carbon, and stirred at room temperature for 6 hours. The non-solvent (ethanol) was slowly added dropwise with vigorous stirring until the solution started to become a white turbid liquid, to obtain a microphase separated casting solution. And (3) filling the casting solution into a glass bottle, placing the glass bottle in a refrigerator at the temperature of minus 20 ℃ for standing for 24 hours to enable the glass bottle to be subjected to phase separation and form a uniform porous structure, taking out the glass bottle, placing the glass bottle in deionized water to replace a solvent, changing water every 12 hours for at least three times, and obtaining the pure polyether sulfone porous adsorption column. The porous adsorption column was observed to have a uniform cellular porous structure from a scanning electron microscope, and the pore diameter and porosity were smaller than those of example 3. The water contact angle of the porous adsorption column is 0 degrees, and the porous adsorption column has good hydrophilicity.
In terms of performance, it can be seen from fig. 3 that the porosity decreases and the mechanical properties further increase, resulting in a continued decrease in water flux. The porous adsorption column prepared in this example had a slightly increased creatinine adsorption capacity as compared with example 3, an increased anti-protein adhesion performance as compared with example 3, and a decreased hemolysis rate as compared with example 3.
Example 5
This example is intended to illustrate the effect of introducing activated carbon by blending on a porous adsorption column, and differs from example 1 in that no activated carbon is added:
95 parts of a polyethersulfone solution (18 parts of polyethersulfone, 82 parts of dimethylformamide) was added to 5 parts of a copolymer (15 parts of methyl methacrylate, 15 parts of N-vinylpyrrolidone, 1 part of azobisisobutyronitrile, 70 parts of dimethylformamide) and stirred at room temperature for 6 hours. The non-solvent (ethanol) was slowly added dropwise with vigorous stirring until the solution started to become a white turbid liquid, to obtain a microphase separated casting solution. And (3) filling the casting solution into a glass bottle, placing the glass bottle in a refrigerator at the temperature of minus 20 ℃ for standing for 24 hours to enable the glass bottle to be subjected to phase separation and form a uniform porous structure, taking out the glass bottle, placing the glass bottle in deionized water to replace a solvent, changing water every 12 hours for at least three times, and obtaining the pure polyether sulfone porous adsorption column. The porous adsorption column was observed from a scanning electron microscope to have a uniform spherical stacked porous structure, and the pore diameter and porosity were increased as compared with example 2. The water contact angle of the porous adsorption column is measured to be 62 degrees, and the porous adsorption column has good hydrophilicity.
In terms of properties, it can be seen from fig. 3 that only due to the addition of the copolymer, the mechanical properties are improved and the porosity is reduced, resulting in a smaller water flux. The porous adsorption column prepared in this example had a creatinine adsorption capacity similar to that of example 1, an anti-protein adhesion performance higher than that of example 1, and a hemolysis rate lower than that of example 1.
Example 6
This example is intended to illustrate the effect of introducing activated carbon by blending on a porous adsorption column, and differs from example 3 in that the maximum dose of activated carbon is added:
Polyether sulfone solution (18 parts of polyether sulfone, 82 parts of dimethylformamide) 89 parts, copolymer (15 parts of methyl methacrylate, 15 parts of N-vinyl pyrrolidone, 1 part of azobisisobutyronitrile, 70 parts of dimethylformamide) 5 parts, activated carbon 6 parts, and stirred at room temperature for 6 hours. The non-solvent (ethanol) was slowly added dropwise with vigorous stirring until the solution started to become a white turbid liquid, to obtain a microphase separated casting solution. And (3) filling the casting solution into a glass bottle, placing the glass bottle in a refrigerator at the temperature of minus 20 ℃ for standing for 24 hours to enable the glass bottle to be subjected to phase separation and form a uniform porous structure, taking out the glass bottle, placing the glass bottle in deionized water to replace a solvent, changing water every 12 hours for at least three times, and obtaining the pure polyether sulfone porous adsorption column. The porous adsorption column was observed to have a uniform cellular porous structure from a scanning electron microscope, and the pore diameter and porosity were smaller than those of example 2. The water contact angle of the porous adsorption column is 0 degrees, and the porous adsorption column has good hydrophilicity.
In terms of performance, it can be seen from fig. 3 that as the mixing amount of activated carbon increases, mechanical properties are improved and porosity is reduced, further resulting in a decrease in water flux. The porous adsorption column prepared in this example has a significantly improved creatinine adsorption capacity as compared with example 3, a reduced protein adhesion resistance as compared with example 3, and an improved hemolysis ratio as compared with example 3.
Comparative example 1
This comparative example is a modified sulfonated polyethersulfone porous microsphere as disclosed in examples 1-3 of chinese patent application CN 117123196A. This comparative example is to illustrate the advantages of the porous material prepared by freeze-to-phase separation over the porous material prepared by liquid-solid phase conversion in terms of adsorption performance. In the adsorption performance test results of examples 1-3 of CN 117123196A, the maximum adsorption capacity of the porous pellets to creatinine is 0.73mg/g, which is far lower than that of the porous adsorption column of example 6 of the patent.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The preparation method of the blending active carbon polyether sulfone porous material prepared by the freeze-induced phase separation method is characterized in that the material comprises the following components in parts by weight:
1) Polyether sulfone solution:
16 to 20 parts of polyether sulfone
80-84 Parts of organic solvent
2) Activated carbon;
3) Copolymer:
10 to 15 parts of methyl methacrylate
10 To 15 parts of N-vinyl pyrrolidone
0.1 To 1 part of oil-soluble azo initiator
4) Non-solvent
The weight ratio of the polyethersulfone solution to the activated carbon to the copolymer is (88-100): (0-6): (0-10);
The preparation method comprises the following steps:
1) Preparation of polyethersulfone solution
Quantitatively weighing 16-20 parts of polyethersulfone, dissolving in 84-80 parts of organic solvent, stirring and dissolving for 12-24 hours to obtain polyethersulfone solution;
2) Preparation of the copolymer
Weighing 10-15 parts of methyl methacrylate, 10-15 parts of N-vinyl pyrrolidone, 0.1-1 part of oil-soluble azo initiator and 80-84 parts of organic solvent quantitatively, adding the prepared polyether sulfone solution, stirring and heating at 70-100 ℃ for 12-24 hours, performing free radical polymerization reaction to obtain copolymer solution, washing the copolymer solution to remove micromolecules and unreacted monomers, and finally drying;
3) Preparation of microphase separation casting solution
According to the polyethersulfone solution: activated carbon: the weight ratio of the copolymer is (88-100): (0-6): (0-10), weighing active carbon and copolymer, adding the prepared polyether sulfone solution, and stirring for 2-6 hours at room temperature; adding a non-solvent until the solution becomes suspended so as to obtain microphase separated casting solution;
4) Forming of porous adsorption column by blending activated carbon and polyether sulfone
And (3) filling the microphase separation casting solution into a glass bottle, placing the glass bottle into a refrigerator at the temperature of minus 40 ℃ to minus 20 ℃ for standing, enabling the glass bottle to be further subjected to phase separation and simultaneously forming a uniform porous structure, taking out the glass bottle, placing the glass bottle into deionized water, and replacing a solvent to obtain the blending active carbon polyether sulfone porous adsorption column.
2. The method of claim 1, wherein the organic solvent is at least one of dimethylformamide, dimethylacetamide, or dimethylsulfoxide.
3. The method of claim 1, wherein the activated carbon is spherical granular activated carbon having a diameter of 5-8 mm.
4. The method of claim 1, wherein the oil-soluble azo initiator is at least one of azobisisobutyronitrile, azobisisoheptonitrile.
5. The method of claim 1, wherein the non-solvent is at least one of water, ethanol, methanol, ethylene glycol, glycerol.
6. The method according to claim 1, wherein the pore size of the porous adsorption column is 50 to 50000nm by controlling the polyethersulfone concentration and the copolymer mixing amount.
7. The blended activated carbon polyethersulfone porous material prepared by the method of any one of claims 1-7.
8. Use of the blended activated carbon polyethersulfone porous material prepared by the method of any one of claims 1-7 in the preparation of blood purification devices.
9. The use according to claim 9, wherein the blended activated carbon polyethersulfone porous adsorption column is used for blood purification, comprising blood perfusion, blood filtration and plasma separation.
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