CN102964523A - Method for preparing cellulose material for adsorbing pathogenic factors - Google Patents
Method for preparing cellulose material for adsorbing pathogenic factors Download PDFInfo
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- CN102964523A CN102964523A CN2012104842993A CN201210484299A CN102964523A CN 102964523 A CN102964523 A CN 102964523A CN 2012104842993 A CN2012104842993 A CN 2012104842993A CN 201210484299 A CN201210484299 A CN 201210484299A CN 102964523 A CN102964523 A CN 102964523A
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Abstract
The invention relates to a method for preparing a cellulose material for adsorbing pathogenic factors. According to the method, a photoinitiator is initiated by ultraviolet lights on the surface of a short cotton fiber, so that free radicals are generated on the surface of the fiber and functional monomer polymerization is initiated; and a functionalized polymer is introduced in a fiber structural unit and then the cellulose material for adsorbing the pathogenic factors is prepared. The grafting reaction efficiency of the method is high, the destructive effect on the material is small, the cellulose material is not prone to chain scission, the increase of the solubility and the stability after the solubility of cellulose is benefited after a water-soluble polymer (polyelectrolyte) is grafted, and graft polymerization and functionalization of the cellulose can be realized within one-step reaction, thus the demands of blood purification on different functional groups are met.
Description
Technical field
The present invention relates to a kind of ultraviolet radiation graft modification for the preparation of the method for the cellulose materials of absorption virulence factor, belong to biomedical material and blood purification field.
Background technology
Mierocrystalline cellulose is the abundantest, the inexpensive and reproducible biomolecules of nature.Mierocrystalline cellulose is on structure, with β-1 by D-Glucose, the macromolecular polysaccharide that the 4-glycosidic link forms, hydroxyl on each dehydrated glucose unit is positioned at C-2, C-3 and C-6 position, reaction property with typical primary alconol and secondary alcohol can pass through a series of chemical modification, produces the functional high molecule material of different purposes.Therefore countries in the world are all attached great importance to cellulosic research and development.
A cellulosic item important application is exactly cellulose adsorbent, and its development and application starts from the beginning of the fifties, has at present the Mierocrystalline cellulose commodity selling of multiple brand and series both at home and abroad.Because the limitation of preparation means, commercially available cellulose adsorbent mostly is greatly powdery or microgranular, and pore structure is not so good, has restricted to a great extent its use range.And spherical cellulose adsorbent has just in time remedied the shortcoming of existing Mierocrystalline cellulose commodity, can control cell size, granularity, the advantage such as have that specific surface is large, transparent performance and mechanical property are good, be easy to operate on processing and the suitable post, and the enrichment that can be used to separation and purification bacterialα-amylase, preparation and separating chiral compound, Purification of Chloroplast DNA, adsorbing metal ions, separates transition metal ion, reclaims valuable gold, radioactive metal, the analyzing blood composition, remove antigen, absorption serum protein in the blood plasma.Particularly in recent years, development along with blood purification technology, when especially critical illness is treated, it is more and more urgent that the demand of whole blood perfusion is carried out in requirement, therefore people are extremely urgent to the good cellulose materials demand of Bc, cause the interest of lot of domestic and international researcher about the research of the preparation of ball shaped cellulose and application.The variation of disease, its potential cause is the variation of virulence factor, thereby the function of the cellulose materials that is used for blood purification has been proposed again diversified requirement, to adapt to the needs for the treatment of various disease.
Affecting one of maximum obstacle of Mierocrystalline cellulose application is that cellulosic solvability is lower, has developed at present the several different methods dissolving cellulos, such as viscose process; Cuprammonium process; Organic or inorganic dissolution with solvents method is as adopting dromisol one oxynitride (US3236669,1966), the ZnCl2 aqueous solution (US5290349,1994), LiCl/DMAc (US4302252,1981), N-methyl oxidation beautiful jade (NIMO) (US2179181,1939; GB1144048,1967; US4246221,1981), NaOH aqua-solution method (JP1777283,1983; US4634470 must use the wood pulp cellulose of processing through steam explosion, and the polymerization degree is lower than 250); Urea-Mierocrystalline cellulose pyroreaction generates cellulose carbamate, then directly is dissolved in and obtains spinning solution (FI61003 in the sig water; FI62318; US4404369); Sodium hydroxide/urea system dissolution method (CN101037479B) etc.These methods all lay particular emphasis on cellulosic dissolving.If in fact can in the solvability of fortifying fibre element on the cellulose modified basis and the stability after the dissolving, then more be conducive to the further application of cellulose materials.
Cellulose modified is the general name of giving again class methods of its new performance when the intrinsic advantage of Mierocrystalline cellulose is not destroyed keeping.Graft Copolymerization of Cellulose is the important method of modifying of a class wherein, mainly is divided into ionic copolymerization and polycondensation, the forms such as ring-opening polymerization and radical polymerization.
Ionic graft copolymer fibre element can be divided into positively charged ion or anionic initiation graft copolymerization.The positively charged ion initiation grafting is to adopt BF
3Or TiCl
4Deng the catalyzer (such as water or the hydrochloric acid of trace) of metal halide and trace, carry out graft copolymerization by forming the Mierocrystalline cellulose carbonium ion.The anionic initiation grafting then is according to the Michael reaction principle, makes the effects such as Mierocrystalline cellulose and sodium amide, rosaline metal-salt form alkoxide, and with the vinyl monomer reaction, used monomer has vinyl cyanide, methacrylic ester, methacrylonitrile etc. again.Solvent during graft copolymerization is liquefied ammonia, tetrahydrofuran (THF) or methyl-sulphoxide.The shortcoming of ionic copolymerization method is to need to carry out in anhydrous medium, and Mierocrystalline cellulose may be degraded in the presence of alkali metal hydroxide in addition, so proportion is less in graft copolymerization is synthetic.
Mierocrystalline cellulose also can carry out grafting by polycondensation and ring-opening polymerization; Many cyclic monomers (such as epoxide, table thioether, epimino or lactan etc.) can be by the active hydroxyl on the Mierocrystalline cellulose, or Mierocrystalline cellulose the slight oxidation carboxyl or the carbonyl that generate, causes ring-opening reaction and generates graft copolymer.
Free yl graft polymerization is used aspect fibre modification early, the formation of free radical can be by initiator the physical method such as chain transfer reaction, energy emission or mechanical stress and adopt the chemical activation method of redox system or initiator to obtain, but aforesaid method also exists efficiency of initiation low, or damage easily cellulosic substrates, or reaction is difficult to the deficiencies such as control.And cause free yl graft polymerization for UV-light, this simple, little to the cellulose materials damage, the method for reacting phase to being easy to control then rarely has report in cellulosic modification.
Summary of the invention
The invention provides a kind of ultraviolet radiation graft modified-cellulose for the preparation of the method for the cellulose materials of absorption virulence factor.Mierocrystalline cellulose after the aforesaid method modification has improved solvability on the one hand, can introduce functional polymer at Mierocrystalline cellulose by the method on the other hand, help to improve its physical strength, can be for the preparation of the material that is used for the various virulence factor absorption of adsorbed plasma.
For achieving the above object, technical scheme of the present invention is as follows:
Ultraviolet radiation graft modified-cellulose of the present invention is for the preparation of the method for the cellulose materials of absorption virulence factor, and it comprises the steps:
1) cotton fibre is immersed in the sodium hydroxide solution process after, washing is to neutral again, drying;
2) under the lucifuge condition, with the cotton short fiber of light trigger and functional monomer solution soaking step (1) gained, filter;
3) surface deposition that step (2) is obtained has the cotton short fiber of light trigger and functional monomer to react under UV-irradiation;
4) with the reacted Mierocrystalline cellulose of solvent wash step (3) gained, remove unreacted monomer and homopolymer;
5) Mierocrystalline cellulose of usefulness dissolution with solvents step (4) gained;
6) with inversed phase emulsification the cellulose solution of step (5) gained is prepared into the function chemical fibre and ties up plain microballoon, prepare the cellulose materials for the absorption virulence factor.
Used light trigger is water-soluble light trigger in the step of aforesaid method (2), and it is selected from benzophenone soluble derivative or isopropyl thioxanthone soluble derivative, and described benzophenone soluble derivative is Quantacure BTC; The isopropyl thioxanthone soluble derivative is Quantacure QTX.And the mass concentration of used light trigger is 0.01%-0.15% in the step of aforesaid method (2), preferred 0.05%-0.1%.
Used functional monomer is vinylformic acid (AA) or MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC) in the step of aforesaid method (2).The mass concentration of the functional monomer that it is used is 0.01%-0.15%, preferred 0.05%-0.1%.
The used UV Light time is 1-20min in the step of aforesaid method (3), preferred 5-15min.Reaction can be carried out in photoreactor under the UV-irradiation, so-called photoreactor refers to be specifically designed to photochemically reactive container, it is characterized in that (generally referring to vertical direction) on the light-path has the lid of a silica glass, the characteristics of silica glass are can absorbing ultraviolet light, are commonly used for the reaction unit of UV-light chemistry reaction.
The used optional water of solvent of washing in the step of aforesaid method (4), the used solvent of step (5) dissolving can be selected the mixing solutions that contains urea-sodium hydroxide.
More specifically, may further comprise the steps:
1) take by weighing gossypin, the adding mass concentration is 18% sodium hydroxide solution, and after 24 hours, it is neutral that suction filtration washes to washing fluid, dries in 20 ℃ of lower pre-treatment;
2) under 4 ℃, under the lucifuge condition, be the cotton short fiber element 4 hours of the light trigger of 0.01%-0.15% and functional monomer solution soaking step (1) gained that mass concentration is 0.01%-0.15% with mass concentration, suction filtration;
3) surface deposition that step (2) is obtained has the cellulosic short fiber of light trigger and functional monomer to place photoreactor, be tiled into the thick cotton short fiber thin layer of 0.1cm-1.0cm in the bottom, add the silica glass loam cake, nitrogen deoxygenation 5-10min, open ultraviolet lamp, illumination 1-20min;
4) be soaked in water Mierocrystalline cellulose after the illumination of cleaning step (3) gained changes water one time every 15min, cleans altogether 4 times, then filters, and removes the homopolymer of unreacted light trigger, monomer and monomer;
5) the cellulose graft thing after the cleaning of step (4) gained is joined urea quality concentration be 12% and the sodium hydroxide mass concentration be to dissolve in 7% urea-sodium hydroxide mixing solutions;
6) cellulose solution of step (5) gained is joined contain in the whiteruss that massfraction is 5%Span-80, stirred 3 hours under the 500rpm, after being warming up to gradually 40 ℃, be incubated 2 hours, take out, clean 4 times with ethyl acetate, clean 3 times with ethanol again, clean 3 times with 20% aqueous ethanolic solution at last, preserve with 20% aqueous ethanolic solution, namely get the cellulose materials for virulence factor absorption.
Hydrogen-capture-type light initiator of the present invention is selected from but is not limited to following several: the benzophenone soluble derivative, and such as Quantacure BTC, Quantacure BPQ and Quantacure ABP; Isopropyl thioxanthone (ITX) soluble derivative is such as Quantacure QTX.Above-mentioned light trigger is water miscible, is suitable for the graft reaction of water-soluble monomer.Preferred photoinitiator is: Quantacure BTC and Quantacure QTX.The structure of each light trigger is as follows:
Light trigger can be selected from benzophenone soluble derivative and isopropyl thioxanthone soluble derivative, be preferably: benzophenone derivates Quantacure BTC and isopropyl thioxanthone soluble derivative Quantacure QTX, its mass concentration that accounts for described solution is 0.01%-0.15%, is preferably 0.05%-0.1%; Functional monomer is vinylformic acid (AA) and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC), and its mass concentration that accounts for described solution is 0.01%-0.15%, is preferably 0.05%-0.1%; The thickness of cotton short fiber thin layer is 0.1-1cm, is preferably 0.1-0.7cm; Light application time is selected from 1-20min, is preferably 5-15min.
Cardinal principle of the present invention is: at solid phase interface, the hydrogen atom of capturing on the methyne on 6 of the cellulosic structure unit by light trigger generates free radical, cause the functional monomer polymerization, in the fibrous texture unit, introduce functional polymer, these functional moleculars can be directly used in the absorption virulence factor, be used for the absorption of low density lipoprotein such as polyacrylic acid, and grafting polymethyl acyl-oxygen ethyl-trimethyl salmiac can be used for bilirubin, inflammatory factor and endotoxic absorption, the simultaneously introducing of these functional polymers helps lend some impetus to the stability after cellulosic dissolving and the dissolving, the physical strength of fortifying fibre element microballoon.
Based on above narration, significant advantage of the present invention and effect are:
1, the graft polymerization initiation reaction occurs in solid phase surface, takes the hydrogen efficiency of initiation by force and is higher than liquid phase homogeneous phase graft reaction;
2, compare radiation graft polymerization, UV-light causes little to the destruction of material itself, is not easy to cause the cellulose materials chain rupture.
3, for adopting the aqueous systems dissolving, the grafting of negatively charged ion or cationic polymers chain makes the easier expansion of polymer chain, the stability after all helping to improve its solvability and dissolve.
4, can in single step reaction, realize cellulosic graft polymerization and functionalization, or introduce functional polymer, be conducive to further functionalization, adapt to blood purification to difference in functionality group demand, realize the individual character functionalization of blood purification material.
Embodiment
Embodiments of the invention below are described in detail in detail.It should be understood that embodiments of the invention are used to illustrate the present invention rather than limitation of the present invention.The improvement that essence according to the present invention is carried out all belongs to the scope of protection of present invention.
Embodiment 1:
1) take by weighing cotton fibre 3g, the sodium hydroxide solution of adding 18% is in 20 ℃ of lower processing 24 hours, and the water flushing is dried to neutrality.
2) get Mierocrystalline cellulose after above-mentioned the drying, adding and containing mass concentration is that 0.05% Quantacure BTC and mass concentration are 0.1% acrylic acid aqueous solution, in 4 ℃, soaks 4 hours under the sealing lucifuge condition, fast suction filtration;
3) have the cellulosic short fiber of light trigger and functional monomer to join in the photoreactor surface deposition behind the suction filtration, be tiled in bottom 0.5cm thickness, add the silica glass loam cake, nitrogen deoxygenation 5min opens ultra violet lamp 10min;
4) close ultraviolet lamp, take out the Mierocrystalline cellulose in the reactor, be soaked in water, change water one time every 15min, clean altogether 4 times, then filter, remove unreacted light trigger, monomer and homopolymer.
5) add in the cellulose graft thing after will cleaning urea quality concentration be 12% and the sodium hydroxide mass concentration be to dissolve in urea-sodium hydroxide solution of 7%.Centrifugal, take out upper solution (the centrifugal bottle bottom only has a small amount of brown insoluble particle material); Join in the whiteruss organic phase that 250g contains 5%Span-80, stirred 3 hours under the 500rpm, be warming up to gradually 40 ℃, kept 2 hours, take out, clean 4 times with ethyl acetate, and then clean 3 times with ethanol, clean 3 times with 20% aqueous ethanolic solution at last, preserve stand-by with 20% aqueous ethanolic solution.The gained cellulose microsphere is designated as EX1.
Embodiment 2:
1) take by weighing cotton fibre 3g, the sodium hydroxide solution of adding 18% is in 20 ℃ of lower processing 24 hours, and the water flushing is dried to neutrality.
2) get Mierocrystalline cellulose after above-mentioned the drying, adding and containing mass concentration is that 0.05%Quantacure BPQ and mass concentration are 0.1% acrylic acid aqueous solution, in 4 ℃, soaks 4 hours under the sealing lucifuge condition, fast suction filtration;
3) have the cellulosic short fiber of light trigger and functional monomer to join in the photoreactor surface deposition behind the suction filtration, be tiled in bottom 0.5cm thickness, add the silica glass loam cake, nitrogen deoxygenation 5min opens ultra violet lamp 10min;
4) close ultraviolet lamp, take out the Mierocrystalline cellulose in the reactor, be soaked in water, change water one time every 15min, clean altogether 4 times, then filter, remove unreacted light trigger, monomer and homopolymer.
5) add in the cellulose graft thing after will cleaning urea quality concentration be 12% and the sodium hydroxide mass concentration be to dissolve in urea-sodium hydroxide solution of 7%.Centrifugal, take out upper solution (the centrifugal bottle bottom only has a small amount of brown insoluble particle material); Join in the whiteruss organic phase that 250g contains 5%Span-80, stirred 3 hours under the 500rpm, be warming up to gradually 40 ℃, kept 2 hours, take out, clean 4 times with ethyl acetate, and then clean 3 times with ethanol, clean 3 times with 20% aqueous ethanolic solution at last, preserve stand-by with 20% aqueous ethanolic solution.The gained cellulose microsphere is designated as EX2.
Embodiment 3:
1) take by weighing cotton fibre 3g, the sodium hydroxide solution of adding 18% is in 20 ℃ of lower processing 24 hours, and the water flushing is dried to neutrality.
2) get Mierocrystalline cellulose after above-mentioned the drying, adding and containing mass concentration is that 0.05% Quantacure ABP and mass concentration are 0.1% acrylic acid aqueous solution, in 4 ℃, soaks 4 hours under the sealing lucifuge condition, fast suction filtration;
3) have the cellulosic short fiber of light trigger and functional monomer to join in the photoreactor surface deposition behind the suction filtration, be tiled in bottom 0.5cm thickness, add the silica glass loam cake, nitrogen deoxygenation 5min opens ultra violet lamp 10min;
4) close ultraviolet lamp, take out the Mierocrystalline cellulose in the reactor, be soaked in water, change water one time every 15min, clean altogether 4 times, then filter, remove unreacted light trigger, monomer and homopolymer.
5) add in the cellulose graft thing after will cleaning urea quality concentration be 12% and the sodium hydroxide mass concentration be to dissolve in urea-sodium hydroxide solution of 7%.Centrifugal, take out upper solution (the centrifugal bottle bottom only has a small amount of brown insoluble particle material); Join in the whiteruss organic phase that 250g contains 5%Span-80, stirred 3 hours under the 500rpm, be warming up to gradually 40 ℃, kept 2 hours, take out, clean 4 times with ethyl acetate, and then clean 3 times with ethanol, clean 3 times with 20% aqueous ethanolic solution at last, preserve stand-by with 20% aqueous ethanolic solution.The gained cellulose microsphere is designated as EX3.
Embodiment 4:
1) take by weighing cotton fibre 3g, the sodium hydroxide solution of adding 18% is in 20 ℃ of lower processing 24 hours, and the water flushing is dried to neutrality.
2) get Mierocrystalline cellulose after above-mentioned the drying, adding and containing mass concentration is that 0.05% Quantacure QTX and mass concentration are 0.1% acrylic acid aqueous solution, in 4 ℃, soaks 4 hours under the sealing lucifuge condition, fast suction filtration;
3) have the cellulosic short fiber of light trigger and functional monomer to join in the photoreactor surface deposition behind the suction filtration, be tiled in bottom 0.5cm thickness, add the silica glass loam cake, nitrogen deoxygenation 5min opens ultra violet lamp 10min;
4) close ultraviolet lamp, take out the Mierocrystalline cellulose in the reactor, be soaked in water, change water one time every 15min, clean altogether 4 times, then filter, remove unreacted light trigger, monomer and homopolymer;
5) add in the cellulose graft thing after will cleaning urea quality concentration be 12% and the sodium hydroxide mass concentration be to dissolve in urea-sodium hydroxide solution of 7%.Centrifugal, take out upper solution (the centrifugal bottle bottom only has a small amount of brown insoluble particle material); Join in the whiteruss organic phase that 250g contains 5%Span-80, stirred 3 hours under the 500rpm, be warming up to gradually 40 ℃, kept 2 hours, take out, clean 4 times with ethyl acetate, and then clean 3 times with ethanol, clean 3 times with 20% aqueous ethanolic solution at last, preserve stand-by with 20% aqueous ethanolic solution.The gained cellulose microsphere is designated as EX4.
Embodiment 5:
Substantially with embodiment 1, difference is that the thickness of the cotton short fiber tiling of step 3 is 0.1cm.The gained cellulose microsphere is designated as EX5.
Embodiment 6:
Substantially with embodiment 1, difference is that the thickness of the cotton short fiber tiling of step 3 is 0.8cm.The gained cellulose microsphere is designated as EX6.
Embodiment 7:
Substantially with embodiment 1, difference is that the thickness of the cotton short fiber tiling of step 3 is 1cm.The gained cellulose microsphere is designated as EX7.
Embodiment 8:
Substantially with embodiment 1, difference is that the concentration of Quantacure BTC in the step 2 is 0.01%.The gained cellulose microsphere is designated as EX8.
Embodiment 9:
Substantially with embodiment 1, difference is that the concentration of Quantacure BTC in the step 2 is 0.1%.The gained cellulose microsphere is designated as EX9.
Embodiment 10:
Substantially with embodiment 1, difference is that the concentration of Quantacure BTC in the step 2 is 0.15%.The gained cellulose microsphere is designated as EX10.
Embodiment 11:
Substantially with embodiment 1, difference is that the concentration of vinylformic acid in the step 2 (AA) is 0.03%.The gained cellulose microsphere is designated as EX11.
Embodiment 12:
Substantially with embodiment 1, difference is that the concentration of vinylformic acid in the step 2 (AA) is 0.05%.The gained cellulose microsphere is designated as EX12.
Embodiment 13:
Substantially with embodiment 1, difference is that the concentration of vinylformic acid in the step 2 (AA) is 0.15%.The gained cellulose microsphere is designated as EX13.
Embodiment 14:
Substantially with embodiment 1, difference is that light application time is 1min in the step 3.The gained cellulose microsphere is designated as EX14.
Embodiment 15:
Substantially with embodiment 1, difference is that light application time is 5min in the step 3.The gained cellulose microsphere is designated as EX15.
Embodiment 16:
Substantially with embodiment 1, difference is that light application time is 15min in the step 3.The gained cellulose microsphere is designated as EX16.
Embodiment 17:
Substantially with embodiment 1, difference is that light application time is 20min in the step (3).The gained cellulose microsphere is designated as EX17.After illumination is cleaned, the general little Huang of Mierocrystalline cellulose, there is micro-microgel in the upper solution after cellulose dissolution is centrifugal, occurs being insoluble on a small quantity the cross-linked polymer of sodium hydroxide/urea system in the centrifugal sediment, is polyacrylic acid crosslinked thing.
Embodiment 18:
Substantially with embodiment 1, difference is that monomer used in the step (2) is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC).The gained cellulose microsphere is designated as EX18.
Embodiment 19:
1) take by weighing cotton fibre 3g, the sodium hydroxide solution of adding 18% is in 20 ℃ of lower processing 24 hours, and the water flushing is dried to neutrality.
2) get Mierocrystalline cellulose after above-mentioned the drying, adding and containing mass concentration is that 0.05% Quantacure QTX and mass concentration are 0.1% acrylic acid aqueous solution, in 4 ℃, soaks 4 hours under the sealing lucifuge condition, fast suction filtration;
3) have the cellulosic short fiber of light trigger and functional monomer to join in the photoreactor surface deposition behind the suction filtration, be tiled in bottom 0.5cm thickness, add the silica glass loam cake, nitrogen deoxygenation 5min opens ultra violet lamp 10min;
4) close ultraviolet lamp, take out the Mierocrystalline cellulose in the reactor, be soaked in water, change water one time every 15min, clean altogether 4 times, then filter, remove unreacted light trigger, monomer and homopolymer.
5) add in the cellulose graft thing after will cleaning urea quality concentration be 12% and the sodium hydroxide mass concentration be to dissolve in urea-sodium hydroxide solution of 7%.Centrifugal, take out upper solution, the centrifugal bottle bottom only has a small amount of brown insoluble particle material; Upper solution a small amount of microgel just occurs after placing 20 days under the room temperature.
Embodiment 20:
1) take by weighing cotton fibre 3g, the sodium hydroxide solution of adding 18% is in 20 ℃ of lower processing 24 hours, and the water flushing is dried to neutrality.
2) get Mierocrystalline cellulose after above-mentioned the drying, adding and containing mass concentration is that 0.05% Quantacure QTX and mass concentration are 0.1% MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC), in 4 ℃, soaks 4 hours under the sealing lucifuge condition, fast suction filtration;
3) have the cellulosic short fiber of light trigger and functional monomer to join in the photoreactor surface deposition behind the suction filtration, be tiled in bottom 0.5cm thickness, add the silica glass loam cake, nitrogen deoxygenation 5min opens ultra violet lamp 10min;
4) close ultraviolet lamp, take out the Mierocrystalline cellulose in the reactor, be soaked in water, change water one time every 15min, clean altogether 4 times, then filter, remove unreacted light trigger, monomer and homopolymer.
5) add in the cellulose graft thing after will cleaning urea quality concentration be 12% and the sodium hydroxide mass concentration be to dissolve in urea-sodium hydroxide solution of 7%.Centrifugal, take out upper solution, the centrifugal bottle bottom only has a small amount of brown insoluble particle material; Upper solution a small amount of microgel just occurs after placing 20 days under the room temperature.
Embodiment 21:
1) take by weighing cotton fibre 3g, the sodium hydroxide solution of adding 18% is in 20 ℃ of lower processing 24 hours, and the water flushing is dried to neutrality.
2) add in the cellulose graft thing after will cleaning urea quality concentration be 12% and the sodium hydroxide mass concentration be to dissolve in urea-sodium hydroxide solution of 7%.Centrifugal, take out upper solution, a small amount of brown insoluble particle material and part microgel shape material are arranged at the centrifugal bottle bottom; Upper solution gel occurs after placing 4 days under the room temperature.
From embodiment 19, embodiment 20 and embodiment 21 can see, compare with the Mierocrystalline cellulose of not grafting, behind grafted polyacrylic acid and the MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC), can promote on the one hand cellulosic fully dissolving, this may be because two kinds of graftomer are polyelectrolyte, electrostatic repulsion forces increase between molecular chain in the dissolution process, so that produce a repulsive force between the Mierocrystalline cellulose crystalline element, solvent molecule is easier to be entered, and helps cellulosic fully dissolving; After helping on the other hand dissolving, the existence of grafted chain itself is so that be not easy to form hydrogen bond between cellulosic molecule, simultaneously the electrostatic repulsion between the grafted chain polyelectrolyte so that cellulosic molecule more be difficult near the formation hydrogen bond, thereby more difficult gelation.
The absorption property test
1) to the absorption of low density lipoprotein
Get EX1-EX17 cellulose microsphere sample, the screening particle diameter is the microballoon of 300-400 μ m, take by weighing the above-mentioned microballoon of 0.3g and place Erlenmeyer flask, add 5ml blood plasma, behind 36 ℃ of lower constant temperature oscillation 2h, take out, centrifugation is got supernatant liquor and is measured the total cholesterol (TC) in the rear blood plasma of absorption, the content high density lipoprotein cholesterol (HDL-C) that low density lipoprotein cholesterol (LDL-C) reaches.To EX1-EX17 totally 17 samples carry out adsorption test, absorption result as the table 1-4 shown in.
The different light triggers of table 1 are on the impact of absorption property
Annotate: TC before the absorption, the concentration of LDL-C and HDL-C is respectively 119mg/dl, 27.4mg/dl and 91.6mg/dl
As can be seen from Table 1, in 3 kinds of benzophenone initiators, along with the water soluble group chain increases, absorption property is on a declining curve, and this may be relevant with the hydrogen initiated polymerization ability of taking by force of these three kinds of light triggers.Isopropyl thioxanthone derivative Quantacure QTX causes the performance of prepared sorbent material and the performance of the sorbent material that benzophenone derivates Quantacure BTC prepares has comparability.Quantacure QTX and Quantacure BTC are with the obvious advantage.
Table 2 Mierocrystalline cellulose tiling thickness is on the impact of absorption property
Annotate: TC before the absorption, the concentration of LDL-C and HDL-C is respectively 119mg/dl, 27.4mg/dl and 91.6mg/dl
As can be seen from Table 2, when Mierocrystalline cellulose thickness too large (such as 1cm), absorption property obviously descends, and when thickness was 0.1cm, absorption property increased, but not clearly, when 0.1-0.7cm, absorption property is more or less the same, and easy handling control, therefore, thickness preferably is controlled at 0.1-0.7cm.
Table 3 initiator concentration is on the impact of absorption property
Annotate: TC before the absorption, the concentration of LDL-C and HDL-C is respectively 119mg/dl, 27.4mg/dl and 91.6mg/dl
As can be seen from Table 3, when photoinitiator concentration too low (0.01%) or too high (0.15%), adsorptive power all descends, this may be because, when initiator concentration was too low, grafted chain quantity was inadequate, and initiator concentration is when too high, and grafted chain density is large, but grafted chain is too short.Initiator concentration preferably is controlled at 0.05%-0.1%.
Table 4 monomer concentration is on the impact of absorption property
Annotate: TC before the absorption, the concentration of LDL-C and HDL-C is respectively 119mg/dl, 27.4mg/dl and 91.6mg/dl
As can be seen from Table 4, when vinylformic acid (AA) concentration too low (0.03%) or when too high (0.15%), adsorptive power all descends, descend obviously when especially AA concentration is low.Monomer concentration preferably is controlled at 0.05%-0.1%.According to the characteristic of UV-induced grafting, we can infer that the concentration of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC) also should be proper at 0.05%-0.1%.
The impact of table 5 light application time
TC before the absorption, the concentration of LDL-C and HDL-C is respectively 119mg/dl, 27.4mg/dl and 90.9mg/dl
As can be seen from Table 5, light application time is lacked very much (such as 1min) or oversize (such as 20min), adsorptive power all descends, the former may be because polyacrylic acid grafted chain short causing too, the latter then may be because light application time is oversize, then may exist micro-microgel relevant in the cellulose solution afterwards with dissolving.Light application time preferably is controlled at 5-15min.
2) to bilirubinic absorption
Get EX185ml, the chromatography column of packing into
In, get severe liver diseases patient 100ml blood plasma, with the flow velocity circulation perfusion of 4.8ml/min absorption 3 hours, the leading indicator detected result was as shown in table 6 before and after the absorption.Compare with certain import and certain homemade goods respectively, from result embodiment 18 prepared cellulose microspheres bilirubin is had higher adsorption rate, can have comparability with certain imported product of domestic listing, be higher than the Adsorption of The Bilirubin of certain homemade goods.
The comparison of the prepared sorbent material of table 6 and commercially produced product absorption property
Tbil before the absorption, the concentration of Dbil and Ibil is respectively: 443umol/L, 307umol/L and 136umol/L
3) absorption of induced by endotoxin
Get EX18, each 0.1g of cellulose microsphere that sodium periodate oxidation and Epichlorohydrin activation legal system are standby, add the blood plasma that 6ml endogenous toxic material concentration is 90EU/mL (blood plasma before adding intracellular toxin through the dilution heat treated, take out influence factor), then place 37 ℃ of shaking tables, Static Adsorption 2 hours, with the endotoxin concns after the gel method test absorption, the result is as shown in table 7.
The absorption property of the endotoxin absorbent of table 7 different methods preparation
As can be seen from Table 7, the EX18 induced by endotoxin absorption property of the inventive method preparation is better than the absorption property of the standby endotoxin absorbent of sodium periodate oxidation and Epichlorohydrin activation legal system.
Claims (12)
1. method of cellulose materials for the preparation of the absorption virulence factor is characterized in that may further comprise the steps:
1) cotton fibre is immersed in the sodium hydroxide solution process after, washing is to neutral again, drying;
2) under the lucifuge condition, with the cotton short fiber of light trigger and functional monomer solution soaking step (1) gained, filter;
3) surface deposition that step (2) is obtained has the cotton short fiber of light trigger and functional monomer to react under UV-irradiation;
4) with the reacted Mierocrystalline cellulose of solvent wash step (3) gained, remove unreacted monomer and homopolymer;
5) Mierocrystalline cellulose of usefulness dissolution with solvents step (4) gained;
6) with inversed phase emulsification the cellulose solution of step (5) gained is prepared into the function chemical fibre and ties up plain microballoon, obtain the cellulose materials for the absorption virulence factor.
2. method according to claim 1, it is characterized in that: the described light trigger of step (2) is water-soluble light trigger.
3. method according to claim 2, it is characterized in that: described water-soluble light trigger is selected from benzophenone soluble derivative or isopropyl thioxanthone soluble derivative.
4. method according to claim 3, it is characterized in that: described benzophenone soluble derivative is Quantacure BTC; The isopropyl thioxanthone soluble derivative is Quantacure QTX.
5. method according to claim 1, it is characterized in that: the mass concentration of the described light trigger of step (2) is 0.01%-0.15%.
6. method according to claim 5, it is characterized in that: the mass concentration of described light trigger is 0.05%-0.1%.
7. method according to claim 1, it is characterized in that: the described functional monomer of step (2) is vinylformic acid (AA) or MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC).
8. method according to claim 1, it is characterized in that: the mass concentration of the described functional monomer of step (2) is 0.01%-0.15%.
9. method according to claim 8, it is characterized in that: the mass concentration of described functional monomer is 0.05%-0.1%.
10. method according to claim 1, it is characterized in that: the described UV Light time of step (3) is 1-20min.
11. method according to claim 10 is characterized in that: the described UV Light time is 5-15min.
12. the method for a kind of cellulose materials for the preparation of adsorbing virulence factor according to claim 1 is characterized in that may further comprise the steps:
1) take by weighing gossypin, the adding mass concentration is 18% sodium hydroxide solution, and after 24 hours, it is neutral that suction filtration washes to washing fluid, dries in 20 ℃ of lower pre-treatment;
2) under 4 ℃, under the lucifuge condition, be the cotton short fiber element 4 hours of the light trigger of 0.01%-0.15% and functional monomer solution soaking step (1) gained that mass concentration is 0.01%-0.15% with mass concentration, suction filtration;
3) surface deposition that step (2) is obtained has the cellulosic short fiber of light trigger and functional monomer to place photoreactor, be tiled into the thick cotton short fiber thin layer of 0.1cm-1.0cm in the bottom, add the silica glass loam cake, nitrogen deoxygenation 5-10min, open ultraviolet lamp, illumination 1-20min;
4) be soaked in water Mierocrystalline cellulose after the illumination of cleaning step (3) gained changes water one time every 15min, cleans altogether 4 times, filters, and removes the homopolymer of unreacted light trigger, monomer and monomer;
5) the cellulose graft thing after the cleaning of step (4) gained is joined urea quality concentration be 12% and the sodium hydroxide mass concentration be to dissolve in 7% urea-sodium hydroxide mixing solutions;
6) cellulose solution of step (5) gained is joined contain in the whiteruss that massfraction is 5%Span-80, stirred 3 hours under the 500rpm, after being warming up to gradually 40 ℃, be incubated 2 hours, take out, clean 4 times with ethyl acetate, clean 3 times with ethanol again, clean 3 times with 20% aqueous ethanolic solution at last, preserve with 20% aqueous ethanolic solution, namely get the cellulose materials for virulence factor absorption.
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| WO2004050750A1 (en) * | 2002-12-04 | 2004-06-17 | Specialty Coatings (Aust) Pty Ltd | Reinforced polymer composition |
| CN101575818A (en) * | 2008-05-08 | 2009-11-11 | 袁志平 | Method for fabricating chemical fiber paste by cotton linters without soda boiling, pollution and basically drainage |
| CN101581051A (en) * | 2008-05-14 | 2009-11-18 | 李跃怡 | Clean pulping method of linters |
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| WO2004050750A1 (en) * | 2002-12-04 | 2004-06-17 | Specialty Coatings (Aust) Pty Ltd | Reinforced polymer composition |
| CN101575818A (en) * | 2008-05-08 | 2009-11-11 | 袁志平 | Method for fabricating chemical fiber paste by cotton linters without soda boiling, pollution and basically drainage |
| CN101581051A (en) * | 2008-05-14 | 2009-11-18 | 李跃怡 | Clean pulping method of linters |
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| CN107486176A (en) * | 2017-09-11 | 2017-12-19 | 广州康盛生物科技有限公司 | A kind of sorbing material for blood purification and preparation method thereof |
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