CN109589944A - A kind of porous polysulfones coated particle, preparation method and application - Google Patents
A kind of porous polysulfones coated particle, preparation method and application Download PDFInfo
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- CN109589944A CN109589944A CN201811522161.1A CN201811522161A CN109589944A CN 109589944 A CN109589944 A CN 109589944A CN 201811522161 A CN201811522161 A CN 201811522161A CN 109589944 A CN109589944 A CN 109589944A
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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Abstract
The invention discloses a kind of porous polysulfones coated particle, preparation method and applications.The preparation method of the porous polysulfones coated particle includes: that polysulfones and expanding agent are dissolved in formation polysulfones casting solution in organic solvent；Adsorption resin particles are blended into the polysulfones casting solution and form mixing casting solution；The mixing casting solution is added dropwise in distilled water and forms porous PS membrane cladding adsorptive resin particle；And hydrophilic modifying is carried out to the porous PS membrane cladding adsorptive resin particle, porous polysulfones coated particle is made.The present invention is using adsorption resin particles to the adsorptivity of blood Metabolites and the biocompatibility of polysulfones, prepare the porous polysulfones coated particle with " removing in real time " function, prepared porous polysulfones coated particle can remove lower-molecular substance in blood Metabolites lactic acid, pyruvic acid, inflammatory factor, bilirubin, immunoglobulin, complement etc. in real time, effectively extend the average life span of red blood cell in blood.
Description
Technical field
The present invention relates to a kind of preparation methods of porous polysulfones coated particle, and in particular to one kind has " removing in real time " function
The porous polysulfones coated particle and the preparation method and application thereof of energy belongs to biological medical polymer material and blood purification technology neck
Domain.
Background technique
The service life average out to of red blood cell 120 days in blood, but can only store in vitro 35 days or so, and in storage two
Apparent red cell morphology function can be observed after week to change, thus caused Adverse transfusion reaction also obviously increases.With body
Interior erythrocyte metabolism product can timely and effective removing it is different, the unwanted metabolic products especially lactic acid heap that storage of red blood cells generates
Product is considered as the early stage inducement of Erythrocyte preservation damage, and Enzyme activity in red blood cell causes energetic supersession to hinder extremely under acidic environment
Hinder, the reduction of atriphos (ATP) content eventually leads to red blood cell dissolved destruction to cause a series of chain effect, and molten
A large amount of unwanted metabolic products that blood generates further have aggravated the damage of red blood cell.
Red blood cell can gradually generate Physiology and biochemistry change during storage, and accumulate some potential detrimental metabolics and produce
Object, this process are referred to as " Erythrocyte preservation damage ".Erythrocyte preservation damage is a great problem for perplexing blood transfusion field, seriously
Erythrocyte preservation quality and period of storage are affected, Erythrocyte preservation damage, which is effectively relieved, will be helpful to the improvement of this case,
" blood is waste " situation is got worse at home, under the background that transfusion safety increasingly has attracted much attention, carries out preserved blood purification to red blood cell
The research that protective effect and preserved blood purify related new technology will have more actual Development volue and wide clinical application
Prospect.
Most of unwanted metabolic products belong to small molecular substance, and molecular weight is generally less than 30,000 dalton, then being
It is no nonspecific " wide spectrum " purification to be carried out to unwanted metabolic products in preserved blood by molecular sieve principle." blood purification "
It is initially applied to field of dialysis, the inflammatory factor, metabolite or toxin in blood can be adsorbed material and remove to reach treatment
Purpose.Seminar is by being implanted into adsorbent material in the whole blood containing ACD, and discovery preserved blood has no obvious haemolysis after storage 21 days,
Its pH value, which has no, to be substantially change, and lactic acid and other unwanted metabolic products are significantly reduced compared with control group, ATP, 2,3- in red blood cell
DPG content is apparently higher than control group (see working foundation).It can by the acidic materials in " removing in real time " preserved blood to infer
It can help to improve Erythrocyte preservation quality, it is red thin for unwanted metabolic products in preserved blood " remove in real time " effect and to storing
Born of the same parents' protection mechanism still needs comprehensively careful research.
In conclusion leading to medium for storing PH due to the acidic materials such as lactic acid, pyruvic acid accumulation during Erythrocyte preservation
Decline, influences the energetic supersession of red blood cell, causes the oxidative damage of red blood cell, dissolved destruction.And caused by Erythrocyte Damage
Free hemoglobin, iron ion, serum potassium, inflammatory factor and Erythrocytes Aged in vitro enter in receptor's body so as to cause blood transfusion not
The generation of good reaction.Accordingly it is proposed that scientific hypothesis thinks: during Erythrocyte preservation, being produced by removing red blood cell in real time
The unwanted metabolic products such as raw lactic acid can be effectively relieved Erythrocyte preservation damage, improve Quality of Erythrocyte, reduce because of red blood cell
The harmful substance that aging and dissolution generate mitigates immunomodulatory effect caused by Erythrocyte preservation damages, to prevent blood transfusion not
The occurrence and development of good reaction.
Amberchrom and Amberlite series absorption resin is widely used in haemodialysis field treatment septicemia and exempts from
Epidemic disease system disorders related syndromes, and achieve very ideal effect.Amberlite cation exchange resin for lactic acid,
Pyruvic acid has good scavenging effect；300 resin of Amberchrom CG is to inflammatory factor, bilirubin, immunoglobulin, complement
Lower-molecular substance has fabulous absorption scavenging effect in, is to be currently known absorption highest for inflammatory factor adsorption efficiency
Agent.In project early-stage study, seminar uses the chromatographic column of Amberchrom CG 300C (average grain diameter 120um) preparation
Preserved blood is filtered, inflammatory factor, bilirubin significantly reduce compared with control group, while albumin, fibrinogen, thromboplastin, solidifying
The macromolecular substances such as hemase original can be effectively retained.It realizes " clear in real time for the bioactive substance in preserved blood
Except ", adsorbent must be with preserved blood Long Term Contact.Amberchrom and Amberlite series adsorbs resin in haemodialysis neck
The prolonged application in domain show its with blood short term contact be it is safe, but seminar had been found that in early-stage study its with store it is red
Cell long-period will lead to the generation of haemolysis when contacting, there are biocompatibility hidden danger.Current biomaterial is mainly stone
Oil based polymers, there are poor biocompatibility, easy blood coagulation and it is at high cost the problems such as.
Summary of the invention
The main purpose of the present invention is to provide a kind of porous polysulfones coated particle with " removing in real time " function and its
Preparation method, thus overcome the deficiencies in the prior art.
Another object of the present invention is to provide the purposes of the porous polysulfones coated particle.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
The embodiment of the invention provides a kind of preparation methods of porous polysulfones coated particle comprising:
Polysulfones and expanding agent are dissolved in formation polysulfones casting solution in organic solvent；
Adsorption resin particles are blended into the polysulfones casting solution and form mixing casting solution；
The mixing casting solution is added dropwise in distilled water and forms porous PS membrane cladding adsorptive resin particle；And
Hydrophilic modifying is carried out to the porous PS membrane cladding adsorptive resin particle, porous polysulfones coated particle is made.
The embodiment of the invention also provides the porous polysulfones coated particles prepared by preceding method.
The embodiment of the invention also provides porous polysulfones coated particles above-mentioned in preparing the purposes in blood purifying product.
Further, the product can remove blood Metabolites, and the blood Metabolites include lactic acid, acetone
Acid, inflammatory factor, bilirubin, immunoglobulin, any one or two or more combinations in complement.
Compared with prior art, beneficial effects of the present invention at least that:
The present invention is using adsorption resin particles to the adsorptivity of blood Metabolites and the biocompatibility of polysulfones, preparation
The porous polysulfones coated particle of " removing in real time " function is provided, prepared porous polysulfones coated particle can remove blood in real time
Lower-molecular substance in liquid metabolite lactic acid, pyruvic acid, inflammatory factor, bilirubin, immunoglobulin, complement etc. effectively extends
The average life span of red blood cell in blood.
Detailed description of the invention
Fig. 1 is the scanning electron of the aggregation of Amberlite CG300C adsorption resin particles used in the embodiment of the present invention 4
Microscope figure.
Fig. 2 is the absorption resin individual particle surface porosity of Amberlite CG300C used in the embodiment of the present invention 4
Scanning electron microscope diagram.
Fig. 3 is the macroscopic view prepared by the embodiment of the present invention 1 with the porous polysulfones coated particle of " removing in real time " function
Shape appearance figure.
Fig. 4 is the surface prepared by the embodiment of the present invention 1 with the porous polysulfones coated particle of " removing in real time " function
Electron microscope.
Fig. 5 is the section prepared by the embodiment of the present invention 1 with the porous polysulfones coated particle of " removing in real time " function
Electron microscope.
Specific embodiment
As previously mentioned, inventor is studied for a long period of time and largely practiced in view of the deficiencies in the prior art, this hair is proposed
Bright technical solution is mainly to provide a kind of preparation method of porous polysulfones coated particle with " removing in real time " function.
This method is to utilize life of the Amberlite series adsorption resin particles to the adsorptivity and PSf (polysulfones) of blood Metabolites
Object compatibility prepares the porous polysulfones coated particle with " removing in real time " function.
The technical solution, its implementation process and principle etc. will be further explained as follows.
Polysulfones (PSf) is to contain alkyl-SO in molecular backbone2The thermoplastic resin of chain link, have abrasion-resistant, high temperature resistant,
The advantages that mechanical strength is big.PSf has preferable biocompatibility relative to other membrane materials, therefore is widely used in haemodialysis
The preparation of membrane material.In the present invention, a certain amount of PSf particle is dissolved first with N-Methyl pyrrolidone (NMP) and (is wherein added one
Quantitative polyethylene glycol oxide (PEO) is used as pore-foaming agent)；Then Amberlite series adsorption resin particles are blended into above-mentioned PSf
In casting solution；Then the casting solution containing Amberlite series adsorption resin particles is added dropwise in distilled water, is prepared porous
PSf film coats adsorptive resin particle；Above-mentioned particle is finally subjected to hydrophilic modifying, so that preparing has " removing in real time " function
The porous polysulfones coated particle of energy.
The one aspect of the embodiment of the present invention provides a kind of preparation method of porous polysulfones coated particle comprising:
Polysulfones and expanding agent are dissolved in formation polysulfones casting solution in organic solvent；
Adsorption resin particles are blended into the polysulfones casting solution and form mixing casting solution；
The mixing casting solution is added dropwise in distilled water and forms porous PS membrane cladding adsorptive resin particle；And
Hydrophilic modifying is carried out to the porous PS membrane cladding adsorptive resin particle, porous polysulfones coated particle is made.
In some preferred embodiments, the preparation method specifically includes: polysulfones particle and expanding agent have been dissolved in
In solvent, and 3-24h is stirred under the conditions of 50-90 DEG C, form polysulfones casting solution, be cooled to room temperature later.
Further, the speed of the stirring is 100-500rpm.
Further, the mass ratio of the polysulfones and expanding agent is 5-15:2-6.
Further, the mass ratio of the polysulfones and organic solvent is 5-15:79-93.
Further, the expanding agent includes polyethylene glycol oxide (PEO), but not limited to this.
Further, the organic solvent includes N-Methyl pyrrolidone (NMP), but not limited to this.
In some preferred embodiments, the preparation method specifically includes: the adsorption resin particles are added to institute
It states in polysulfones casting solution, and stirs 10-60min, later static layering, and remove supernatant liquid, obtain containing absorption resin
The mixing casting solution of grain, continues thereafter with stirring.
Further, the adsorption resin particles are 2:3-5 with the mass ratio for mixing casting solution.
Further, the adsorption resin particles include Amberlite series adsorption resin particles, the Amberlite
Serial adsorption resin particles preferably include Amberlite FPA51, Amberlite XT30, Amberlite CG300C or
Amberlite CG300M resin particle etc., but not limited to this.
In some preferred embodiments, the preparation method specifically includes: will be described mixed with the dropwise addition height of 10-30cm
Alloying film liquid is added dropwise in distilled water, forms porous PS membrane cladding adsorptive resin particle, then post-processed.
Further, the post-processing includes: to be transferred to the porous PS membrane cladding adsorptive resin particle of acquisition
It in clean distilled water, and saves 5-7 days, then is dried in vacuo, vacuum preservation.
In some preferred embodiments, the preparation method specifically includes:
In room temperature condition and protective atmosphere, by n-vinyl pyrrolidone, vinyltriethoxysilane and azo
Bis-isobutyronitrile dissolves in a solvent and stirs 10-30min, then adjusts temperature to 40-100 DEG C of progress polymerization reaction 6-24h,
The reaction mixture P (VP-VTES) comprising prepolymer is obtained, then the reaction mixture comprising prepolymer is mixed into shape with water
At pre-polymer solution；
The porous PS membrane cladding adsorptive resin particle is immersed in the pre-polymer solution and stirs 1-5h, then
It is molten that the porous PS membrane cladding adsorptive resin particle of the microswelling obtained is transferred to the citric acid that concentration is 0.5-1.5wt%
In liquid, and 8-10h is heated at 30-80 DEG C, so that the porous polysulfones coated particle be made.
Further, the quality of the n-vinyl pyrrolidone, vinyltriethoxysilane and azodiisobutyronitrile
Than for 5.5-7.5:3.5-5.5:0.12-0.16.
Further, the mass ratio of the n-vinyl pyrrolidone and solvent is 5.5-7.5:100-300.
Further, the solvent includes vinyltriethoxysilane, N-Methyl pyrrolidone or triethyl phosphate, but
It is without being limited thereto.
Further, the volume ratio of the reaction mixture comprising prepolymer and water is 1:5-5:1.
Wherein, as the more preferably case study on implementation of the present invention one, the porous polysulfones with " removing in real time " function
The preparation method of coated particle the following steps are included:
5.0-15.0 grams of pretreated PSf particle, 2.0-6.0 grams of polyethylene glycol oxide (PEO) are dissolved in by step (1)
In 79.0-93.0 grams of N-Methyl pyrrolidone (NMP), mechanical stirring 20 hours under the conditions of 70-90 DEG C；Then by above-mentioned casting film
Liquid is cooled to room temperature；
Wherein, the casting solution mechanical stirring rate is 100-500rpm；The polyethylene glycol oxide and N- methyl pyrrole
Pyrrolidone can be bought by market and be obtained；
20 grams of Amberlite series adsorption resin particles are added in the casting solution of step (1) preparation by step (2), machine
Tool stirs 10-60 minutes；The extra casting solution in upper layer is removed after static layering, is obtained 30-50 grams and is adsorbed containing Amberlite series
The casting solution of resin particle continues thereafter with stirring；
Wherein, the Amberlite series adsorption resin particles be Amberlite FPA51, Amberlite XT30,
Amberlite CG300C and Amberlite CG300M；Amberlite series adsorption resin particles are added to step (1) preparation
Casting solution after need mechanical stirring.
The casting solution containing Amberlite series adsorption resin particles that step (3) prepares above-mentioned steps (2) is (constantly
Stirring), it is added drop-wise in room temperature distilled water with certain altitude；The porous PSf film cladding adsorptive resin particle of preparation is transferred to
Into clean distilled water, and save 5-7 days.Particle vacuum drying treatment then is prepared by above-mentioned, and vacuum saves；
Wherein, the casting solution exit containing Amberlite series adsorption resin particles is apart from distilled water level
The height in face is 10-30 centimetres；Particle is manufactured in such a way that non-solvent mutually separates and casting solution is added dropwise with gravity in step (3).
Step (4) under the conditions of room temperature, nitrogen protection, by 5.50-7.50 grams of n-vinyl pyrrolidone (NVP),
3.50-5.50 grams of vinyltriethoxysilane (VTES) and 0.12-0.16 grams of azodiisobutyronitrile (AIBN) are dissolved in 100-
300 grams of triethyl phosphates (TEP) are simultaneously stirred 10-30 minutes.Then temperature is controlled at 40-100 DEG C, heating 6-24h induces poly-
It closes reaction and obtains prepolymer P (VP-VTES).Then, with P (VP-VTES)/TEP/ water=1:1 (V/V) mixing, step (3) are made
Standby drying PSf film cladding adsorptive resin particle impregnates in the above solution, stirs 1-5 hours.Then by the PSf of microswelling
Film cladding adsorptive resin particle is transferred in the citric acid solution of 0.5-1.5wt%, and heats 8-10h at 30-80 DEG C, from
And prepare the porous polysulfones coated particle with " removing in real time " function.
Wherein, step (4) organic solvent is vinyltriethoxysilane, N-Methyl pyrrolidone, triethyl phosphate etc.,
But not limited to this.
Further, step (4) is prepared the porous polysulfones coated particle needs with " removing in real time " function and is stored in
Dipping pretreatment 5-7 days in physiological saline.
The other side of the embodiment of the present invention additionally provides the porous polysulfones coated particle prepared by preceding method.
Further, the diameter of the porous polysulfones coated particle be 0.2-20mm, 0.2-500 μm of the thickness of clad,
The aperture of hole contained by clad is 0.05-5 μm.
The other side of the embodiment of the present invention additionally provides porous polysulfones coated particle above-mentioned in preparing blood purification
Purposes in product.
Further, the product can remove blood Metabolites, and the blood Metabolites include lactic acid, acetone
Any one in acid, inflammatory factor, bilirubin, immunoglobulin, complement etc. in lower-molecular substance or two or more combinations,
Effectively extend the average life span of red blood cell in blood.
Further, the purposes includes: by porous polysulfones coated particle dipping pretreatment 5-7 in physiological saline
It, is used further to remove blood Metabolites later.
In conclusion the present invention is using adsorption resin particles to the adsorptivity of blood Metabolites and the biofacies of polysulfones
Capacitive prepares the porous polysulfones coated particle with " removing in real time " function, and prepared porous polysulfones coated particle can
Low-molecular material in blood Metabolites lactic acid, pyruvic acid, inflammatory factor, bilirubin, immunoglobulin, complement etc. is removed in real time
Matter effectively extends the average life span of red blood cell in blood.
In order to make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with several preferred embodiments
And attached drawing, explanation is further explained in detail to technical solution of the present invention.It should be appreciated that specific implementation described herein
Example is only used to explain the present invention, but experiment condition therein and setup parameter are not construed as to basic technical scheme of the present invention
Limitation.And protection scope of the present invention is not limited to following embodiments.In addition, each embodiment party of invention described below
Involved technical characteristic can be combined with each other as long as they do not conflict with each other in formula.
Embodiment 1
15.0 grams of pretreated PSf particles, 6.0 grams of polyethylene glycol oxides (PEO) are dissolved in 79.0 grams of N- methylpyrroles
In alkanone (NMP), under the conditions of 70 DEG C, with revolving speed mechanical stirring 10 hours of 500rpm；Then above-mentioned casting solution is cooled to
Room temperature；20.0 grams of Amberlite FPA51 adsorption resin particles are added in the casting solution of step (1) preparation, mechanical stirring
30 minutes；The extra casting solution in upper layer is removed after static layering, is obtained 30.0 grams and is contained Amberlite FPA51 adsorption resin particles
Casting solution, continue thereafter with stirring；Casting containing Amberlite FPA51 adsorption resin particles prepared by above-mentioned steps (2)
Film liquid (is stirred continuously), is added drop-wise in room temperature distilled water with 10cm height；The porous PSf film of preparation is coated into adsorptive resin
Grain is transferred in clean distilled water, and is saved 5 days.Particle vacuum drying treatment then is prepared by above-mentioned, and vacuum saves；?
Under the conditions of room temperature, nitrogen protection, by 5.50 grams of n-vinyl pyrrolidone (NVP), 3.5 grams of vinyltriethoxysilane
(VTES) 100 grams of triethyl phosphates (TEP) are dissolved in and are stirred 10 minutes with 0.12 gram of azodiisobutyronitrile (AIBN).Then will
Temperature is controlled at 80 DEG C, and heating 20h induces polymerization reaction and obtains prepolymer P (VP-VTES).Then, with P (VP-VTES)/TEP/
Water=1:1 (V/V) mixing impregnates the drying PSf film cladding adsorptive resin particle of step (3) preparation in the above solution,
Stirring 1 hour.Then the PSf film cladding adsorptive resin particle of microswelling is transferred in the citric acid solution of 0.5wt%, and
It is heated 8 hours at 50 DEG C, to prepare the porous polysulfones coated particle with " removing in real time " function, macro morphology figure
As shown in figure 3, surface electron microscope is as shown in figure 4, section electron microscope is as shown in Figure 5.
The porous polysulfones coated particle diameter of preparation is about 3.5mm, and coating thickness is 260 μm, and aperture is 0.2 μm.It will
This particle is fitted into chromatographic column, Jing Yuhan 0.5g/L lactic acid, pyruvic acid arterial blood come into full contact with after, through detecting, after filtering
Lactic acid content < 50mg/L, acetone acid content < 5mg/L, content of hemoglobin do not change substantially.It can be seen that the present embodiment
Porous polysulfones coated particle have the function of " remove in real time " blood Metabolites, while there is preferable biocompatibility, have
Effect extends the average life span of red blood cell in blood.
Comparative example 1
Amberlite FPA51 is fitted into chromatographic column, Jing Yuhan 0.5g/L lactic acid, pyruvic acid arterial blood sufficiently connect
After touch, through detecting, lactic acid content < 50mg/L after filtering, acetone acid content < 5mg/L, content of hemoglobin reduction by 60%.
Embodiment 2
10.0 grams of PSf particles, 4.0 grams of polyethylene glycol oxides (PEO) are dissolved in 86.0 grams of N-Methyl pyrrolidones (NMP)
In, under the conditions of 80 DEG C, with revolving speed mechanical stirring 20 hours of 400rpm；Then above-mentioned casting solution is cooled to room temperature；By 20
Gram Amberlite XT30 adsorption resin particles are added in the casting solution of step (1) preparation, and mechanical stirring 40 minutes；Static point
The extra casting solution in upper layer is removed after layer, 40 grams of casting solutions containing Amberlite XT30 adsorption resin particles is obtained, with subsequent
Continuous stirring；Casting solution (being stirred continuously) containing Amberlite XT30 adsorption resin particles prepared by above-mentioned steps (2), with
15cm height is added drop-wise in room temperature distilled water；The porous PSf film cladding adsorptive resin particle of preparation is transferred to clean steaming
In distilled water, and save 6 days.Particle vacuum drying treatment then is prepared by above-mentioned, and vacuum saves；In room temperature, nitrogen protection item
Under part, by 6.50 grams of n-vinyl pyrrolidone (NVP), 4.50 grams of vinyltriethoxysilane (VTES) and 0.14 gram of azo
Bis-isobutyronitrile (AIBN) is dissolved in 200 grams of N-Methyl pyrrolidones (NMP) and stirs 20 minutes.Then temperature is controlled 80
DEG C, heating 20h induces polymerization reaction and obtains prepolymer P (VP-VTES).Then, with P (VP-VTES)/NMP/ water=3:1 (V/V)
The drying PSf film cladding adsorptive resin particle of step (3) preparation is impregnated in the above solution, is stirred 2 hours by mixing.With
The PSf film cladding adsorptive resin particle of microswelling is transferred in the citric acid solution of 1.0wt% afterwards, and is heated at 60 DEG C
9 hours, to prepare the porous polysulfones coated particle with " removing in real time " function.
The porous polysulfones coated particle diameter of preparation is about 2mm, and coating thickness is 60 μm, and aperture is 3 μm.By this particle
Be fitted into chromatographic column, Jing Yuhan 0.5g/L lactic acid, pyruvic acid arterial blood come into full contact with after, through detecting, lactic acid contains after filtering
Amount < 50mg/L, acetone acid content < 5mg/L, content of hemoglobin do not change substantially.It can be seen that the present embodiment is porous
Polysulfones coated particle has the function of " removing in real time " blood Metabolites, while having preferable biocompatibility, effectively extends
The average life span of red blood cell in blood.
Comparative example 2
Amberlite XT30 is fitted into chromatographic column, Jing Yuhan 0.5g/L lactic acid, pyruvic acid arterial blood sufficiently connect
After touch, through detecting, lactic acid content < 50mg/L after filtering, acetone acid content < 5mg/L, content of hemoglobin reduction by 55%.
Embodiment 3
15.0 grams of pretreated PSf particles, 6.0 grams of polyethylene glycol oxides (PEO) are dissolved in 79.0 grams of N- methylpyrroles
In alkanone (NMP), under the conditions of 90 DEG C, with revolving speed mechanical stirring 3 hours of 400rpm；Above-mentioned casting solution is then cooled to room
Temperature；20 grams of Amberlite FPA51 adsorption resin particles are added in the casting solution of step (1) preparation, mechanical stirring 50 is divided
Clock；The extra casting solution in upper layer is removed after static layering, obtains 50 grams of casting films containing Amberlite FPA51 adsorption resin particles
Liquid continues thereafter with stirring；(no by the casting solution containing Amberlite FPA51 adsorption resin particles of above-mentioned steps (2) preparation
Disconnected stirring), it is added drop-wise in room temperature distilled water with 15cm height；By the porous PSf film cladding adsorptive resin particle transfer of preparation
To into clean distilled water, and save 7 days.Particle vacuum drying treatment then is prepared by above-mentioned, and vacuum saves；Room temperature,
Under the conditions of nitrogen protection, by 7.50 grams of n-vinyl pyrrolidone (NVP), 5.50 grams of vinyltriethoxysilane (VTES) and
0.16 gram of azodiisobutyronitrile (AIBN) is dissolved in 300 grams of triethyl phosphates (TEP) and stirs 30 minutes.Then temperature is controlled
At 100 DEG C, heating 6h induces polymerization reaction and obtains prepolymer P (VP-VTES).Then, with P (VP-VTES)/TEP/ water=1:5
(V/V) it mixes, the drying PSf film cladding adsorptive resin particle of step (3) preparation is impregnated in the above solution, stirring 3 is small
When.Then the PSf film cladding adsorptive resin particle of microswelling is transferred in the citric acid solution of 1.5wt%, and at 70 DEG C
Lower heating 10 hours, to prepare the porous polysulfones coated particle with " removing in real time " function.
The porous polysulfones coated particle diameter of preparation is about 4mm, and coating thickness is 260 μm, and aperture is 0.2 μm.By this
Particle is fitted into chromatographic column, Jing Yuhan 0.5g/L lactic acid, pyruvic acid arterial blood come into full contact with after, it is newborn after filtering through detecting
Acid content < 50mg/L, acetone acid content < 5mg/L, content of hemoglobin do not change substantially.It can be seen that the present embodiment
Porous polysulfones coated particle has the function of " removing in real time " blood Metabolites, while having preferable biocompatibility, effectively
Extend the average life span of red blood cell in blood.
Comparative example 3
Amberlite FPA51 is fitted into chromatographic column, Jing Yuhan 0.5g/L lactic acid, pyruvic acid arterial blood sufficiently connect
After touch, through detecting, lactic acid content < 50mg/L after filtering, acetone acid content < 5mg/L, content of hemoglobin reduction by 60%.
Embodiment 4
5.0 grams of pretreated PSf particles, 2.0 grams of polyethylene glycol oxides (PEO) are dissolved in 93.0 grams of N- crassitudes
In ketone (NMP), under the conditions of 50 DEG C, with revolving speed mechanical stirring 24 hours of 100rpm；Above-mentioned casting solution is then cooled to room
Temperature；20.0 grams of Amberlite CG300C adsorption resin particles are added in the casting solution of step (1) preparation, mechanical stirring 60
Minute；The extra casting solution in upper layer is removed after static layering, is obtained 30.0 grams and is contained Amberlite CG300C adsorption resin particles
Casting solution, continue thereafter with stirring；Casting containing Amberlite CG300C adsorption resin particles prepared by above-mentioned steps (2)
Film liquid (is stirred continuously), is added drop-wise in room temperature distilled water with 30cm height；The porous PSf film of preparation is coated into adsorptive resin
Grain is transferred in clean distilled water, and is saved 5 days.Particle vacuum drying treatment then is prepared by above-mentioned, and vacuum saves；?
Under the conditions of room temperature, nitrogen protection, by 5.50 grams of n-vinyl pyrrolidone (NVP), 3.5 grams of vinyltriethoxysilane
(VTES) 100 grams of triethyl phosphates (TEP) are dissolved in and are stirred 10 minutes with 0.12 gram of azodiisobutyronitrile (AIBN).Then will
Temperature is controlled at 80 DEG C, and heating 20h induces polymerization reaction and obtains prepolymer P (VP-VTES).Then, with P (VP-VTES)/TEP/
Water=1:2 (V/V) mixing impregnates the drying PSf film cladding adsorptive resin particle of step (3) preparation in the above solution,
Stirring 1 hour.Then the PSf film cladding adsorptive resin particle of microswelling is transferred in the citric acid solution of 0.5wt%, and
It is heated 8 hours at 50 DEG C, to prepare the porous polysulfones coated particle with " removing in real time " function.Wherein, this implementation
The scanning electron microscope diagram of Amberlite CG300C adsorption resin particles aggregation used in example is as shown in Figure 1, absorption tree
The scanning electron microscope diagram of rouge individual particle surface porosity is as shown in Figure 2.
The porous polysulfones coated particle diameter about 1 of preparation is mm, and coating thickness is 60 μm, and aperture is 3 μm.By this particle
It is fitted into chromatographic column, after the arterial blood of Jing Yuhan 0.5g/L bilirubin comes into full contact with, through detecting, content of bilirubin after filtering <
0.5mg/L, content of hemoglobin do not change substantially.It can be seen that the porous polysulfones coated particle of the present embodiment has " in fact
When remove " blood Metabolites function, while there is preferable biocompatibility, effectively extend the average longevity of red blood cell in blood
Life.
Comparative example 4
Amberlite CG300C is fitted into chromatographic column, the arterial blood of Jing Yuhan 0.5g/L bilirubin comes into full contact with
Afterwards, through detecting, content of bilirubin < 0.5mg/L after filtering, content of hemoglobin reduces by 65%.
Embodiment 5
10.0 grams of pretreated PSf particles, 4.0 grams of polyethylene glycol oxides (PEO) are dissolved in 86.0 grams of N- methylpyrroles
In alkanone (NMP), under the conditions of 80 DEG C, with revolving speed mechanical stirring 20 hours of 300rpm；Then above-mentioned casting solution is cooled to
Room temperature；20 grams of Amberlite CG300C adsorption resin particles are added in the casting solution of step (1) preparation, mechanical stirring 10
Minute；The extra casting solution in upper layer is removed after static layering, obtains 40 grams containing Amberlite CG300C adsorption resin particles
Casting solution continues thereafter with stirring；Casting film containing Amberlite CG300C adsorption resin particles prepared by above-mentioned steps (2)
Liquid (is stirred continuously), is added drop-wise in room temperature distilled water with 20cm height；The porous PSf film of preparation is coated into adsorptive resin particle
It is transferred in clean distilled water, and saves 6 days.Particle vacuum drying treatment then is prepared by above-mentioned, and vacuum saves；In room
Under the conditions of temperature, nitrogen protection, by 6.50 grams of n-vinyl pyrrolidone (NVP), 4.50 grams of vinyltriethoxysilane
(VTES) 200 grams of triethyl phosphates (TEP) are dissolved in and are stirred 20 minutes with 0.14 gram of azodiisobutyronitrile (AIBN).Then will
Temperature is controlled at 40 DEG C, and heating induces polymerization reaction for 24 hours and obtains prepolymer P (VP-VTES).Then, with P (VP-VTES)/TEP/
Water=5:1 (V/V) mixing impregnates the drying PSf film cladding adsorptive resin particle of step (3) preparation in the above solution,
Stirring 2 hours.Then the PSf film cladding adsorptive resin particle of microswelling is transferred in the citric acid solution of 1.0wt.%,
And heated 9 hours at 80 DEG C, to prepare the porous polysulfones coated particle with " removing in real time " function.
The porous polysulfones coated particle diameter of preparation is about 2mm, and coating thickness is 150 μm, and aperture is 0.6 μm.By this
Particle is fitted into chromatographic column, and after the arterial blood of Jing Yuhan 0.5g/L bilirubin comes into full contact with, through detecting, bilirubin contains after filtering
Amount < 0.5mg/L, content of hemoglobin do not change substantially.It can be seen that the porous polysulfones coated particle of the present embodiment has
" removing in real time " blood Metabolites function, while there is preferable biocompatibility, red blood cell is flat effectively in extension blood
The equal service life.
Comparative example 5
Amberlite CG300C is fitted into chromatographic column, the arterial blood of Jing Yuhan 0.5g/L bilirubin comes into full contact with
Afterwards, through detecting, content of bilirubin < 0.5mg/L after filtering, content of hemoglobin reduces by 60%.
Embodiment 6
15.0 grams of pretreated PSf particles, 6.0 grams of polyethylene glycol oxides (PEO) are dissolved in 79.0 grams of N- methylpyrroles
In alkanone (NMP), under the conditions of 90 DEG C, with revolving speed mechanical stirring 20 hours of 400rpm；Then above-mentioned casting solution is cooled to
Room temperature；20 grams of Amberlite CG300M adsorption resin particles are added in the casting solution of step (1) preparation, mechanical stirring 50
Minute；The extra casting solution in upper layer is removed after static layering, obtains 50 grams containing Amberlite CG300CM adsorption resin particles
Casting solution continues thereafter with stirring；Casting containing Amberlite CG300CM adsorption resin particles prepared by above-mentioned steps (2)
Film liquid (is stirred continuously), is added drop-wise in room temperature distilled water with 15cm height；The porous PSf film of preparation is coated into adsorptive resin
Grain is transferred in clean distilled water, and is saved 7 days.Particle vacuum drying treatment then is prepared by above-mentioned, and vacuum saves；?
Under the conditions of room temperature, nitrogen protection, by 7.50 grams of n-vinyl pyrrolidone (NVP), 5.50 grams of vinyltriethoxysilane
(VTES) 300 grams of triethyl phosphates (TEP) are dissolved in and are stirred 30 minutes with 0.16 gram of azodiisobutyronitrile (AIBN).Then will
Temperature is controlled at 80 DEG C, and heating 20h induces polymerization reaction and obtains prepolymer P (VP-VTES).Then, with P (VP-VTES)/TEP/
Water=1:3 (V/V) mixing impregnates the drying PSf film cladding adsorptive resin particle of step (3) preparation in the above solution,
Stirring 5 hours.Then the PSf film cladding adsorptive resin particle of microswelling is transferred in the citric acid solution of 1.5wt%, and
It is heated 10 hours at 30 DEG C, to prepare the porous polysulfones coated particle with " removing in real time " function.
The porous polysulfones coated particle diameter of preparation is about 3mm, and coating thickness is 150 μm, and aperture is 1 μm.By this
Grain is fitted into chromatographic column, after the arterial blood of Jing Yuhan 0.5g/L inflammatory factor comes into full contact with, through detecting, and inflammatory factor after filtering
Content < 0.5mg/L, content of hemoglobin do not change substantially.It can be seen that the porous polysulfones coated particle of the present embodiment has
There is " removing in real time " blood Metabolites function, while there is preferable biocompatibility, effectively extends red blood cell in blood
Average life span.
Comparative example 6
Amberlite CG300M is fitted into chromatographic column, the arterial blood of Jing Yuhan 0.5g/L inflammatory factor comes into full contact with
Afterwards, through detecting, Inflammatory Factors Contents < 0.5mg/L after filtering, content of hemoglobin reduces by 60%.
In addition, inventor also utilizes the alternate embodiments such as listed other raw materials and other process conditions above
Various raw materials and corresponding process conditions in 1-6 have carried out corresponding test, and obtaining porous polysulfones coated particle can remove in real time
Lower-molecular substance in blood Metabolites lactic acid, pyruvic acid, inflammatory factor, bilirubin, immunoglobulin, complement etc., effectively prolongs
The average life span of red blood cell in long blood, it is substantially similar to embodiment 1-6 product.
It should be pointed out that the above described specific embodiments of the present invention, be not intended to limit the scope of the present invention..
Any any other various changes and modifications in accordance with the technical idea of the present invention, should be included in right of the present invention
It is required that protection scope in.
Claims (10)
1. a kind of preparation method of porous polysulfones coated particle, characterized by comprising:
Polysulfones and expanding agent are dissolved in formation polysulfones casting solution in organic solvent；
Adsorption resin particles are blended into the polysulfones casting solution and form mixing casting solution；
The mixing casting solution is added dropwise in distilled water and forms porous PS membrane cladding adsorptive resin particle；And
Hydrophilic modifying is carried out to the porous PS membrane cladding adsorptive resin particle, porous polysulfones coated particle is made.
2. preparation method according to claim 1, it is characterised in that specifically include: polysulfones particle and expanding agent are dissolved in
In organic solvent, and 3-24h is stirred under the conditions of 50-90 DEG C, form polysulfones casting solution, be cooled to room temperature later；Preferably, institute
The speed for stating stirring is 100-500rpm.
3. preparation method according to claim 1 or 2, it is characterised in that: the mass ratio of the polysulfones and expanding agent is 5-
15:2-6；And/or the mass ratio of the polysulfones and organic solvent is 5-15:79-93；And/or the expanding agent includes polyoxy
Change ethylene；And/or the organic solvent includes N-Methyl pyrrolidone.
4. preparation method according to claim 1, it is characterised in that specifically include: the adsorption resin particles are added to
In the polysulfones casting solution, and 10-60min is stirred, later static layering, and remove supernatant liquid, obtained containing absorption resin
The mixing casting solution of particle, continues thereafter with stirring.
5. preparation method according to claim 1 or 4, it is characterised in that: the adsorption resin particles with mix casting solution
Mass ratio be 2:3-5；And/or the adsorption resin particles include Amberlite series adsorption resin particles；Preferably, institute
Stating Amberlite series adsorption resin particles includes Amberlite FPA51, Amberlite XT30, Amberlite
CG300C or Amberlite CG300M resin particle.
6. preparation method according to claim 1, it is characterised in that specifically include: with the dropwise addition height of 10-30cm by institute
It states mixing casting solution to be added dropwise in distilled water, forms porous PS membrane cladding adsorptive resin particle, then post-processed；It is preferred that
, the post-processing include: the porous PS membrane of acquisition cladding adsorptive resin particle is transferred in clean distilled water, and
It saves 5-7 days, then is dried in vacuo, vacuum preservation.
7. preparation method according to claim 1, it is characterised in that specifically include:
In room temperature condition and protective atmosphere, by two isobutyl of N-Methyl pyrrolidone, vinyltriethoxysilane and azo
Nitrile dissolves in a solvent and stirs 10-30min, then adjusts temperature to 40-100 DEG C of progress polymerization reaction 6-24h, is wrapped
Reaction mixture containing prepolymer, then the reaction mixture comprising prepolymer and water are mixed to form pre-polymer solution；
The porous PS membrane cladding adsorptive resin particle is immersed in the pre-polymer solution and stirs 1-5h, then by institute
The porous PS membrane cladding adsorptive resin particle of the microswelling obtained is transferred to the citric acid solution that concentration is 0.5-1.5wt%
In, and 8-10h is heated at 30-80 DEG C, so that the porous polysulfones coated particle be made.
8. preparation method according to claim 7, it is characterised in that: the n-vinyl pyrrolidone, three second of vinyl
The mass ratio of oxysilane and azodiisobutyronitrile is 5.5-7.5:3.5-5.5:0.12-0.16；And/or the N- vinyl
The mass ratio of pyrrolidones and solvent is 5.5-7.5:100-300；And/or the solvent include vinyltriethoxysilane,
N-Methyl pyrrolidone and triethyl phosphate；And/or the volume ratio of the reaction mixture comprising prepolymer and water is 1:5-
5:1.
9. the porous polysulfones coated particle prepared by any one of claim 1-8 the method；Preferably, the porous polysulfones
The diameter of coated particle is 0.2-20mm, and 0.2-500 μm of the thickness of clad, the aperture of hole contained by clad is 0.05-5 μ
m。
10. porous polysulfones coated particle as claimed in claim 9 is in preparing the purposes in blood purifying product；Preferably, described
Product can remove blood Metabolites, and the blood Metabolites include lactic acid, pyruvic acid, inflammatory factor, bilirubin, are immunized
Any one in globulin, complement or two or more combinations；Preferably, the purposes includes: to coat porous polysulfones
Particle dipping pretreatment 5-7 days in physiological saline are used further to remove blood Metabolites later.
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| CN107649102A (en) * | 2017-09-30 | 2018-02-02 | 宁波市中心血站 | A kind of preparation method of compound doughnut polymeric adsorbent |
| CN108031454A (en) * | 2017-12-19 | 2018-05-15 | 陈荣胜 | Possesses blood-purifying adsorbing agent of physics specific selectivity and preparation method thereof |
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| CN107649102A (en) * | 2017-09-30 | 2018-02-02 | 宁波市中心血站 | A kind of preparation method of compound doughnut polymeric adsorbent |
| CN108031454A (en) * | 2017-12-19 | 2018-05-15 | 陈荣胜 | Possesses blood-purifying adsorbing agent of physics specific selectivity and preparation method thereof |
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