CN105478094A - Aminated poly-glycidyl methacrylate crosslinked composite microsphere and preparation method as well as application thereof - Google Patents
Aminated poly-glycidyl methacrylate crosslinked composite microsphere and preparation method as well as application thereof Download PDFInfo
- Publication number
- CN105478094A CN105478094A CN201510990399.7A CN201510990399A CN105478094A CN 105478094 A CN105478094 A CN 105478094A CN 201510990399 A CN201510990399 A CN 201510990399A CN 105478094 A CN105478094 A CN 105478094A
- Authority
- CN
- China
- Prior art keywords
- glycidyl methacrylate
- poly
- cross
- complex microsphere
- linked
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M1/00—Suction or pumping devices for medical purposes; Devices for carrying-off, for treatment of, or for carrying-over, body-liquids; Drainage systems
- A61M1/14—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Heart & Thoracic Surgery (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Vascular Medicine (AREA)
- Urology & Nephrology (AREA)
- Emergency Medicine (AREA)
- Engineering & Computer Science (AREA)
- Anesthesiology (AREA)
- Biomedical Technology (AREA)
- Hematology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to an aminated poly-glycidyl methacrylate crosslinked composite microsphere, being of a porous structure prepared from a matrix polymer and aminated poly-glycidyl methacrylatewherein the matrix polymer is a web template, the aminated poly-glycidyl methacrylate are crosslinked into a web of the matrix polymer, and the mass ratio of the matrix polymer to the aminated poly-glycidyl methacrylate is (1 to 3) : 1. The porosity of the composite microsphere is 75-90 percent, and the specific surface area is 7-20m<2>/g. The invention relates to a preparation method of the aminated poly-glycidyl methacrylate crosslinked composite microsphere, comprising the following steps: (1) polymerization reaction; (2) preparation of the poly-glycidyl methacrylate crosslinked composite microsphere; (3) modification of the poly-glycidyl methacrylate crosslinked composite microsphere. A high polymer adsorbent greater in porosity and specific surface area, controllable in size, stable in nature, and used for clearing bilirubin during blood perfusion can be obtained.
Description
Technical field
The invention belongs to adsorbent for bilirubin field, be specifically related to a kind of amination poly (glycidyl methacrylate) and be cross-linked complex microsphere and preparation method thereof.
Background technology
Bilirubin is the product of heme catabolism degraded, is a kind of endogenous toxin.Under normal physiological conditions, haemocyanin is combined with bilirubin, is drained after helping bilirubin to be transferred to liver.Hepatopath is due to hepatic dysfunction, and bilirubin metabolism approach is obstructed, and in blood, unconjugated bilirubin content increases, and the bilirubin of excessive concentrations especially unconjugated bilirubin can the normal function of interference cell, causes systemic toxicity symptom.When the concentration of blood mesobilirubin exceedes certain value, can obstructive jaundice be caused, even acute renal failure occur.
Effectively can be removed the bilirubin of patient's body middle and high concentration by blood perfusion technique, thus effectively treat the hyperbilirubinemias such as jaundice.Having high-adsorption-capacity (compatibility) with the adsorbent of good blood compatibility is that blood perfusion technique is successfully crucial.Blood perfusion removes the polymeric sorbent of bilirubin, and domestic and international researcher has carried out some exploratory development work.In recent years, China removes bilirubinic adsorbent research report using macromolecular material as blood perfusion also has a lot, as HB-H-6 class macroporous anion exchange resin and the agent of styrene cationic exchange resin adsorption, many micropores amine resin adsorbent, high polymer microfiltration membranes etc.These adsorbents respectively have superiority, but also there is many drawbacks that can not evade, as low in ion exchange resin absorption specificity, and high polymer microfiltration membranes cost is higher.Chen Zhiping etc. adopt suspension polymerization to obtain aminated microballoon (Chen Zhiping, Gao Baojiao, Yang Xiaofeng. Acta PhySico-Chimica Sinica [J] .2008,24 (8): 1417-1424), utilize electrostatic interaction that is amino and bilirubin molecule, adsorbent is made to have specific absorption, but owing to adopting direct suspension polymerisation, thus obtained microsphere is too fine and close, and porosity is low, specific area is not high, makes adsorption effect unsatisfactory.Meanwhile, due to microballoon sphere diameter less (200 microns), it is for needing larger pressure during blood perfusion.On the other hand, process for suspension polymerization condition is wayward, makes product property unstable.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, a kind of amination poly (glycidyl methacrylate) is provided to be cross-linked complex microsphere and preparation method thereof, larger to obtain porosity and specific area, size is controlled, removes the polymeric sorbent of bilirubin in the blood perfusion of stable in properties.
Amination poly (glycidyl methacrylate) of the present invention is cross-linked complex microsphere, the loose structure microballoon be made up of matrix polymer and amination poly (glycidyl methacrylate), described matrix polymer is network template, described amination poly (glycidyl methacrylate) is crosslinking in the network of matrix polymer, and the mass ratio of matrix polymer and amination poly (glycidyl methacrylate) is (1 ~ 3): 1.
Above-mentioned amination poly (glycidyl methacrylate) is cross-linked complex microsphere, and porosity is 75 ~ 90%, and specific area is 7 ~ 20m
2/ g.Complex microsphere size can need to determine according to application.
Above-mentioned amination poly (glycidyl methacrylate) is cross-linked complex microsphere, and described matrix polymer is the one in polyether sulfone, polystyrene, Kynoar.
Amination poly (glycidyl methacrylate) of the present invention is cross-linked the preparation method of complex microsphere, and processing step is as follows:
(1) polymerisation
10 ~ 20 mass parts matrix polymers are dissolved in the solvent of 80 ~ 90 mass parts, treat that matrix polymer dissolves completely and obtain matrix polymer solution, GMA is added in described matrix polymer solution, crosslinking agent and initator forming reactions system, after removing oxygen is vacuumized to reaction system, react 18 ~ 24 hours in 50 ~ 95 DEG C in nitrogen protection with under stirring, reaction terminates rear stopping heating and stirs, gained reactant liquor is placed after 18 ~ 24 hours and filter, gained filtrate is poly (glycidyl methacrylate) and is cross-linked complex microsphere and prepares liquid,
During forming reactions system, the addition of GMA is 4% ~ 15% of matrix polymer solution quality; The addition of crosslinking agent presses the mol ratio of crosslinking agent and GMA for (0.5 ~ 2.5): 100 measure; The addition of initator presses the mol ratio of initator and GMA for (0.25 ~ 2.5): 100 measure;
(2) poly (glycidyl methacrylate) is cross-linked the preparation of complex microsphere
The preparation that poly (glycidyl methacrylate) is cross-linked complex microsphere uses microballoon preparation facilities, described microballoon preparation facilities comprises gas control valve, fluid reservoir, filter screen, liquid control valve and syringe needle, described fluid reservoir is closed container, described gas control valve is arranged in the air inlet pipe that is connected with fluid reservoir top, described filter screen is arranged on on the drain pipe be connected bottom fluid reservoir, described syringe needle is arranged on the liquid outlet place with the drain pipe end be connected bottom fluid reservoir, described liquid control valve is arranged on on the drain pipe be connected bottom fluid reservoir and between filter screen and syringe needle,
Step (1) gained poly (glycidyl methacrylate) being cross-linked complex microsphere prepares in the fluid reservoir of liquid loading microballoon preparation facilities, then operating gas control valve applies constant air pressure to the liquid level in fluid reservoir, and open liquid control valve and make poly (glycidyl methacrylate) be cross-linked complex microsphere to prepare liquid and be frozen into poly (glycidyl methacrylate) be cross-linked complex microsphere by flowing out to be dropped in coagulating bath after filter screen from the syringe needle of microballoon preparation facilities, continue after the poly (glycidyl methacrylate) solidified be cross-linked complex microsphere leach from coagulating bath, soak to remove by deionized water and remain in poly (glycidyl methacrylate) and be cross-linked solvent on complex microsphere,
(3) poly (glycidyl methacrylate) is cross-linked the modification of complex microsphere
Poly (glycidyl methacrylate) prepared by step (2) is cross-linked complex microsphere 10 ~ 20 mass parts and aminating agent solution 80 ~ 90 mass parts adds in reaction vessel, under agitation within 18 ~ 24 hours, form amination poly (glycidyl methacrylate) in 30 ~ 70 DEG C of aminating reactions and be cross-linked complex microsphere, then amination poly (glycidyl methacrylate) is cross-linked complex microsphere to leach from aminating agent solution, soaks to remove by deionized water and remain in amination poly (glycidyl methacrylate) and be cross-linked aminating agent on complex microsphere.
In the step (2) of said method, applying constant air pressure to the liquid level in fluid reservoir is ooze speed in order to what control that poly (glycidyl methacrylate) is cross-linked that complex microsphere prepares liquid, and makes the speed that oozes keep stable.Test shows, under certain condition (poly (glycidyl methacrylate) be cross-linked that complex microsphere prepares that fluid viscosity is certain, syringe needle internal diameter determine), constant air pressure is larger, poly (glycidyl methacrylate) be cross-linked complex microsphere prepare liquid drip speed faster.
In the step (2) of said method, the syringe needle internal diameter of described microballoon preparation facilities is 0.5 ~ 0.7mm, syringe needle is 5 ~ 15cm apart from the height of coagulating bath liquid level, and poly (glycidyl methacrylate) is cross-linked complex microsphere, and to prepare the speed that drop falls into coagulating bath be 0.5 ~ 3/s.
In the step (1) of said method, described matrix polymer is the one in polyether sulfone, polystyrene, Kynoar, solvent is N, dinethylformamide, N, any one in N-dimethylacetylamide, dimethyl sulfoxide (DMSO), crosslinking agent is N, N'-methylene-bisacrylamide, and initator is any one in dibenzoyl peroxide, azodiisobutyronitrile; Aminating agent solution described in step (2) by aminating agent and deionized water formulated with the mass ratio of 1:3, described aminating agent is the one in ethylenediamine, 1,6-hexamethylene diamine, diethylenetriamine.
In step (2) in said method, described coagulating bath is the deionization water-bath of 20 ~ 50 DEG C.
In said method, step (1) gained poly (glycidyl methacrylate) is cross-linked complex microsphere and prepares liquid and vacuumize or pass into nitrogen and carry out deaeration process.
In the step (2) of said method, soaking the temperature of deionized water used when poly (glycidyl methacrylate) is cross-linked complex microsphere by deionized water is 50 ~ 60 DEG C, changes deionized water at least one times in immersion process; Soaking the temperature of deionized water used when amination poly (glycidyl methacrylate) is cross-linked complex microsphere by deionized water in step (3) is 50 ~ 60 DEG C, changes deionized water at least one times in immersion process.
Amination poly (glycidyl methacrylate) of the present invention is cross-linked complex microsphere as the application of removing bilirubinic adsorbent in blood perfusion.
Compared with prior art, the present invention has following beneficial effect:
1, the present invention be blood perfusion remove bilirubin provide a kind of absorption and elimination effect excellent polymeric sorbent---amination poly (glycidyl methacrylate) is cross-linked complex microsphere, amination poly (glycidyl methacrylate) of the present invention is used to be cross-linked complex microsphere, be 6 ~ 13mg/g to the adsorbance of the bilirubin solution mesobilirubin of concentration 100mg/L, clearance rate is 75 ~ 90%.
2, the method for the invention adopts the mode of in-situ polymerization, be crosslinking between matrix polymer lattice chain by directly micro-for functional polymer poly (glycidyl methacrylate), network structure makes microballoon have larger porosity (75 ~ 88%) and specific area (7 ~ 16m
2/ g), the amino on the microballoon of amination is simultaneously by the specific adsorbing bilirubin of electrostatic interaction, and the chain hydrophobic structure in matrix polymer also has good adsorption capacity to there being certain hydrophobic bilirubin molecule equally.
3, the method for the invention obtains sorbent microspheres by the form extruded, and Microsphere Size can need to control flexibly and change according to application, and it is controlled that gained amination poly (glycidyl methacrylate) is cross-linked complex microsphere sized macroscopic, more convenient use.
4, the method for the invention technique is simple and easy to control, and cost is low, and the amination poly (glycidyl methacrylate) prepared is cross-linked complex microsphere physics, stable chemical nature, is beneficial to large-scale production and application.
Accompanying drawing explanation
Fig. 1 is the structural representation of the microballoon preparation facilities used in the method for the invention.In figure, 1-gas control valve, 2-fluid reservoir, 2-1-top cover, 2-2-tank body, 3-filter screen, 4-liquid control valve, 5-syringe needle.
Fig. 2 is that amination poly (glycidyl methacrylate) prepared by embodiment 1 is cross-linked the Electronic Speculum figure (a is complex microsphere profile, and b is the longitudinal sectional drawing of a, and c is the enlarged drawing of b) of complex microsphere section.
Fig. 3 is the (infrared spectrum that number in the figure a), non-amination poly (glycidyl methacrylate) is cross-linked complex microsphere (number in the figure b), amination poly (glycidyl methacrylate) is cross-linked complex microsphere (number in the figure c) of matrix polymer in embodiment 2.
Fig. 4 is that the amination poly (glycidyl methacrylate) that each embodiment obtains is cross-linked the adsorption isotherm experiment result figure (adsorption temp 25 DEG C of complex microsphere to the bilirubin solution of different initial concentration, bilirubin solution pH=7.2 ~ 7.4, bilirubin solution is by phosphate buffered saline).
Detailed description of the invention
Be cross-linked complex microsphere and preparation method thereof below by detailed description of the invention to amination poly (glycidyl methacrylate) of the present invention to be described further with application.
In following embodiment, microballoon preparation facilities used as shown in Figure 1, comprises gas control valve 1, fluid reservoir 2, filter screen 3, liquid control valve 4 and syringe needle 5; Described fluid reservoir 2 is closed container, is combined by cylindrical tank 2-2 and top cover 2-1, top cover is provided with and makes fluid reservoir have bubble-tight rubber seal; Described gas control valve 1 is hand-operated valve, is arranged in the air inlet pipe that is connected with fluid reservoir top cover, for controlling the air pressure in fluid reservoir; Install filter screen for convenience, be divided into epimere drain pipe and hypomere drain pipe with the drain pipe be connected bottom fluid reservoir 2, the combination end of two sections of drain pipes is provided with flange and is furnished with sealing ring, and described filter screen 3 is clamped between the flange of two sections of drain pipes; Described syringe needle 5 is arranged on the liquid outlet place of hypomere drain pipe end, and described liquid control valve 1 is hand-operated valve, to be arranged on hypomere drain pipe and to be positioned on syringe needle 5.In this microballoon preparation facilities, fluid reservoir, air inlet pipe and drain pipe are stainless steel manufacture, and filter screen is stainless (steel) wire, and its order number is 200 orders.
In following embodiment, the porosity of prepared complex microsphere and sphere diameter are obtained by following formulae discovery:
W
bfor complex microsphere weight in wet base, W
afor complex microsphere dry weight, ρ
wfor the density of water, ρ
pfor matrix polymer density.
Embodiment 1
In the present embodiment, to be cross-linked the preparation method of complex microsphere as follows for amination poly (glycidyl methacrylate):
(1) polymerisation
14 parts of polyether sulfones are dissolved in the N of 86 parts, in N-dimethylacetylamide, be heated to 90 DEG C and stir polyether sulfone is dissolved completely obtain polyether sulfone solution, GMA is added in gained polyether sulfone solution, crosslinking agent N, N'-methylene-bisacrylamide and initator azodiisobutyronitrile, nitrogen is passed into after vacuumizing removing oxygen, in nitrogen protection, stirring reaction 24 hours at 90 DEG C, reaction terminates rear stopping heating and stirs, filter to get filtrate after reaction gained reactant liquor is placed 24 hours, gained filtrate is poly (glycidyl methacrylate) and is cross-linked complex microsphere and prepares liquid, be cross-linked complex microsphere to gained poly (glycidyl methacrylate) to prepare in liquid and pass into nitrogen and carry out deaeration process,
During forming reactions system, the addition of GMA is 8 parts; The mol ratio of crosslinking agent and GMA is 2.5:100; The mol ratio of initator and GMA is 1.5:100.
(2) poly (glycidyl methacrylate) is cross-linked the preparation of complex microsphere
Step (1) gained poly (glycidyl methacrylate) being cross-linked complex microsphere prepares in the fluid reservoir of liquid loading microballoon preparation facilities, then operating gas control valve applies the constant air pressure of 0.15MPa to the liquid level in fluid reservoir by air compressor, and open liquid control valve and make poly (glycidyl methacrylate) be cross-linked complex microsphere to prepare liquid and be frozen into poly (glycidyl methacrylate) in 50 DEG C of water-baths be cross-linked complex microsphere by flowing out to be dropped into after filter screen from the syringe needle of microballoon preparation facilities, described syringe needle is 15cm apart from coagulating bath liquid level, syringe needle internal diameter 0.5mm, dripping speed is 0.5/s, then the microballoon solidified is leached from coagulating bath, soak microballoon by the deionized waters of 50 DEG C and remove residual solvent in 24 hours, period changes deionized water 2 times, finally microballoon is leached.
(3) poly (glycidyl methacrylate) is cross-linked the modification of complex microsphere
Step (2) gained poly (glycidyl methacrylate) is cross-linked complex microsphere 20 parts and 1, 6-hexamethylene diamine aminating agent solution 80 parts adds in reaction vessel, stir at 70 DEG C and within 12 hours, carry out aminated reaction formation amination poly (glycidyl methacrylate) and be cross-linked complex microsphere, described aminating agent solution by hexamethylene diamine and deionized water formulated with the mass ratio of 1:3, then amination poly (glycidyl methacrylate) is cross-linked complex microsphere to leach from aminating agent solution, soak amination poly (glycidyl methacrylate) by 60 DEG C of deionized waters and be cross-linked the residual amination reagent of complex microsphere 24h removal, period changes deionized water 4 times, finally amination poly (glycidyl methacrylate) is cross-linked complex microsphere to leach.The sphere diameter that gained amination poly (glycidyl methacrylate) is cross-linked complex microsphere is 2.0mm, and porosity is 83%, and the specific area measured with nitrogen adsorption methods is for 12m
2/ g.By the internal structure of scanning electron microscopic observation thus obtained microsphere, see Fig. 2.As seen from Figure 2, microballoon inside presents the loose structure differed in size.
Complex microsphere is cross-linked to the poly (glycidyl methacrylate) of matrix polymer polyether sulfone, step (2) non-amination, amination poly (glycidyl methacrylate) be cross-linked complex microsphere do respectively Fourier transform infrared spectroscopy experiment, it the results are shown in Figure 3.As can be seen from Figure 3, GMA is successful polymerization in matrix polymer polyether sulfone, and successful amination.
Embodiment 2
In the present embodiment, to be cross-linked the preparation method of complex microsphere as follows for amination poly (glycidyl methacrylate):
(1) polymerisation
10 parts of polyether sulfones are dissolved in the N of 90 parts, in N-dimethylacetylamide, be heated to 60 DEG C and stir polyether sulfone is dissolved completely obtain polyether sulfone solution, GMA is added in gained polyether sulfone solution, crosslinking agent N, N'-methylene-bisacrylamide and initator azodiisobutyronitrile, nitrogen is passed into after vacuumizing removing oxygen, in nitrogen protection, stirring reaction 18 hours at 60 DEG C, reaction terminates rear stopping heating and stirs, filter to get filtrate after reaction gained reactant liquor is placed 24 hours, gained filtrate is poly (glycidyl methacrylate) and is cross-linked complex microsphere and prepares liquid, be cross-linked complex microsphere to gained poly (glycidyl methacrylate) to prepare in liquid and pass into nitrogen and carry out deaeration process,
During forming reactions system, the addition of GMA is 4 parts; The mol ratio of crosslinking agent and GMA is 0.5:100; The mol ratio of initator and GMA is 0.5:100.
(2) poly (glycidyl methacrylate) is cross-linked the preparation of complex microsphere
Step (1) gained poly (glycidyl methacrylate) being cross-linked complex microsphere prepares in the fluid reservoir of liquid loading microballoon preparation facilities, then operating gas control valve applies the constant air pressure of 0.1MPa to the liquid level in fluid reservoir by air compressor, and open liquid control valve and make poly (glycidyl methacrylate) be cross-linked complex microsphere to prepare liquid and be frozen into poly (glycidyl methacrylate) in 20 DEG C of water-baths be cross-linked complex microsphere by flowing out to be dropped into after filter screen from the syringe needle of microballoon preparation facilities, described syringe needle is 15cm apart from coagulating bath liquid level, syringe needle internal diameter 0.7mm, dripping speed is 1.5/s, then the microballoon solidified is leached from coagulating bath, soak microballoon by the deionized waters of 50 DEG C and remove residual solvent in 24 hours, period changes deionized water 1 time, finally microballoon is leached,
(3) poly (glycidyl methacrylate) is cross-linked the modification of complex microsphere
Step (2) gained poly (glycidyl methacrylate) being cross-linked complex microsphere 10 parts adds in reaction vessel with diethylenetriamine aminating agent solution 90 parts, stir at 30 DEG C and within 24 hours, carry out aminated reaction formation amination poly (glycidyl methacrylate) and be cross-linked complex microsphere, described aminating agent solution by hexamethylene diamine and deionized water formulated with the mass ratio of 1:3, then amination poly (glycidyl methacrylate) is cross-linked complex microsphere to leach from aminating agent solution, soak amination poly (glycidyl methacrylate) by 50 DEG C of deionized waters and be cross-linked the residual amination reagent of complex microsphere 24h removal, period changes deionized water 1 time, finally amination poly (glycidyl methacrylate) is cross-linked complex microsphere to leach.The sphere diameter that gained amination poly (glycidyl methacrylate) is cross-linked complex microsphere is 2.3mm, and porosity is 75%, and the specific area measured with nitrogen adsorption methods is for 7m
2/ g.
Embodiment 3
In the present embodiment, to be cross-linked the preparation method of complex microsphere as follows for amination poly (glycidyl methacrylate):
(1) polymerisation
12 parts of polystyrene are dissolved in the N of 88 parts, in N-dimethylacetylamide, be heated to 60 DEG C and stir polystyrene is dissolved completely obtain polystyrene solution, GMA is added in gained polystyrene solution, crosslinking agent N, N'-methylene-bisacrylamide and initator azodiisobutyronitrile, nitrogen is passed into after vacuumizing removing oxygen, in nitrogen protection, stirring reaction 18 hours at 60 DEG C, reaction terminates rear stopping heating and stirs, filter to get filtrate after reaction gained reactant liquor is placed 24 hours, gained filtrate is poly (glycidyl methacrylate) and is cross-linked complex microsphere and prepares liquid,
During forming reactions system, the addition of GMA is 6 parts; The mol ratio of crosslinking agent and GMA is 1:100; The mol ratio of initator and GMA is 0.5:100.
(2) poly (glycidyl methacrylate) is cross-linked the preparation of complex microsphere
Step (1) gained poly (glycidyl methacrylate) being cross-linked complex microsphere prepares in the fluid reservoir of liquid loading microballoon preparation facilities, then operating gas control valve applies the constant air pressure of 0.15MPa to the liquid level in fluid reservoir by air compressor, and open liquid control valve and make poly (glycidyl methacrylate) be cross-linked complex microsphere to prepare liquid and be frozen into poly (glycidyl methacrylate) in 35 DEG C of water-baths be cross-linked complex microsphere by flowing out to be dropped into after filter screen from the syringe needle of microballoon preparation facilities, described syringe needle is 5cm apart from coagulating bath liquid level, syringe needle internal diameter 0.7mm, dripping speed is 2/s, then the microballoon solidified is leached from coagulating bath, soak microballoon by the deionized waters of 50 DEG C and remove residual solvent in 10 hours, period changes deionized water 3 times, finally microballoon is leached,
(3) poly (glycidyl methacrylate) is cross-linked the modification of complex microsphere
Step (2) gained poly (glycidyl methacrylate) being cross-linked complex microsphere 20 parts adds in reaction vessel with diethylenetriamine aminating agent solution 80 parts, stir at 70 DEG C and within 8 hours, carry out aminated reaction formation amination poly (glycidyl methacrylate) and be cross-linked complex microsphere, described aminating agent solution by hexamethylene diamine and deionized water formulated with the mass ratio of 1:3, then amination poly (glycidyl methacrylate) is cross-linked complex microsphere to leach from aminating agent solution, soak amination poly (glycidyl methacrylate) by 50 DEG C of deionized waters and be cross-linked the residual amination reagent of complex microsphere 24h removal, period changes deionized water 1 time, finally amination poly (glycidyl methacrylate) is cross-linked complex microsphere to leach.The sphere diameter that gained amination poly (glycidyl methacrylate) is cross-linked complex microsphere is 2.4mm, and porosity is 80%, and the specific area measured with nitrogen adsorption methods is for 9m
2/ g.
Embodiment 4
In the present embodiment, to be cross-linked the preparation method of complex microsphere as follows for amination poly (glycidyl methacrylate):
(1) polymerisation
14 parts of polystyrene are dissolved in the N of 86 parts, in N-dimethylacetylamide, be heated to 95 DEG C and stir polystyrene is dissolved completely obtain polystyrene solution, GMA is added in gained polystyrene solution, crosslinking agent N, N'-methylene-bisacrylamide and initator azodiisobutyronitrile, nitrogen is passed into after vacuumizing removing oxygen, in nitrogen protection, stirring reaction 24 hours at 90 DEG C, reaction terminates rear stopping heating and stirs, filter to get filtrate after reaction gained reactant liquor is placed 24 hours, gained filtrate is poly (glycidyl methacrylate) and is cross-linked complex microsphere and prepares liquid, be cross-linked complex microsphere to gained poly (glycidyl methacrylate) to prepare liquid and vacuumize and carry out deaeration process,
During forming reactions system, the addition of GMA is 8 parts; The mol ratio of crosslinking agent and GMA is 2:100; The mol ratio of initator and GMA is 1:100.
(2) poly (glycidyl methacrylate) is cross-linked the preparation of complex microsphere
Step (1) gained poly (glycidyl methacrylate) being cross-linked complex microsphere prepares in the fluid reservoir of liquid loading microballoon preparation facilities, then operating gas control valve applies 0.38MPa constant air pressure by air compressor to the liquid level in fluid reservoir, and open liquid control valve and make poly (glycidyl methacrylate) be cross-linked complex microsphere to prepare liquid and be frozen into poly (glycidyl methacrylate) in 35 DEG C of water-baths be cross-linked complex microsphere by flowing out to be dropped into after filter screen from the syringe needle of microballoon preparation facilities, described syringe needle is 5cm apart from coagulating bath liquid level, syringe needle internal diameter 0.5mm, dripping speed is 3/s, then the microballoon solidified is leached from coagulating bath, soak microballoon by the deionized waters of 60 DEG C and remove residual solvent in 10 hours, period changes deionized water 2 times, finally microballoon is leached,
(3) poly (glycidyl methacrylate) is cross-linked the modification of complex microsphere
Step (2) gained poly (glycidyl methacrylate) is cross-linked complex microsphere 20 parts and 1, 6-hexamethylene diamine aminating agent solution 80 parts adds in reaction vessel, stir at 70 DEG C and within 24 hours, carry out aminated reaction formation amination poly (glycidyl methacrylate) and be cross-linked complex microsphere, described aminating agent solution by hexamethylene diamine and deionized water formulated with the mass ratio of 1:3, then amination poly (glycidyl methacrylate) is cross-linked complex microsphere to leach from aminating agent solution, soak amination poly (glycidyl methacrylate) by 50 DEG C of deionized waters and be cross-linked the residual amination reagent of complex microsphere 24h removal, period changes deionized water 2 times, finally amination poly (glycidyl methacrylate) is cross-linked complex microsphere to leach.The sphere diameter that gained amination poly (glycidyl methacrylate) is cross-linked complex microsphere is 2.3mm, and porosity is 75%, and the specific area measured with nitrogen adsorption methods is for 9m
2/ g.
Embodiment 5
In the present embodiment, to be cross-linked the preparation method of complex microsphere as follows for amination poly (glycidyl methacrylate):
(1) polymerisation
20 parts of Kynoar are dissolved in the N of 80 parts, in N-dimethylacetylamide, be heated to 75 DEG C and stir polyether sulfone is dissolved completely obtain Kynoar solution, GMA is added in gained Kynoar solution, crosslinking agent N, N'-methylene-bisacrylamide and initator azodiisobutyronitrile, nitrogen is passed into after vacuumizing removing oxygen, in nitrogen protection, stirring reaction 24 hours at 75 DEG C, reaction terminates rear stopping heating and stirs, filter to get filtrate after reaction gained reactant liquor is placed 24 hours, gained filtrate is poly (glycidyl methacrylate) and is cross-linked complex microsphere and prepares liquid, be cross-linked complex microsphere to gained poly (glycidyl methacrylate) to prepare liquid and vacuumize and carry out deaeration process,
During forming reactions system, the addition of GMA is 8 parts; The mol ratio of crosslinking agent and GMA is 1:100; The mol ratio of initator and GMA is 1:100.
(2) poly (glycidyl methacrylate) is cross-linked the preparation of complex microsphere
Step (1) gained poly (glycidyl methacrylate) being cross-linked complex microsphere prepares in the fluid reservoir of liquid loading microballoon preparation facilities, then operating gas control valve applies the constant air pressure of 0.32MPa to the liquid level in fluid reservoir by air compressor, and open liquid control valve and make poly (glycidyl methacrylate) be cross-linked complex microsphere to prepare liquid and be frozen into poly (glycidyl methacrylate) in 35 DEG C of water-baths be cross-linked complex microsphere by flowing out to be dropped into after filter screen from the syringe needle of microballoon preparation facilities, described syringe needle is 15cm apart from coagulating bath liquid level, syringe needle internal diameter 0.5mm, dripping speed is 2/s, then the microballoon solidified is leached from coagulating bath, soak microballoon by the deionized waters of 50 DEG C and remove residual solvent in 10 hours, period changes deionized water 1 time, finally microballoon is leached,
(3) poly (glycidyl methacrylate) is cross-linked the modification of complex microsphere
Step (2) gained poly (glycidyl methacrylate) being cross-linked complex microsphere 20 parts adds in reaction vessel with diethylenetriamine amine aminating agent solution 80 parts, stir at 50 DEG C and within 18 hours, carry out aminated reaction formation amination poly (glycidyl methacrylate) and be cross-linked complex microsphere, described aminating agent solution by hexamethylene diamine and deionized water formulated with the mass ratio of 1:3, then amination poly (glycidyl methacrylate) is cross-linked complex microsphere to leach from aminating agent solution, soak amination poly (glycidyl methacrylate) by 50 DEG C of deionized waters and be cross-linked the residual amination reagent of complex microsphere 20h removal, period changes deionized water 1 time, finally amination poly (glycidyl methacrylate) is cross-linked complex microsphere to leach.The sphere diameter that gained amination poly (glycidyl methacrylate) is cross-linked complex microsphere is 2.0mm, and porosity is 85%, the specific area 11m measured with nitrogen adsorption methods
2/ g.
Embodiment 6
In the present embodiment, to be cross-linked the preparation method of complex microsphere as follows for amination poly (glycidyl methacrylate):
(1) polymerisation
15 parts of Kynoar are dissolved in the N of 85 parts, in N-dimethylacetylamide, be heated to 75 DEG C and stir polyether sulfone is dissolved completely obtain Kynoar solution, GMA is added in gained Kynoar solution, crosslinking agent N, N'-methylene-bisacrylamide and initator azodiisobutyronitrile, nitrogen is passed into after vacuumizing removing oxygen, in nitrogen protection, stirring reaction 24 hours at 75 DEG C, reaction terminates rear stopping heating and stirs, filter to get filtrate after reaction gained reactant liquor is placed 24 hours, gained filtrate is poly (glycidyl methacrylate) and is cross-linked complex microsphere and prepares liquid, be cross-linked complex microsphere to gained poly (glycidyl methacrylate) to prepare liquid and vacuumize and carry out deaeration process,
During forming reactions system, the addition of GMA is 12 parts; The mol ratio of crosslinking agent and GMA is 2.5:100; The mol ratio of initator and GMA is 1:100.
(2) poly (glycidyl methacrylate) is cross-linked the preparation of complex microsphere
Step (1) gained poly (glycidyl methacrylate) being cross-linked complex microsphere prepares in the fluid reservoir of liquid loading microballoon preparation facilities, then operating gas control valve applies the constant air pressure of 0.22MPa to the liquid level in fluid reservoir by air compressor, and open liquid control valve and make poly (glycidyl methacrylate) be cross-linked complex microsphere to prepare liquid and be frozen into poly (glycidyl methacrylate) in 35 DEG C of water-baths be cross-linked complex microsphere by flowing out to be dropped into after filter screen from the syringe needle of microballoon preparation facilities, described syringe needle is 8cm apart from coagulating bath liquid level, syringe needle internal diameter 0.5mm, dripping speed is 1/s, then the microballoon solidified is leached from coagulating bath, soak microballoon by the deionized waters of 60 DEG C and remove residual solvent in 10 hours, period changes deionized water 2 times, finally microballoon is leached and both obtain poly (glycidyl methacrylate) crosslinked microsphere.
(3) poly (glycidyl methacrylate) is cross-linked the modification of complex microsphere
Step (2) gained poly (glycidyl methacrylate) is cross-linked complex microsphere 20 parts and 1, 6-hexamethylene diamine aminating agent solution 80 parts adds in reaction vessel, stir at 50 DEG C and within 24 hours, carry out aminated reaction formation amination poly (glycidyl methacrylate) and be cross-linked complex microsphere, described aminating agent solution by hexamethylene diamine and deionized water formulated with the mass ratio of 1:3, then amination poly (glycidyl methacrylate) is cross-linked complex microsphere to leach from aminating agent solution, soak amination poly (glycidyl methacrylate) by 60 DEG C of deionized waters and be cross-linked the residual amination reagent of complex microsphere 24h removal, period changes deionized water 2 times, finally amination poly (glycidyl methacrylate) is cross-linked complex microsphere to leach.The sphere diameter that gained amination poly (glycidyl methacrylate) is cross-linked complex microsphere is 1.8mm, and porosity is 88%, the specific area 16m measured with nitrogen adsorption methods
2/
g.
Adsorption isotherm experiment:
Get amination poly (glycidyl methacrylate) prepared by each embodiment to be cross-linked complex microsphere 30mg and to put into the certain density bilirubin solution of 5mL, in lucifuge, vibrate to adsorption equilibrium in 25 DEG C of water-baths, calculate adsorbance (mg/g).Parallelly do 6 groups of experiments, each group bilirubin solution concentration is respectively 100mg/L, 150mg/L, 200mg/L, 300mg/L, 400mg/L, 500mg/L, the results are shown in Figure 4.
Adsorbance computing formula is as follows:
Q
e＝(C
0-C
e)V/100m
Wherein Q
efor adsorbance, C
0for bilirubin solution initial concentration, C
ethe concentration of bilirubin solution during for reaching adsorption equilibrium, v is the volume of bilirubin solution, and m is the quality that amination poly (glycidyl methacrylate) is cross-linked complex microsphere.
The Measurement and Computation of clearance rate:
Each embodiment gained amination poly (glycidyl methacrylate) is cross-linked complex microsphere and puts into the adsorption column that syringe makes 5cm respectively, be that the bilirubin solution of 100mg/L crosses post process with 0.5 ~ 1mL flow velocity by 20mL concentration, calculate clearance rate, added in table 1.The computing formula of clearance rate is as follows:
Bilirubin solution concentration × 100% before bilirubin solution concentration/mistake post after bilirubin clearance rate=mistake post
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Clearance rate (%) | 88 | 75 | 80 | 82 | 83 | 90 |
Claims (10)
1. an amination poly (glycidyl methacrylate) is cross-linked complex microsphere, it is characterized in that the loose structure microballoon that this complex microsphere is made up of matrix polymer and amination poly (glycidyl methacrylate), described matrix polymer is network template, described amination poly (glycidyl methacrylate) is crosslinking in the network of matrix polymer, and the mass ratio of matrix polymer and amination poly (glycidyl methacrylate) is (1 ~ 3): 1.
2. amination poly (glycidyl methacrylate) is cross-linked complex microsphere according to claim 1, and it is characterized in that the porosity of this complex microsphere is 75 ~ 90%, specific area is 7 ~ 20m
2/ g.
3. according to claim 1 or 2, amination poly (glycidyl methacrylate) is cross-linked complex microsphere, it is characterized in that described matrix polymer is the one in polyether sulfone, polystyrene, Kynoar.
4. amination poly (glycidyl methacrylate) is cross-linked a preparation method for complex microsphere, it is characterized in that processing step is as follows:
(1) polymerisation
10 ~ 20 mass parts matrix polymers are dissolved in the solvent of 80 ~ 90 mass parts, treat that matrix polymer dissolves completely and obtain matrix polymer solution, GMA is added in described matrix polymer solution, crosslinking agent and initator forming reactions system, after removing oxygen is vacuumized to reaction system, react 18 ~ 24 hours in 50 ~ 95 DEG C in nitrogen protection with under stirring, reaction terminates rear stopping heating and stirs, gained reactant liquor is placed after 18 ~ 24 hours and filter, gained filtrate is poly (glycidyl methacrylate) and is cross-linked complex microsphere and prepares liquid,
During forming reactions system, the addition of GMA is 4% ~ 15% of matrix polymer solution quality; The addition of crosslinking agent presses the mol ratio of crosslinking agent and GMA for (0.5 ~ 2.5): 100 measure; The addition of initator presses the mol ratio of initator and GMA for (0.25 ~ 2.5): 100 measure;
(2) poly (glycidyl methacrylate) is cross-linked the preparation of complex microsphere
The preparation that poly (glycidyl methacrylate) is cross-linked complex microsphere uses microballoon preparation facilities, described microballoon preparation facilities comprises gas control valve (1), fluid reservoir (2), filter screen (3), liquid control valve (4) and syringe needle (5), described fluid reservoir (2) is closed container, described gas control valve (1) is arranged in the air inlet pipe that is connected with fluid reservoir top, described filter screen (3) is arranged on on the drain pipe be connected bottom fluid reservoir (2), described syringe needle (5) is arranged on the liquid outlet place of the drain pipe end be connected with fluid reservoir (2) bottom, described liquid control valve (4) is arranged on and is positioned between filter screen (3) and syringe needle (5) with on the drain pipe that is connected of fluid reservoir (2) bottom,
Step (1) gained poly (glycidyl methacrylate) being cross-linked complex microsphere prepares in the fluid reservoir of liquid loading microballoon preparation facilities, then operating gas control valve applies constant air pressure to the liquid level in fluid reservoir, and open liquid control valve and make poly (glycidyl methacrylate) be cross-linked complex microsphere to prepare liquid and be frozen into poly (glycidyl methacrylate) be cross-linked complex microsphere by flowing out to be dropped in coagulating bath after filter screen from the syringe needle of microballoon preparation facilities, continue after the poly (glycidyl methacrylate) solidified be cross-linked complex microsphere leach from coagulating bath, soak to remove by deionized water and remain in poly (glycidyl methacrylate) and be cross-linked solvent on complex microsphere,
(3) poly (glycidyl methacrylate) is cross-linked the modification of complex microsphere
Poly (glycidyl methacrylate) prepared by step (2) is cross-linked complex microsphere 10 ~ 20 mass parts and aminating agent solution 80 ~ 90 mass parts adds in reaction vessel, under agitation within 18 ~ 24 hours, form amination poly (glycidyl methacrylate) in 30 ~ 70 DEG C of aminating reactions and be cross-linked complex microsphere, then amination poly (glycidyl methacrylate) is cross-linked complex microsphere to leach from aminating agent solution, soaks to remove by deionized water and remain in amination poly (glycidyl methacrylate) and be cross-linked aminating agent on complex microsphere.
5. amination poly (glycidyl methacrylate) is cross-linked the preparation method of complex microsphere according to claim 4, it is characterized in that the syringe needle internal diameter of microballoon preparation facilities described in step (2) is 0.5 ~ 0.7mm, syringe needle is 5 ~ 15cm apart from the height of coagulating bath liquid level, and poly (glycidyl methacrylate) is cross-linked complex microsphere, and to prepare the speed that drop falls into coagulating bath be 0.5 ~ 3/s.
6. according to claim 4 or 5, amination poly (glycidyl methacrylate) is cross-linked the preparation method of complex microsphere, it is characterized in that matrix polymer described in step (1) is the one in polyether sulfone, polystyrene, Kynoar, solvent is N, dinethylformamide, N, any one in N-dimethylacetylamide, dimethyl sulfoxide (DMSO), crosslinking agent is N, N'-methylene-bisacrylamide, and initator is any one in dibenzoyl peroxide, azodiisobutyronitrile; Aminating agent solution described in step (2) by aminating agent and deionized water formulated with the mass ratio of 1:3, described aminating agent is the one in ethylenediamine, 1,6-hexamethylene diamine, diethylenetriamine.
7. according to claim 4 or 5, amination poly (glycidyl methacrylate) is cross-linked the preparation method of complex microsphere, it is characterized in that coagulating bath described in step (2) is the deionization water-bath of 20 ~ 50 DEG C.
8. according to claim 4 or 5, amination poly (glycidyl methacrylate) is cross-linked the preparation method of complex microsphere, it is characterized in that gained poly (glycidyl methacrylate) in step (1) to be cross-linked complex microsphere and prepares liquid and vacuumize or pass into nitrogen and carry out deaeration process.
9. according to claim 4 or 5, amination poly (glycidyl methacrylate) is cross-linked the preparation method of complex microsphere, it is characterized in that soaking the temperature of deionized water used when poly (glycidyl methacrylate) is cross-linked complex microsphere by deionized water in step (2) is 50 ~ 60 DEG C, changes deionized water at least one times in immersion process; Soaking the temperature of deionized water used when amination poly (glycidyl methacrylate) is cross-linked complex microsphere by deionized water in step (3) is 50 ~ 60 DEG C, changes deionized water at least one times in immersion process.
10. in claims 1 to 3, amination poly (glycidyl methacrylate) described in arbitrary claim is cross-linked complex microsphere as the application of removing bilirubinic adsorbent in blood perfusion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510990399.7A CN105478094B (en) | 2015-12-25 | 2015-12-25 | Amination poly (glycidyl methacrylate) crosslinking complex microsphere and preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510990399.7A CN105478094B (en) | 2015-12-25 | 2015-12-25 | Amination poly (glycidyl methacrylate) crosslinking complex microsphere and preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105478094A true CN105478094A (en) | 2016-04-13 |
| CN105478094B CN105478094B (en) | 2018-04-20 |
Family
ID=55665579
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510990399.7A Active CN105478094B (en) | 2015-12-25 | 2015-12-25 | Amination poly (glycidyl methacrylate) crosslinking complex microsphere and preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105478094B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106238016A (en) * | 2016-09-13 | 2016-12-21 | 苏州驿通滤材科技有限公司 | A kind of preparation method of bilirubin removal hemoperfusion resin sorbent |
| CN108743929A (en) * | 2018-06-14 | 2018-11-06 | 四川大学 | A kind of preparation method and purposes of the urase gel micro-ball as urea scavenger |
| CN111892681A (en) * | 2020-07-09 | 2020-11-06 | 江苏理工学院 | Preparation method and application of modified polymer microsphere adsorbent |
| CN114213581A (en) * | 2021-12-20 | 2022-03-22 | 南京亘闪生物科技有限公司 | Preparation method of hydrophilic polyacrylate crosslinked microspheres |
| CN114262465A (en) * | 2021-11-03 | 2022-04-01 | 赛分科技扬州有限公司 | Polyacrylate-based sphere and amine salt modification method thereof |
| CN115414921A (en) * | 2022-08-30 | 2022-12-02 | 赛分科技扬州有限公司 | Surface modification method of ion exchange filler |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001088047A (en) * | 1999-09-22 | 2001-04-03 | Honda Motor Co Ltd | Motor-driven wrench |
| CN101798372A (en) * | 2010-04-13 | 2010-08-11 | 苏州大学 | Polymer microsphere and preparation method thereof |
| CN103788301A (en) * | 2014-01-26 | 2014-05-14 | 上海交通大学 | Preparation method of chelation microspheres for adsorbing neodymium |
| CN104479354A (en) * | 2014-11-18 | 2015-04-01 | 四川大学 | In situ polymerization micro-crosslinking sodium polyacrylate modified polyether sulfone microspheres as well as preparation method and application thereof |
| CN104785225A (en) * | 2015-04-15 | 2015-07-22 | 浙江大学 | Method for preparing antiphase weak anion exchange mixed mode chromatographic stationary phase by using organic polymer as substrate |
-
2015
- 2015-12-25 CN CN201510990399.7A patent/CN105478094B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001088047A (en) * | 1999-09-22 | 2001-04-03 | Honda Motor Co Ltd | Motor-driven wrench |
| CN101798372A (en) * | 2010-04-13 | 2010-08-11 | 苏州大学 | Polymer microsphere and preparation method thereof |
| CN103788301A (en) * | 2014-01-26 | 2014-05-14 | 上海交通大学 | Preparation method of chelation microspheres for adsorbing neodymium |
| CN104479354A (en) * | 2014-11-18 | 2015-04-01 | 四川大学 | In situ polymerization micro-crosslinking sodium polyacrylate modified polyether sulfone microspheres as well as preparation method and application thereof |
| CN104785225A (en) * | 2015-04-15 | 2015-07-22 | 浙江大学 | Method for preparing antiphase weak anion exchange mixed mode chromatographic stationary phase by using organic polymer as substrate |
Non-Patent Citations (1)
| Title |
|---|
| 姜鑫 等: "功能化聚醚砜微球对胆红素的吸附研究", 《2015年全国高分子学术论文报告会》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106238016A (en) * | 2016-09-13 | 2016-12-21 | 苏州驿通滤材科技有限公司 | A kind of preparation method of bilirubin removal hemoperfusion resin sorbent |
| CN106238016B (en) * | 2016-09-13 | 2019-01-11 | 苏州驿通滤材科技有限公司 | A kind of bilirubin removal preparation method of blood perfusion resin sorbent |
| CN108743929A (en) * | 2018-06-14 | 2018-11-06 | 四川大学 | A kind of preparation method and purposes of the urase gel micro-ball as urea scavenger |
| CN108743929B (en) * | 2018-06-14 | 2021-07-27 | 四川大学 | Preparation method and application of urease gel microspheres used as urea scavenger |
| CN111892681A (en) * | 2020-07-09 | 2020-11-06 | 江苏理工学院 | Preparation method and application of modified polymer microsphere adsorbent |
| CN111892681B (en) * | 2020-07-09 | 2022-03-25 | 江苏理工学院 | Preparation method and application of modified polymer microsphere adsorbent |
| CN114262465A (en) * | 2021-11-03 | 2022-04-01 | 赛分科技扬州有限公司 | Polyacrylate-based sphere and amine salt modification method thereof |
| CN114213581A (en) * | 2021-12-20 | 2022-03-22 | 南京亘闪生物科技有限公司 | Preparation method of hydrophilic polyacrylate crosslinked microspheres |
| CN115414921A (en) * | 2022-08-30 | 2022-12-02 | 赛分科技扬州有限公司 | Surface modification method of ion exchange filler |
| CN115414921B (en) * | 2022-08-30 | 2024-05-14 | 赛分科技扬州有限公司 | Surface modification method of ion exchange filler |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105478094B (en) | 2018-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105478094A (en) | Aminated poly-glycidyl methacrylate crosslinked composite microsphere and preparation method as well as application thereof | |
| Moghbeli et al. | Nanosilica reinforced ion-exchange polyHIPE type membrane for removal of nickel ions: Preparation, characterization and adsorption studies | |
| Díaz-Álvarez et al. | Supported liquid membrane-protected molecularly imprinted beads for micro-solid phase extraction of sulfonamides in environmental waters | |
| Kyzas et al. | Relating interactions of dye molecules with chitosan to adsorption kinetic data | |
| CN107670513A (en) | A kind of plant polyphenol modifying polymer film and preparation method and application | |
| Wan et al. | Phosphate adsorption on novel hydrogel beads with interpenetrating network (IPN) structure in aqueous solutions: kinetics, isotherms and regeneration | |
| Guo et al. | Novel sandwich structure adsorptive membranes for removal of 4-nitrotoluene from water | |
| JP2004066153A (en) | Organic porous body having selective boron adsorption capability and boron removal module and ultrapure water production apparatus using the same | |
| Hu et al. | Poly (N-vinyl imidazole) gel composite porous membranes for rapid separation of dyes through permeating adsorption | |
| CN105435653A (en) | Composite nano filtration membrane with high selectivity on removing divalent ions and preparation method thereof | |
| Qiao et al. | Fabrication and characterization of porous cellulose beads with high strength and specific surface area via preliminary chemical cross-linking reaction for protein separation | |
| CN103756002B (en) | A kind of porous magnetic spherex and preparation method thereof | |
| Jiang et al. | Functional polyethersulfone particles for the removal of bilirubin | |
| Huang et al. | Phenol adsorption on α, α′-dichloro-p-xylene (DCX) and 4, 4′-bis (chloromethyl)-1, 1′-biphenyl (BCMBP) modified XAD-4 resins from aqueous solutions | |
| CN104945555B (en) | Prepare method and its application of Modified with Polar Monomer superhigh cross-linking type interpenetrating polymer networks | |
| Lian et al. | Microfluidic fabrication of porous polydimethylsiloxane microparticles for the treatment of toluene-contaminated water | |
| González-López et al. | Highly porous lignin composites for dye removal in batch and continuous-flow systems | |
| Ansari et al. | Investigation of the removal and recovery of nitrate by an amine-enriched composite under different fixed-bed column conditions | |
| Wolska et al. | Removal of bisphenol a from aqueous solution by molecularly imprinted polymers | |
| He et al. | Porous block polymer composite membranes for uranium uptake | |
| Beiler et al. | Poly (2-hydroxyethyl acrylate-co-ethyleneglycol dimethacrylate) monoliths synthesized by radiation polymerization in a mold | |
| Dulman et al. | Adsorption of anionic textile dye Acid Green 9 from aqueous solution onto weak or strong base anion exchangers | |
| Wang et al. | Preparation of inverse opal adsorbent by water-soluble colloidal crystal template to obtain ultrahigh adsorption capacity for salicylic acid removal from aqueous solution | |
| Hu et al. | Poly (N-vinyl imidazole) gel-filled membrane adsorbers for highly efficient removal of dyes from water | |
| Abumelha | Enhancing brilliant green dye removal via bio composite chitosan and food-grade algae capsulated ruthenium metal-organic framework: Optimization of adsorption parameters by box-behnken design |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |