CN100462140C - Channel augmentative method for fiber sphere separating medium - Google Patents
Channel augmentative method for fiber sphere separating medium Download PDFInfo
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- CN100462140C CN100462140C CNB2007100670874A CN200710067087A CN100462140C CN 100462140 C CN100462140 C CN 100462140C CN B2007100670874 A CNB2007100670874 A CN B2007100670874A CN 200710067087 A CN200710067087 A CN 200710067087A CN 100462140 C CN100462140 C CN 100462140C
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- 239000008107 starch Substances 0.000 claims abstract description 31
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 238000002955 isolation Methods 0.000 claims description 39
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- -1 xanthate ester Chemical class 0.000 claims description 20
- 230000003321 amplification Effects 0.000 claims description 16
- 238000003199 nucleic acid amplification method Methods 0.000 claims description 16
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- 238000001816 cooling Methods 0.000 claims description 13
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 10
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- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 10
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000005642 Oleic acid Substances 0.000 claims description 10
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 10
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 10
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- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 235000019483 Peanut oil Nutrition 0.000 claims description 4
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 4
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- 125000000524 functional group Chemical group 0.000 description 2
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a pore channel expanding method for a cellulose sphere separated substrate, with steps of: 1) preparing compound water phase by mixing gelling starch solution and cellulose xanthate viscose and agitating the same uniformly; 2) thermosetting to form a ball shape by combining an oil phase and a surfactant to form an inverse suspension disperse system, and rising the temperature; 3) removing starch by washing the solidified microsphere by boiled water for five times, adding amylase solution after cooled, then table separating, and water washing; 4) regenerating to obtain the sphere separated substrate by washing the microsphere using organic solvent and regenerating via acid, thus a macropore cellulose sphere separated substrate is obtained. The cellulose sphere separated substrate of the invention has characteristics of large aperture and high pore-size distribution, in addition to advantages of good hydrophilicity, degree of sphericity, acid and alkali resistance and low cost. A test experiment shows that the substrate is applicable to biological macromolecule chromatographic separation medium.
Description
Technical field
The present invention relates to the duct amplification method of the spherical isolation medium of a kind of cellulose.
Background technology
Developing rapidly of biotechnology and industrialization proposed more and more higher requirement to the bio-separation process, and biological technology products is the purity height often, and impurity component is had specific (special) requirements, also will keep biologically active as far as possible simultaneously.Chromatographic technique is that large biological molecule separates one of high-efficiency method, is usually used in the polishing purification process, produces the biological technology products of some high added values.The key of chromatography is exactly a chromatography media, has determined separative efficiency and production cost.The chromatography medium adopts porous material to prepare more at present, to increase specific area, improves adsorption capacity.
Cellulose is one of cheap, the abundantest natural polymer.The ball shaped cellulose isolation medium is applied to the downstream process of Bio-engineering Products with the hydrophily of its height, extremely low non-specific adsorption and higher mechanical strength as chromatography substrate.With the cellulose xanthate ester viscose is raw material, adopt " the hot method of reproduction of anti-phase suspension ", the cellulose microsphere that can prepare good sphericity, have certain inner duct, derive easily, and can in viscose glue, add the Expanded Bed Adsorption medium that some inert particles (as titanium dioxide or stainless steel powder etc.) formation has specific function, related invention is granted patent (ZL02111928.7 and ZL03142163.6).But, the duct of natural moulding is often less than normal in the cellulose regenerated process, can more seriously influence adsorbing separation and have large biological molecule than the large space size.Therefore, suitably increase the channel diameter of microballoon inside, will help the quick of large biological molecule and efficiently separate.
The method in present conventional isolation medium amplification duct mainly contains following two kinds.When preparing, adds by microballoon CaCO
3Superfines forms bigger aperture (J.Appl.Polym.Sci.1999,74:1278-1285 with the acid dissolving again; Number of patent application 200510013278.3), but CaCO
3Powder is graininess, can not form the spatial network duct after removing with acid, is not to be well suited for the rapid diffusion of protein and other in medium.(silicate journal, 2005,33 (8): 975-979), but polyethylene glycol is difficult to remove from cellulose microsphere, and the effect of drilling is not good enough yet to also have report interpolation polyethylene glycol that inorganic medium is carried out drilling.Seeking more effectively, the duct amplification method is the key of dealing with problems.
Starch is a kind of natural polysaccharide cheap and easy to get, its aqueous solution is able to gelatinization in boiling water, the physical property of gelatinized starch (as density, viscosity and colloid proterties) is quite similar with the cellulose xanthate ester viscose, both can mix well, and starch is very easy to be become little molecule glucose by amylorrhexis.The present invention is by adding gelatinized starch in the cellulose xanthate ester viscose, remove starch with amylorrhexis after solidifying balling-up, obtain having the ball shaped cellulose isolation medium of macropore cellulose skeleton structure, through further chemically derived adsorbent and the chromatography media that make with multiple functional group.
Cellulose and starch all are the raw materials of industry that very is easy to get, and up to now, also both are not combined the report of developing the spherical isolation medium of macropore cellulose
Summary of the invention
The duct amplification method that the purpose of this invention is to provide the spherical isolation medium of a kind of cellulose.
The duct amplification method of the spherical isolation medium of cellulose: in the cellulose xanthate ester viscose, add gelatinized starch, remove starch after the curing balling-up, obtain having the spherical isolation medium of macropore cellulose skeleton structure.
Starch is cornstarch, wheaten starch, tapioca, glutinous rice starch.The mass percentage concentration of gelatinized starch is 3～8%.The mass percent that the amount of lake starch accounts for compound water is 2～20%.
The concrete steps of the duct amplification method of the spherical isolation medium of cellulose are as follows:
1) prepares compound water
At room temperature be that 3～8% gelatinization of starch solution and cellulose xanthate ester viscose mix with concentration, stir, be warming up to 25～35 ℃, continue to stir 30～45 minutes, obtain compound water, the mass percent that the amount of lake starch accounts for compound water is 2～20%;
2) balling-up that is heating and curing that suspends
Add 4～6 times of oils decentralized photos and the surfactant of compound water quality in the whipping process, 25～35 ℃ of low suspensions disperseed 30～60 minutes, were warming up to 90～95 ℃, be incubateds 1.5～2 hours, and viscose glue curing obtains microballoon.
3) remove starch
Microballoon after solidifying is filtered out from oil phase, boiling water with 1～2 times of volume washs 3～6 times, cooling back adds mass concentration 2～3% amylase solutions of 1～2 times of microsphere volume, and shaking table reaction 1～2 hour is washed 3～5 times with the deionized water of 1～2 times of volume.
4) regeneration obtains spherical isolation medium
With the methyl alcohol of 2～3 times of volumes, the ethanolic solution that contains 30% acetate or the regeneration of 10% sulfuric acid solution, deionized water washing then, obtain the spherical isolation medium of macroporous type cellulose.
Mass ratio 200:1～the 1000:1 of described oils decentralized photo and surfactant.The oils decentralized photo is mixture, transformer oil or the peanut oil of pump oil and chlorobenzene, and wherein, pump oil is 3:1～6:1 with the mass ratio of chlorobenzene.
The invention has the advantages that: 1) aperture of microballoon inside increases, and accelerates the transmission speed of large biological molecule, is adapted to the chromatography operation requirement under the high flow rate; 2) preparation technology is simple, is easy to control and amplification; 3) with low cost, environmental pollution is little.
Description of drawings
Fig. 1 is the stereoscan photograph that the present invention prepares the spherical isolation medium of cellulose surface;
Fig. 2 is the stereoscan photograph that the present invention prepares the spherical isolation medium of cellulose inside.
The specific embodiment
The present invention takes " the hot method of reproduction of anti-phase suspension " on preparation technology, by add gelatinized starch in the cellulose xanthate ester viscose, remove starch after the curing balling-up, obtains having the spherical particle of cellulose of macroporous structure.Therefore, the spherical particle of the cellulose of being developed is through further chemically derived adsorbent and the chromatography media with multiple functional group that make.Prepare spherical isolation medium with macropore cellulose skeleton structure by the method.Cellulose skeleton is a cellulose xanthate ester viscose glue regrowth, and cellulosic quality percentage composition is 6.5～9% in the spherical isolation medium, and the water percentage composition is 75～90%.The spherical isolation medium of cellulose skeleton structure has tangible macroporous structure, and average pore size has reached 60～150nm, and the maximum diameter of hole can reach 0.3～1 μ m, and cell size is 80～95%, and specific area is 25～40m
2/ cm
3
The concrete steps of the duct amplification method of the spherical isolation medium of cellulose are as follows:
1) prepares compound water
At room temperature be that 3～8% gelatinization of starch solution and cellulose xanthate ester viscose mix with concentration, stir, be warming up to 25～35 ℃, continue to stir 30～45 minutes, obtain compound water, the mass percent that the amount of lake starch accounts for compound water is 2～20%;
2) balling-up that is heating and curing that suspends
Add 4～6 times of oils decentralized photos and the surfactant of compound water quality in the whipping process, 25～35 ℃ of low suspensions disperseed 30～60 minutes, were warming up to 90～95 ℃, be incubateds 1.5～2 hours, and viscose glue curing obtains microballoon.
3) remove starch
Microballoon after solidifying is filtered out from oil phase, boiling water with 1～2 times of volume washs 3～6 times, cooling back adds mass concentration 2～3% amylase solutions of 1～2 times of microsphere volume, and shaking table reaction 1～2 hour is washed 3～5 times with the deionized water of 1～2 times of volume.
4) regeneration obtains spherical isolation medium
With the methyl alcohol of 2～3 times of volumes, the ethanolic solution that contains 30% acetate or the regeneration of 10% sulfuric acid solution, deionized water washing then, obtain the spherical isolation medium of macroporous type cellulose.
Mass ratio 200:1～the 1000:1 of described oils decentralized photo and surfactant.The oils decentralized photo is mixture, transformer oil or the peanut oil of pump oil and chlorobenzene, and wherein, pump oil is 3:1～6:1 with the mass ratio of chlorobenzene.Surfactant is oleic acid and Span 80.
The invention will be further described by the following examples:
Embodiment 1
In the 500ml there-necked flask, add 50g cellulose xanthate ester viscose glue (the plain 4.1g of fibre-bearing, CS
21.5g NaOH 3.1g, viscosity is 6800cSt) and 1g concentration be 5% gelatinization tapioca, stirred 20 minutes under the room temperature; Be warming up to 30 ℃ and stir half an hour; Add mixing oil phase (pump oil: chlorobenzene=5:1, mass ratio) and the 2ml oleic acid of 300g, adjusting speed of agitator to 500 rev/min by pump oil and chlorobenzene preparation, it is constant to keep rotating speed, and 30 ℃ of low suspensions disperseed 45 minutes, were warming up to 90 ℃ in 15 minutes, be incubated 1.5 hours, curing obtains white microballoon; Microballoon is filtered out from oil phase, boiling water washing 5 times, the cooling back adds 2% amylase solution of 1 times of microsphere volume, and shaking table reaction 1 hour washes with water clean; With the ethanolic solution regeneration that contains 30% acetate 1 hour, use the methyl alcohol of 2 times of volumes and massive laundering to wash then, obtain the about 34ml of the spherical isolation medium of macroporous type cellulose, wet true density is 1.13g/cm
3, moisture content is 78%, specific area is 26.9m
2/ cm
3, average pore radius is 63.7nm, the largest hole radius can reach about 0.3 μ m.
Embodiment 2
In the 500ml there-necked flask, add 50g cellulose xanthate ester viscose glue (the plain 4.1g of fibre-bearing, CS
21.5g NaOH 3.1g, viscosity is 6800cSt) and 10g concentration be 5% gelatinization tapioca, stirred 20 minutes under the room temperature; Be warming up to 30 ℃ and stir half an hour; Add mixing oil phase (pump oil: chlorobenzene=5:1, mass ratio) and the 2ml oleic acid of 300g, adjusting speed of agitator to 500 rev/min by pump oil and chlorobenzene preparation, it is constant to keep rotating speed, and 30 ℃ of low suspensions disperseed 45 minutes, were warming up to 90 ℃ in 15 minutes, be incubated 1.5 hours, curing obtains white microballoon; Microballoon is filtered out from oil phase, boiling water washing 5 times, the cooling back adds 2% amylase solution of 1 times of microsphere volume, and shaking table reaction 1 hour washes with water clean; With the ethanolic solution regeneration that contains 30% acetate 1 hour, use the methyl alcohol of 3 times of volumes and massive laundering to wash then, obtain the about 38ml of the spherical isolation medium of macroporous type cellulose, wet true density is 1.09g/cm
3, moisture content is 90%, specific area is 38.1m
2/ cm
3, the calculating average pore radius is 141.6nm, the largest hole radius can reach about 1 μ m.
Embodiment 3
In the 500ml there-necked flask, add 50g cellulose xanthate ester viscose glue (the plain 4.1g of fibre-bearing, CS
21.5g NaOH 3.1g, viscosity is 6800cSt) and 5g concentration be 8% gelatinization cornstarch, stirred 20 minutes under the room temperature; Be warming up to 30 ℃ and stir half an hour; Add mixing oil phase (pump oil: chlorobenzene=5:1, mass ratio) and the 2ml oleic acid of 300g, adjusting speed of agitator to 500 rev/min by pump oil and chlorobenzene preparation, it is constant to keep rotating speed, and 30 ℃ of low suspensions disperseed 45 minutes, were warming up to 90 ℃ in 15 minutes, be incubated 1.5 hours, curing obtains white microballoon; Microballoon is filtered out from oil phase, boiling water washing 5 times, the cooling back adds 2% amylase solution of 1 times of microsphere volume, and shaking table reaction 1 hour washes with water clean; With the ethanolic solution regeneration that contains 30% acetate 1 hour, use the methyl alcohol of 2 times of volumes and massive laundering to wash then, obtain the about 36ml of the spherical isolation medium of macroporous type cellulose, wet true density is 1.12g/cm
3, moisture content is 83%, specific area is 31.4m
2/ cm
3, the calculating average pore radius is 82.3nm, the largest hole radius can reach about 0.8 μ m.
Embodiment 4
In the 500ml there-necked flask, add 50g cellulose xanthate ester viscose glue (the plain 4.1g of fibre-bearing, CS
21.5g NaOH 3.1g, viscosity is 6800cSt) and 5g concentration be 3% gelatinization glutinous rice starch, stirred 20 minutes under the room temperature; Be warming up to 30 ℃ and stir half an hour; Add mixing oil phase (pump oil: chlorobenzene=5:1, mass ratio) and the 2ml oleic acid of 300g, adjusting speed of agitator to 500 rev/min by pump oil and chlorobenzene preparation, it is constant to keep rotating speed, and 30 ℃ of low suspensions disperseed 45 minutes, were warming up to 90 ℃ in 15 minutes, be incubated 1.5 hours, curing obtains white microballoon; Microballoon is filtered out from oil phase, boiling water washing 5 times, the cooling back adds 2% amylase solution of 1 times of microsphere volume, and shaking table reaction 1 hour washes with water clean; With the ethanolic solution regeneration that contains 30% acetate 1 hour, use the methyl alcohol of 3 times of volumes and massive laundering to wash then, obtain the about 36ml of microballoon, wet true density is 1.12g/cm
3, moisture content is 85%, specific area is 30.4m
2/ cm
3, the calculating average pore radius is 79.3nm, the largest hole radius can reach about 0.8 μ m.
Embodiment 5
In the 500ml there-necked flask, add 50g cellulose xanthate ester viscose glue (the plain 4.1g of fibre-bearing, CS
21.5g NaOH 3.1g, viscosity is 6800cSt) and 5g concentration be 6% gelatinization wheaten starch, stirred 20 minutes under the room temperature; Be warming up to 30 ℃ and stir half an hour; Add mixing oil phase (pump oil: chlorobenzene=5:1, mass ratio) and the 2ml oleic acid of 300g, adjusting speed of agitator to 500 rev/min by pump oil and chlorobenzene preparation, it is constant to keep rotating speed, and 30 ℃ of low suspensions disperseed 45 minutes, were warming up to 90 ℃ in 15 minutes, be incubated 1.5 hours, curing obtains white microballoon; Microballoon is filtered out from oil phase, boiling water washing 5 times, the cooling back adds 2% amylase solution of 1 times of microsphere volume, and shaking table reaction 1 hour washes with water clean; With the ethanolic solution regeneration that contains 30% acetate 1 hour, use the methyl alcohol of 2 times of volumes and massive laundering to wash then, obtain the about 36ml of the spherical isolation medium of macroporous type cellulose, wet true density is 1.11g/cm
3, moisture content is 88%, specific area is 34.5m
2/ cm
3, the calculating average pore radius is 93.1nm, the largest hole radius can reach about 0.7 μ n.
Embodiment 6
In the 500ml there-necked flask, add 50g cellulose xanthate ester viscose glue (the plain 4.1g of fibre-bearing, CS
21.5g NaOH 3.1g, viscosity is 6800cSt) and 3g concentration be 5% gelatinization tapioca, stirred 20 minutes under the room temperature; Be warming up to 30 ℃ and stir half an hour; Add mixing oil phase (pump oil: chlorobenzene=5:1, mass ratio) and the 2ml oleic acid of 300g, adjusting speed of agitator to 500 rev/min by pump oil and chlorobenzene preparation, it is constant to keep rotating speed, and 30 ℃ of low suspensions disperseed 45 minutes, were warming up to 90 ℃ in 15 minutes, be incubated 1.5 hours, curing obtains white microballoon; Microballoon is filtered out from oil phase, boiling water washing 5 times, the cooling back adds 2% amylase solution of 1 times of microsphere volume, and shaking table reaction 1 hour washes with water clean; With the ethanolic solution regeneration that contains 30% acetate 1 hour, use the methyl alcohol of 3 times of volumes and massive laundering to wash then, obtain the about 36ml of the spherical isolation medium of macroporous type cellulose, wet true density is 1.12g/cm
3, moisture content is 82%, specific area is 28.4m
2/ cm
3, the calculating average pore radius is 70.3nm, the largest hole radius can reach about 0.5 μ m.
Embodiment 7
In the 500ml there-necked flask, add 50g cellulose xanthate ester viscose glue (the plain 4.1g of fibre-bearing, CS
21.5g NaOH 3.1g, viscosity is 6800cSt) and 5g concentration be 5% gelatinization tapioca, stirred 20 minutes under the room temperature; Be warming up to 30 ℃ and stir half an hour; Add mixing oil phase (pump oil: chlorobenzene=5:1, mass ratio) and the 2ml oleic acid of 300g, adjusting speed of agitator to 500 rev/min by pump oil and chlorobenzene preparation, it is constant to keep rotating speed, and 30 ℃ of low suspensions disperseed 45 minutes, were warming up to 90 ℃ in 15 minutes, be incubated 1.5 hours, curing obtains white microballoon; Microballoon is filtered out from oil phase, boiling water washing 5 times, the cooling back adds 2% amylase solution of 1 times of microsphere volume, and shaking table reaction 1 hour washes with water clean; With the ethanolic solution regeneration that contains 30% acetate 1 hour, use the methyl alcohol of 3 times of volumes and massive laundering to wash then, obtain the about 36ml of the spherical isolation medium of macroporous type cellulose, wet true density is 1.12g/cm
3, moisture content is 84%, specific area is 32.2m
2/ cm
3, the calculating average pore radius is 83.1nm, the largest hole radius can reach about 0.7 μ m.
Embodiment 8
In the 500ml there-necked flask, add 50g cellulose xanthate ester viscose glue (the plain 4.1g of fibre-bearing, CS
21.5g NaOH 3.1g, viscosity is 6800cSt) and 7g concentration be 5% gelatinization tapioca, stirred 20 minutes under the room temperature; Be warming up to 30 ℃ and stir half an hour; Add mixing oil phase (pump oil: chlorobenzene=5:1, mass ratio) and the 2ml oleic acid of 300g, adjusting speed of agitator to 500 rev/min by pump oil and chlorobenzene preparation, it is constant to keep rotating speed, and 30 ℃ of low suspensions disperseed 45 minutes, were warming up to 90 ℃ in 15 minutes, be incubated 1.5 hours, curing obtains white microballoon; Microballoon is filtered out from oil phase, boiling water washing 5 times, the cooling back adds 2% amylase solution of 1 times of microsphere volume, and shaking table reaction 1 hour washes with water clean; With the ethanolic solution regeneration that contains 30% acetate 1 hour, use the methyl alcohol of 2 times of volumes and massive laundering to wash then, obtain the about 38ml of the spherical isolation medium of macroporous type cellulose, wet true density is 1.11g/cm
3, moisture content is 88%, specific area is 34.8m
2/ cm
3, the calculating average pore radius is 123.1nm, the largest hole radius can reach about 1 μ m.
Embodiment 9
In the 500ml there-necked flask, add 50g cellulose xanthate ester viscose glue (the plain 4.1g of fibre-bearing, CS
21.5g NaOH 3.1g, viscosity is 6800cSt) and 5g concentration be 5% gelatinization tapioca, stirred 20 minutes under the room temperature; Be warming up to 30 ℃ and stir half an hour; Add 280g transformer oil and 1.2g Span 80, regulate speed of agitator to 550 rev/min, it is constant to keep rotating speed, and 30 ℃ of low suspensions disperseed 45 minutes, were warming up to 90 ℃ in 15 minutes, be incubateds 1.5 hours, and curing obtains white microballoon; Microballoon is filtered out from oil phase, boiling water washing 5 times, the cooling back adds 2% amylase solution of 1 times of microsphere volume, and shaking table reaction 1 hour washes with water clean; With the ethanolic solution regeneration that contains 30% acetate 1 hour, use the methyl alcohol of 2 times of volumes and massive laundering to wash then, obtain the about 33ml of the spherical isolation medium of macroporous type cellulose, wet true density is 1.12g/cm
3, moisture content is 85%, specific area is 30.5m
2/ cm
3, the calculating average pore radius is 80.2nm, the largest hole radius can reach about 0.7 μ m.
Embodiment 10
In the 500ml there-necked flask, add 50g cellulose xanthate ester viscose glue (the plain 4.1g of fibre-bearing, CS
21.5g NaOH 3.1g, viscosity is 6800cSt) and 5g concentration be 5% gelatinization tapioca, stirred 20 minutes under the room temperature; Be warming up to 30 ℃ and stir half an hour; Add 300g peanut oil and 1.5g Span 80, regulate speed of agitator to 650 rev/min, it is constant to keep rotating speed, and 30 ℃ of low suspensions disperseed 45 minutes, were warming up to 90 ℃ in 15 minutes, be incubateds 1.5 hours, and curing obtains white microballoon; Microballoon is filtered out from oil phase, boiling water washing 5 times, the cooling back adds 2% amylase solution of 1 times of microsphere volume, and shaking table reaction 1 hour washes with water clean; With the ethanolic solution regeneration that contains 30% acetate 1 hour, use the methyl alcohol of 3 times of volumes and massive laundering to wash then, obtain the about 35ml of the spherical isolation medium of macroporous type cellulose, wet true density is 1.12g/cm
3, moisture content is 83%, specific area is 31.8m
2/ cm
3, the calculating average pore radius is 85.5nm, the largest hole radius can reach about 0.7 μ m.
Claims (7)
1. the duct amplification method of the spherical isolation medium of cellulose is characterized in that: add gelatinized starch in the cellulose xanthate ester viscose, remove starch after the curing balling-up, obtain having the spherical isolation medium of macropore cellulose skeleton structure.
2. the duct amplification method of the spherical isolation medium of a kind of cellulose according to claim 1 is characterized in that described starch is cornstarch, wheaten starch, tapioca or glutinous rice starch.
3. the duct amplification method of the spherical isolation medium of a kind of cellulose according to claim 1, the mass percentage concentration that it is characterized in that described gelatinized starch is 3～8%.
4. the duct amplification method of the spherical isolation medium of a kind of cellulose according to claim 1 is characterized in that the concrete steps of method are as follows:
1) prepares compound water
At room temperature be that 3～8% gelatinization of starch solution and cellulose xanthate ester viscose mix with concentration, stir, be warming up to 25～35 ℃, continue to stir 30～45 minutes, obtain compound water, the mass percent that the amount of gelatinized starch accounts for compound water is 2～20%;
2) balling-up that is heating and curing that suspends
Add 4～6 times of oils decentralized photos and the surfactant of compound water quality in the whipping process, 25～35 ℃ of low suspensions disperseed 30～60 minutes, were warming up to 90～95 ℃, be incubateds 1.5～2 hours, and viscose glue curing obtains microballoon;
3) remove starch
Microballoon after solidifying is filtered out from oil phase, boiling water with 1～2 times of volume washs 3～6 times, cooling back adds mass concentration 2～3% amylase solutions of 1～2 times of microsphere volume, and shaking table reaction 1～2 hour is washed 3～5 times with the deionized water of 1～2 times of volume;
4) regeneration obtains spherical isolation medium
With the methyl alcohol of 2～3 times of volumes with contain the ethanolic solution or the regeneration of 10% sulfuric acid solution of 30% acetate, deionized water washing then obtains the spherical isolation medium of macroporous type cellulose.
5. the duct amplification method of the spherical isolation medium of a kind of cellulose according to claim 4 is characterized in that the mass ratio 200:1～1000:1 of described oils decentralized photo and surfactant.
6. the duct amplification method of the spherical isolation medium of a kind of cellulose according to claim 4 is characterized in that described surfactant is oleic acid and Span80.
7. the duct amplification method of the spherical isolation medium of a kind of cellulose according to claim 4 is characterized in that described oils decentralized photo is mixture, transformer oil or the peanut oil of pump oil and chlorobenzene, and wherein, pump oil is 3:1～6:1 with the mass ratio of chlorobenzene.
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| CN1586705A (en) * | 2004-07-16 | 2005-03-02 | 浙江大学 | Process for preparing macroporous cellulose sodium sulfate-polydimethyl diallyl ammonium chloride biolgoical micro capsule |
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