CN102964523B - 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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- CN102964523B CN102964523B CN201210484299.3A CN201210484299A CN102964523B CN 102964523 B CN102964523 B CN 102964523B CN 201210484299 A CN201210484299 A CN 201210484299A CN 102964523 B CN102964523 B CN 102964523B
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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 the method for a kind of ultraviolet radiation graft modification for the preparation of 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 structure, with β-1 by D-Glucose, the macromolecular polysaccharide of 4-glycosidic link composition, hydroxyl on each dehydrated glucose unit is positioned at C-2, C-3 and C-6 position, there is the reaction property of typical primary alconol and secondary alcohol, can pass through a series of chemical modification, produce 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 multiple brand and serial Mierocrystalline cellulose commodity selling both at home and abroad.Due to the limitation of preparation means, commercially available cellulose adsorbent is mostly 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 made up the shortcoming of existing Mierocrystalline cellulose commodity, can control cell size, granularity, have that specific surface is large, transparent performance and the advantage such as mechanical property is good, be easy to operate on processing applicable 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, analyzing blood composition, remove antigen, absorption serum protein in blood plasma.Particularly in recent years, along with the development of blood purification technology, especially when critical illness is treated, it is more and more urgent that the demand of whole blood perfusion is carried out in requirement, people are extremely urgent to the good cellulose materials demand of Bc, therefore cause the interest of lot of domestic and international researcher about the preparation of ball shaped cellulose and the research of application.The variation of disease, its potential cause is the variation of virulence factor, thereby the function of the cellulose materials for blood purification has been proposed again to diversified requirement, to adapt to treat the needs of various disease.
Affecting Mierocrystalline cellulose, to apply one of maximum obstacle be that cellulosic solvability is lower, developed at present several different methods dissolving cellulos, as viscose process; Cuprammonium process; Organic or inorganic dissolution with solvents method is as adopted 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, is then directly dissolved in and in sig water, obtains spinning solution (FI61003; FI62318; US4404369); Sodium hydroxide/urea system dissolution method (CN101037479B) etc.These methods all lay particular emphasis on cellulosic dissolving.If in fact can be on cellulose modified basis fortifying fibre element solvability and dissolve after stability, be more conducive to the further application of cellulose materials.
Cellulose modified is the general name of giving again class methods of its new performance in the intrinsic advantage of Mierocrystalline cellulose is not destroyed retaining.Graft Copolymerization of Cellulose is the important method of modifying of a class wherein, is mainly 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.Positively charged ion initiation grafting is to adopt BF
3or TiCl
4deng metal halide and micro-catalyzer (as the water of trace or hydrochloric acid), carry out graft copolymerization by forming Mierocrystalline cellulose carbonium ion.Anionic initiation grafting is according to Michael reaction principle, makes the effect such as Mierocrystalline cellulose and sodium amide, rosaline metal-salt form alkoxide, then reacts with vinyl monomer, and monomer used has vinyl cyanide, methacrylic ester, methacrylonitrile etc.Solvent when graft copolymerization is liquefied ammonia, tetrahydrofuran (THF) or methyl-sulphoxide.The shortcoming of ionic copolymerization method is in anhydrous medium, to carry out, and under alkali metal hydroxide exists, Mierocrystalline cellulose may be degraded 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 (as epoxide, table thioether, epimino or lactan etc.), can be by the active hydroxyl on 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 applied early aspect fibre modification, the formation of free radical can and adopt the chemical activation method of redox system or initiator to obtain by physical methods such as the chain transfer reaction of initiator, energy emission or mechanical stresses, but aforesaid method also exists efficiency of initiation low, or easily damage 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 cellulose materials damage, reacting phase, to the method that is easy to control, rarely has report in cellulosic modification.
Summary of the invention
The invention provides the method for a kind of ultraviolet radiation graft modified-cellulose for the preparation of the cellulose materials of absorption virulence factor.Mierocrystalline cellulose after aforesaid method modification has improved solvability on the one hand, can on Mierocrystalline cellulose, introduce by the method on the other hand functional polymer, contribute to improve its physical strength, can be for the preparation of the material 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) after cotton fibre being immersed in sodium hydroxide solution and processing, then washing is to neutral, dry;
2), under lucifuge condition, with the cotton short fiber of light trigger and functional monomer solution soaking step (1) gained, filter;
3) surface deposition step (2) being 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 use dissolution with solvents step (4) gained;
6) with inversed phase emulsification, the cellulose solution of step (5) gained is prepared into function cellulose microballoon, prepares the cellulose materials for adsorbing virulence factor.
In the step (2) of aforesaid method, light trigger used is water-soluble light trigger, and it is selected from benzophenone soluble derivative or isopropyl thioxanthone soluble derivative, and described benzophenone soluble derivative is Quantacure BTC; Isopropyl thioxanthone soluble derivative is Quantacure QTX.And the mass concentration of light trigger used is 0.01%-0.15% in the step (2) of aforesaid method, preferably 0.05%-0.1%.
In the step (2) of aforesaid method, functional monomer used is vinylformic acid (AA) or MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC).The mass concentration of its functional monomer used is 0.01%-0.15%, preferably 0.05%-0.1%.
In the step (3) of aforesaid method, the UV Light time used is 1-20min, preferably 5-15min.Under UV-irradiation, reaction can be carried out in photoreactor, so-called photoreactor refers to and is specifically designed to photochemically reactive container, it is characterized in that on light-path, (generally referring to vertical direction) has the lid of a silica glass, the feature of silica glass is to absorb UV-light, is commonly used for the reaction unit of UV-light chemistry reaction.
The washing optional water of solvent used in the step (4) of aforesaid method, step (5) is dissolved solvent used can select the mixing solutions containing urea-sodium hydroxide.
More specifically, comprise the following steps:
1) take gossypin, adding mass concentration is 18% sodium hydroxide solution, pre-treatment after 24 hours at 20 DEG C, and suction filtration rinses to washing fluid as neutral, dries;
2) at 4 DEG C, the cotton short fiber element of functional monomer solution soaking step (1) gained that the light trigger that is 0.01%-0.15% by mass concentration under lucifuge condition and mass concentration are 0.01%-0.15% 4 hours, suction filtration;
3) surface deposition step (2) being obtained has the cellulosic short fiber of light trigger and functional monomer to be placed in photoreactor, be laid into the cotton short fiber thin layer that 0.1cm-1.0cm is thick in bottom, add silica glass upper cover, nitrogen deoxygenation 5-10min, open ultraviolet lamp, illumination 1-20min;
4) Mierocrystalline cellulose being soaked in water 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 sodium hydroxide mass concentration urea-sodium hydroxide mixing solutions that is 7% in dissolve;
6) cellulose solution of step (5) gained is joined and contained in the whiteruss that massfraction is 5%Span-80, under 500rpm, stir 3 hours, be warming up to gradually after 40 DEG C, be incubated 2 hours, take out, with ethyl acetate cleaning 4 times, clean 3 times with ethanol again, finally clean 3 times with 20% aqueous ethanolic solution, preserve with 20% aqueous ethanolic solution, obtain 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: benzophenone soluble derivative, and as Quantacure BTC, Quantacure BPQ and Quantacure ABP; Isopropyl thioxanthone (ITX) soluble derivative, 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 cellulosic structure unit by light trigger generates free radical, cause functional monomer polymerization, in fibrous texture unit, introduce functional polymer, these functional moleculars can be directly used in absorption virulence factor, if polyacrylic acid is for the absorption of low density lipoprotein, and grafting polymethyl acyl-oxygen ethyl-trimethyl salmiac can be used for bilirubin, inflammatory factor and endotoxic absorption, the introducing of these functional polymers simultaneously helps lend some impetus to the stability after cellulosic dissolving and dissolving, the physical strength of fortifying fibre element microballoon.
Based on above narration, significant advantage of the present invention and effect are:
1, graft polymerization initiation reaction occurs in solid phase surface, takes hydrogen efficiency of initiation by force 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 cellulose materials chain rupture.
3, for adopting aqueous systems to dissolve, the grafting of negatively charged ion or cationic polymers chain is more easily expanded polymer chain, all contributes to improve the stability after its solvability and dissolving.
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 are below described in detail in detail.It should be understood that embodiments of the invention are for illustrating the present invention instead of 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 cotton fibre 3g, add 18% sodium hydroxide solution at 20 DEG C, to process 24 hours, water rinses to neutral, dries.
2) get the Mierocrystalline cellulose after above-mentioned drying, adding and containing mass concentration is the acrylic acid aqueous solution that 0.05% Quantacure BTC and mass concentration are 0.1%, in 4 DEG C, soaks 4 hours suction filtration fast under sealing lucifuge condition;
3) have the cellulosic short fiber of light trigger and functional monomer to join in photoreactor the surface deposition after suction filtration, be laid in bottom 0.5cm thickness, add silica glass upper cover, nitrogen deoxygenation 5min, opens ultra violet lamp 10min;
4) close ultraviolet lamp, take out the Mierocrystalline cellulose in 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) by the cellulose graft thing after cleaning, add urea quality concentration be 12% and the sodium hydroxide mass concentration urea-sodium hydroxide solution that is 7% in dissolve.Centrifugal, take out upper solution (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, under 500rpm, stir 3 hours, be warming up to gradually 40 DEG C, keep 2 hours, take out, with ethyl acetate clean 4 times, and then with ethanol clean 3 times, finally clean 3 times with 20% aqueous ethanolic solution, stand-by with 20% aqueous ethanolic solution preservation.Gained cellulose microsphere is designated as EX1.
Embodiment 2:
1) take cotton fibre 3g, add 18% sodium hydroxide solution at 20 DEG C, to process 24 hours, water rinses to neutral, dries.
2) get the Mierocrystalline cellulose after above-mentioned drying, adding and containing mass concentration is the acrylic acid aqueous solution that 0.05%Quantacure BPQ and mass concentration are 0.1%, in 4 DEG C, soaks 4 hours suction filtration fast under sealing lucifuge condition;
3) have the cellulosic short fiber of light trigger and functional monomer to join in photoreactor the surface deposition after suction filtration, be laid in bottom 0.5cm thickness, add silica glass upper cover, nitrogen deoxygenation 5min, opens ultra violet lamp 10min;
4) close ultraviolet lamp, take out the Mierocrystalline cellulose in 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) by the cellulose graft thing after cleaning, add urea quality concentration be 12% and the sodium hydroxide mass concentration urea-sodium hydroxide solution that is 7% in dissolve.Centrifugal, take out upper solution (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, under 500rpm, stir 3 hours, be warming up to gradually 40 DEG C, keep 2 hours, take out, with ethyl acetate clean 4 times, and then with ethanol clean 3 times, finally clean 3 times with 20% aqueous ethanolic solution, stand-by with 20% aqueous ethanolic solution preservation.Gained cellulose microsphere is designated as EX2.
Embodiment 3:
1) take cotton fibre 3g, add 18% sodium hydroxide solution at 20 DEG C, to process 24 hours, water rinses to neutral, dries.
2) get the Mierocrystalline cellulose after above-mentioned drying, adding and containing mass concentration is the acrylic acid aqueous solution that 0.05% Quantacure ABP and mass concentration are 0.1%, in 4 DEG C, soaks 4 hours suction filtration fast under sealing lucifuge condition;
3) have the cellulosic short fiber of light trigger and functional monomer to join in photoreactor the surface deposition after suction filtration, be laid in bottom 0.5cm thickness, add silica glass upper cover, nitrogen deoxygenation 5min, opens ultra violet lamp 10min;
4) close ultraviolet lamp, take out the Mierocrystalline cellulose in 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) by the cellulose graft thing after cleaning, add urea quality concentration be 12% and the sodium hydroxide mass concentration urea-sodium hydroxide solution that is 7% in dissolve.Centrifugal, take out upper solution (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, under 500rpm, stir 3 hours, be warming up to gradually 40 DEG C, keep 2 hours, take out, with ethyl acetate clean 4 times, and then with ethanol clean 3 times, finally clean 3 times with 20% aqueous ethanolic solution, stand-by with 20% aqueous ethanolic solution preservation.Gained cellulose microsphere is designated as EX3.
Embodiment 4:
1) take cotton fibre 3g, add 18% sodium hydroxide solution at 20 DEG C, to process 24 hours, water rinses to neutral, dries.
2) get the Mierocrystalline cellulose after above-mentioned drying, adding and containing mass concentration is the acrylic acid aqueous solution that 0.05% Quantacure QTX and mass concentration are 0.1%, in 4 DEG C, soaks 4 hours suction filtration fast under sealing lucifuge condition;
3) have the cellulosic short fiber of light trigger and functional monomer to join in photoreactor the surface deposition after suction filtration, be laid in bottom 0.5cm thickness, add silica glass upper cover, nitrogen deoxygenation 5min, opens ultra violet lamp 10min;
4) close ultraviolet lamp, take out the Mierocrystalline cellulose in 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) by the cellulose graft thing after cleaning, add urea quality concentration be 12% and the sodium hydroxide mass concentration urea-sodium hydroxide solution that is 7% in dissolve.Centrifugal, take out upper solution (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, under 500rpm, stir 3 hours, be warming up to gradually 40 DEG C, keep 2 hours, take out, with ethyl acetate clean 4 times, and then with ethanol clean 3 times, finally clean 3 times with 20% aqueous ethanolic solution, stand-by with 20% aqueous ethanolic solution preservation.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.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.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.Gained cellulose microsphere is designated as EX7.
Embodiment 8:
Substantially with embodiment 1, difference is that the concentration of Quantacure BTC in step 2 is 0.01%.Gained cellulose microsphere is designated as EX8.
Embodiment 9:
Substantially with embodiment 1, difference is that the concentration of Quantacure BTC in step 2 is 0.1%.Gained cellulose microsphere is designated as EX9.
Embodiment 10:
Substantially with embodiment 1, difference is that the concentration of Quantacure BTC in step 2 is 0.15%.Gained cellulose microsphere is designated as EX10.
Embodiment 11:
Substantially with embodiment 1, difference is that the concentration of vinylformic acid in step 2 (AA) is 0.03%.Gained cellulose microsphere is designated as EX11.
Embodiment 12:
Substantially with embodiment 1, difference is that the concentration of vinylformic acid in step 2 (AA) is 0.05%.Gained cellulose microsphere is designated as EX12.
Embodiment 13:
Substantially with embodiment 1, difference is that the concentration of vinylformic acid in step 2 (AA) is 0.15%.Gained cellulose microsphere is designated as EX13.
Embodiment 14:
Substantially with embodiment 1, difference is that in step 3, light application time is 1min.Gained cellulose microsphere is designated as EX14.
Embodiment 15:
Substantially with embodiment 1, difference is that in step 3, light application time is 5min.Gained cellulose microsphere is designated as EX15.
Embodiment 16:
Substantially with embodiment 1, difference is that in step 3, light application time is 15min.Gained cellulose microsphere is designated as EX16.
Embodiment 17:
Substantially with embodiment 1, difference is that in step (3), light application time is 20min.Gained cellulose microsphere is designated as EX17.After illumination is cleaned, the general micro-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 centrifugal sediment, is polyacrylic acid crosslinked thing.
Embodiment 18:
Substantially with embodiment 1, difference is that monomer used in step (2) is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC).Gained cellulose microsphere is designated as EX18.
Embodiment 19:
1) take cotton fibre 3g, add 18% sodium hydroxide solution at 20 DEG C, to process 24 hours, water rinses to neutral, dries.
2) get the Mierocrystalline cellulose after above-mentioned drying, adding and containing mass concentration is the acrylic acid aqueous solution that 0.05% Quantacure QTX and mass concentration are 0.1%, in 4 DEG C, soaks 4 hours suction filtration fast under sealing lucifuge condition;
3) have the cellulosic short fiber of light trigger and functional monomer to join in photoreactor the surface deposition after suction filtration, be laid in bottom 0.5cm thickness, add silica glass upper cover, nitrogen deoxygenation 5min, opens ultra violet lamp 10min;
4) close ultraviolet lamp, take out the Mierocrystalline cellulose in 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) by the cellulose graft thing after cleaning, add urea quality concentration be 12% and the sodium hydroxide mass concentration urea-sodium hydroxide solution that is 7% in dissolve.Centrifugal, take out upper solution, centrifugal bottle bottom only has a small amount of brown insoluble particle material; Upper solution is placed after 20 days and is just occurred a small amount of microgel under room temperature.
Embodiment 20:
1) take cotton fibre 3g, add 18% sodium hydroxide solution at 20 DEG C, to process 24 hours, water rinses to neutral, dries.
2) get the Mierocrystalline cellulose after above-mentioned 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 DEG C, soaks 4 hours suction filtration fast under sealing lucifuge condition;
3) have the cellulosic short fiber of light trigger and functional monomer to join in photoreactor the surface deposition after suction filtration, be laid in bottom 0.5cm thickness, add silica glass upper cover, nitrogen deoxygenation 5min, opens ultra violet lamp 10min;
4) close ultraviolet lamp, take out the Mierocrystalline cellulose in 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) by the cellulose graft thing after cleaning, add urea quality concentration be 12% and the sodium hydroxide mass concentration urea-sodium hydroxide solution that is 7% in dissolve.Centrifugal, take out upper solution, centrifugal bottle bottom only has a small amount of brown insoluble particle material; Upper solution is placed after 20 days and is just occurred a small amount of microgel under room temperature.
Embodiment 21:
1) take cotton fibre 3g, add 18% sodium hydroxide solution at 20 DEG C, to process 24 hours, water rinses to neutral, dries.
2) by the cellulose graft thing after cleaning, add urea quality concentration be 12% and the sodium hydroxide mass concentration urea-sodium hydroxide solution that is 7% in dissolve.Centrifugal, take out upper solution, a small amount of brown insoluble particle material and part microgel shape material are arranged at centrifugal bottle bottom; Upper solution is placed after 4 days and is occurred gel under room temperature.
From embodiment 19, embodiment 20 and embodiment 21 can see, compared with the Mierocrystalline cellulose of not grafting, after grafted polyacrylic acid and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC), can promote on the one hand cellulosic dissolving completely, this may be because two kinds of graftomer are polyelectrolyte, in dissolution process, between molecular chain, electrostatic repulsion forces increases, make to produce a repulsive force between Mierocrystalline cellulose crystalline element, solvent molecule more easily enters, and contributes to cellulosic dissolving completely; After contributing on the other hand to dissolve, the existence of grafted chain itself makes to be not easy to form hydrogen bond between cellulosic molecule, and the electrostatic repulsion between grafted chain polyelectrolyte is more difficult near forming hydrogen bond cellulosic molecule simultaneously, thus more difficult gelation.
Absorption property test
1) absorption to low density lipoprotein
Get EX1-EX17 cellulose microsphere sample, screening particle diameter is the microballoon of 300-400 μ m, take the above-mentioned microballoon of 0.3g and be placed in Erlenmeyer flask, add 5ml blood plasma, at 36 DEG C, after constant temperature oscillation 2h, take out, centrifugation, get supernatant liquor measure the total cholesterol (TC) in blood plasma after absorption, low density lipoprotein cholesterol (LDL-C) and content high density lipoprotein cholesterol (HDL-C).To EX1-EX17 totally 17 samples carry out adsorption test, absorption result as table 1-4 as shown in.
The impact of the different light triggers of table 1 on absorption property
Note: TC before 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 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 sorbent material prepared by benzophenone derivates Quantacure BTC has comparability.Quantacure QTX and Quantacure BTC are with the obvious advantage.
The impact of table 2 Mierocrystalline cellulose tiling thickness on absorption property
Note: TC before 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 (as 1cm), absorption property obviously declines, and in the time that thickness is 0.1cm, absorption property increases, but not clearly, in the time of 0.1-0.7cm, absorption property is more or less the same, and easy handling control, therefore, thickness is preferably controlled at 0.1-0.7cm.
The impact of table 3 initiator concentration on absorption property
Note: TC before 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, in the time of photoinitiator concentration too low (0.01%) or too high (0.15%), adsorptive power all declines, this may be due to, when initiator concentration is too low, grafted chain quantity is inadequate, and initiator concentration is when too high, grafted chain density is large, but grafted chain is too short.Initiator concentration is preferably controlled at 0.05%-0.1%.
The impact of table 4 monomer concentration on absorption property
Note: TC before 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 declines, when especially AA concentration is low, decline obviously.Monomer concentration is preferably 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 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 too short (as 1min) or oversize (as 20min), adsorptive power all declines, the former may be due to too short causing of polyacrylic acid grafted chain, the latter may be because light application time is oversize, may exist micro-microgel relevant with cellulose solution after dissolving.Light application time is preferably controlled at 5-15min.
2) to bilirubinic absorption
Get EX185ml, pack chromatography column into
in, get severe liver diseases patient 100ml blood plasma, to adsorb 3 hours with the flow velocity circulation perfusion of 4.8ml/min, before and after absorption, leading indicator detected result is as shown in table 6.Compare with certain import and certain homemade goods respectively, the prepared cellulose microsphere of embodiment 18 has higher adsorption rate to bilirubin from the results of view, can have comparability with certain imported product of domestic listing, 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 absorption, the concentration of Dbil and Ibil is respectively: 443umol/L, 307umol/L and 136umol/L
3) absorption of induced by endotoxin
Get EX18, the each 0.1g of cellulose microsphere that sodium periodate oxidation and Epichlorohydrin activation legal system are standby, (blood plasma is adding before intracellular toxin through dilution heat treated to add the blood plasma that 6ml endogenous toxic material concentration is 90EU/mL, take out influence factor), then be placed in 37 DEG C of shaking tables, Static Adsorption 2 hours, with the endotoxin concns after gel method test absorption, result is as shown in table 7.
The absorption property of endotoxin absorbent prepared by table 7 different methods
As can be seen from Table 7, the EX18 induced by endotoxin absorption property that prepared by the inventive method is better than the absorption property of sodium periodate oxidation and the standby endotoxin absorbent of Epichlorohydrin activation legal system.
Claims (11)
1. for the preparation of the method for cellulose materials for absorption virulence factor, it is characterized in that comprising the following steps:
1) after cotton fibre being immersed in sodium hydroxide solution and processing, then washing is to neutral, dry;
2) under lucifuge condition, with the cotton short fiber of light trigger and functional monomer solution soaking step (1) gained, filter, described functional monomer is vinylformic acid (AA) or MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC);
3) surface deposition step (2) being 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 use dissolution with solvents step (4) gained;
6) with inversed phase emulsification, the cellulose solution of step (5) gained is prepared into function cellulose microballoon, obtains the cellulose materials for adsorbing virulence factor.
2. method according to claim 1, is characterized in that: the described light trigger of step (2) is water-soluble light trigger.
3. method according to claim 2, 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, is characterized in that: described benzophenone soluble derivative is Quantacure BTC; Isopropyl thioxanthone soluble derivative is Quantacure QTX.
5. method according to claim 1, 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, is characterized in that: the mass concentration of described light trigger is 0.05%-0.1%.
7. method according to claim 1, is characterized in that: the mass concentration of the functional monomer described in step (2) is 0.01%-0.15%.
8. method according to claim 7, is characterized in that: the mass concentration of described functional monomer is 0.05%-0.1%.
9. method according to claim 1, is characterized in that: the described UV Light time of step (3) is 1-20min.
10. method according to claim 9, is characterized in that: the described UV Light time is 5-15min.
The method of 11. a kind of cellulose materialss for the preparation of absorption virulence factor according to claim 1, is characterized in that comprising the following steps:
1) take gossypin, adding mass concentration is 18% sodium hydroxide solution, pre-treatment after 24 hours at 20 DEG C, and suction filtration rinses to washing fluid as neutral, dries;
2) at 4 DEG C, the cotton short fiber element of functional monomer solution soaking step (1) gained that the light trigger that is 0.01%-0.15% by mass concentration under lucifuge condition and mass concentration are 0.01%-0.15% 4 hours, suction filtration;
3) surface deposition step (2) being obtained has the cellulosic short fiber of light trigger and functional monomer to be placed in photoreactor, be laid into the cotton short fiber thin layer that 0.1cm-1.0cm is thick in bottom, add silica glass upper cover, nitrogen deoxygenation 5-10min, open ultraviolet lamp, illumination 1-20min;
4) Mierocrystalline cellulose being soaked in water 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 sodium hydroxide mass concentration urea-sodium hydroxide mixing solutions that is 7% in dissolve;
6) cellulose solution of step (5) gained is joined and contained in the whiteruss that massfraction is 5%Span-80, under 500rpm, stir 3 hours, be warming up to gradually after 40 DEG C, be incubated 2 hours, take out, with ethyl acetate cleaning 4 times, clean 3 times with ethanol again, finally clean 3 times with 20% aqueous ethanolic solution, preserve with 20% aqueous ethanolic solution, obtain the cellulose materials for virulence factor absorption.
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