CN1089618C - Process for preparing porous filler of regenerated cellulose for gel permeation chromatographic column - Google Patents
Process for preparing porous filler of regenerated cellulose for gel permeation chromatographic column Download PDFInfo
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- CN1089618C CN1089618C CN98113654A CN98113654A CN1089618C CN 1089618 C CN1089618 C CN 1089618C CN 98113654 A CN98113654 A CN 98113654A CN 98113654 A CN98113654 A CN 98113654A CN 1089618 C CN1089618 C CN 1089618C
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- chromatographic column
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- filler
- gel permeation
- permeation chromatographic
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Abstract
The present invention discloses a method for preparing porous cylindrical filler of regenerated cellulose for a gel permeation chromatographic column. The present invention has the method that 6 to 10% of cellulose cuprammonium solution is evenly mixed with a macromolecule pore forming agent according to different proportions; mixed liquid is extruded into a filament shape, is solidified in 0 to 10% of a NaOH water solution from 20 to 40 DEG C, is regenerated in an H2SO4 water solution and finally is cut into a cylinder with a proper length to obtain gel permeation chromatographic filler. A chromatographic column made by the filler can be used for classifying, separating and purifying macro molecules such as high molecular biopolymers, synthetic polymers, etc. in water or various organic solvents. The prepared gel permeation chromatographic column has the characteristics of convenience, high speed and low cost.
Description
The present invention relates to a kind of method of preparative chromatography post porous aggregate, specifically is exactly to utilize cotton linter pulp, polyethylene glycol, konjacmannan gelatin to be raw material, prepares the method for porous regenerated cellulose cylinder filler.It belongs to technical field of polymer chemistry, also belongs to the chromatography technical field.
All very important in industrial production and research with the separation of preparation type gel permeation chromatographic column, classification or the big molecule of purifying biological or synthetic polymer.Especially not only energy-conservation for large biological molecule with the chromatographic column separation, and can protect big molecule to exempt from thermal denaturation.Crosslinked polystyrene, glucan, agar-agar and polyacrylamide and the Bio-sil of the general employing of chromatographic column filler.Because these filler manufacture crafts are complicated, and strict control working condition.Therefore chromatographic column filler is all very expensive for a long time.Cellulose, polyethylene glycol, konjacmannan and gelatin abundant raw material and inexpensive, utilizing them is that raw material production preparative scale chromatography column packing not only can reduce cost, and helps the development and utilization regenerated resources.
In recent years there is the new development of cellulose family chromatographic column filler research mainly to adopt cellulose/17.5%NaOH aqueous solution (day disclosure special permission communique, A, flat 2-2335944,1990), the dark liquid of 9.2% cellulose viscose glue (day disclosure special permission communique, A, clear 63-92603,1988), cellulose/calcium thiocyanate solution (J.Chromatogr.A, 720,151,1996) be mixed with the porous cellulose bead of filler material with other additive.The weak point of these methods is to be difficult to make large aperture cellulose pearl filler, and particle is thin, the phase resistance that flows is bigger, thereby has placed restrictions on its application aspect separation, classification and purified high-molecular material.
Purpose of the present invention provides a kind of method of preparative chromatography post porous aggregate, and it is that raw material prepares porous regenerated cellulose cylinder filler by cuprammonium process that this method will adopt cotton linter pulp, is used for preparation type gel permeation chromatographic column.The manufacture craft of this filler should be simple, and is easy to operate, can be made into various different apertures, especially wide-aperture filler.The chromatographic column that this filler is made is easy, quick, inexpensive, and is applicable to that water and various organic solvents do to flow mutually, separable, classification and the various natural and synthetic polymer substances of purifying.
For realizing that the measure that the object of the invention adopted is:
A kind of method for preparing porous filler of regenerated cellulose for gel permeation chromatographic column, this method is to be that the 0-1 macromolecule pore former doubly of content of cellulose evenly mixes with the cellulose cuprammonia of 6-10wt% and weight, injection is extruded and is formed the filamentous with certain diameter and enter in the 0-20wt%NaOH aqueous solution and solidify under 20-40 ℃ then, again at 4-10wt%H
2SO
4Regenerate in the aqueous solution, after the water flushing silk is cut into the cylinder particle of Len req.
By technical scheme of the present invention, described cellulose cuprammonia is for what prepare by the method described in the document CN1091144, and described pore former is polyethylene glycol, konjacmannan or gelatin etc.
The preparation of porous regenerated cellulose cylinder filler, its pore size is by different molecular weight polyethylene glycol and konjacmannan control, and they are moved out of cellulosic solidifying with the regenerative process major part, play the pore former effect.Obtain various different apertures by different formulations and technology, especially wide-aperture porous filler of regenerated cellulose.For example use konjacmannan (viscosity average molecular weigh M
n=4.2 * 10
-4) when making pore former, the cellulose cuprammonia solidifies in 40 ℃ of hot water and at 10wt%H
2SO
4Its surface apertures of regeneration back reaches 360mm in the aqueous solution, and cross-sectional aperture is 1400mm.Solidify in the 10wt%NaOH aqueous solution for the cellulose cuprammonia of pore former and at 4wt%H with polyethylene glycol (M=2000)
2SO
4Its surface apertures of cylindrical multi-hole granule of regenerating in the aqueous solution is 140nm, and cross-sectional aperture is 600nm.The surface apertures that does not add the regenerated cellulose porous grain of any pore former is 90nm, cross-sectional aperture is 180nm, because regenerated cellulose has good high and low temperature resistance and solvent resistance, therefore this filler can be-40-100 ℃ normal down the use, can make water and various organic solvents do to flow mutually by the chromatographic column of this filler equipment.Be used for the separating of polysaccharide, protein and synthetic polymer, classification and purifying.This porous aggregate is prepared into the cylinder of 300 μ m * 1200 μ m, thereby the phase resistance that helps reducing flowing improves service efficiency.The gel permeation chromatographic column that adopts the filler in different apertures to equip by a certain percentage can be used for the big molecule of different molecular weight.For 500mm * 20mm chromatographic column preparation amount every day is the 4-7g polymer substance.
Key technology of the present invention is to join that the macromolecule as pore former requires to shift out from regenerated cellulose solidifying and regenerative process in the cellulose copper ammon solution, forms uniform loose structure thus.The kind of pore former, molecular weight and consumption, the curing of the plain liquid of CUP and actified solution and temperature all have material impact to the aperture and the porosity of porous regenerated fiber crude granule.
The present invention has substantive different compared to the prior art, and marked improvement is arranged.The present invention is mixed with porous regenerated cellulose cylinder filler and is used for preparation type gel permeation chromatographic column with CUP cellulose solution and polyethylene glycol or konjacmannan first.The pore size of filler is controlled easily, and easily makes the large aperture filler.The filler production technology is simple, easy to operate and cost of manufacture is low, and therefore the preparation type gel permeation chromatographic column that is particularly suitable for producing in enormous quantities is used.
Below in conjunction with specific embodiment technical measures of the present invention are further described:
Embodiment 1
By former method (patent publication No. CN1091144A) preparation 6wt% cellulose copper ammon solution (I), configuration 20wt% polyethylene glycol (PEG2000) aqueous solution (II).Is to mix at 1: 1 I and II by the weight ratio of cellulose and polyethylene glycol, extrudes this mixed liquor by syringe then, forms diameter and solidifies 5min for the 0.3mm filamentous enters in the 10wt%NaOH aqueous solution, again at 4wt%H
2SO
4Regenerate in the aqueous solution, wash 30min with flowing water at last.Silk is cut into the long cylinder particle of 0.5-1.5mm and is kept in 20% isopropyl alcohol/2% formaldehyde, be numbered RCG-2.
Embodiment 2
The 6wt% cellulose cuprammonia that does not add polyethylene glycol is prepared the regenerated cellulose grain by aforesaid operations, be numbered RCG.1.
In the 550mm * 20mm glass column of packing into after RCG-2 and the RCG-1 mixing in 3: 1 by volume, make preparation type glue penetration chromatographic column thus.It is fine that this post is respectively applied for its grading effect of the classification of glucose in the aqueous solution and dimethyl sulfoxide solution, and the dispersity index of fraction (Mw/Mn) is 1.4-1.6.Day preparation is also flowed for water and methyl-sulfoxide and to be respectively 6.5 and 4g mutually.
Embodiment 3
The konjacmannan solution (III) for preparing 8% cellulose copper ammon solution (I) and 12wt%.Is to mix at 7: 3 I and III by the weight ratio of cellulose and konjacmannan, extrudes mixed liquor by syringe then, forms diameter and enters for the 0.3mm filamentous, solidify in 40 ℃ of aqueous solution, and at 10wt%H
2SO
4Regenerate in the aqueous solution, rinse well with flowing water at last.Below operation is same as embodiment 1.
Claims (2)
1. preparation method who prepares the type porous filler of regenerated cellulose for gel permeation chromatographic column, it is characterized in that this method is is that 0-1 macromolecule pore former polyethylene glycol, konjacmannan or the gelatin doubly of content of cellulose evenly mixes with the cellulose cuprammonia of 6-10wt% and weight, injection is extruded and is formed the filamentous with certain diameter and enter in the 0-10wt%NaOH aqueous solution and solidify under 20-40 ℃ then, again at 4-10wt%H
2SO
4Regenerate in the aqueous solution, final rinse water is cut into silk the Cylinder particle of Len req.
By the described method of claim 1 obtain that porous aggregate filling preparation type gel chromatographic columns is used for that water separates with organic solvent system, classification and purified high-molecular material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113654A CN1089618C (en) | 1998-07-30 | 1998-07-30 | Process for preparing porous filler of regenerated cellulose for gel permeation chromatographic column |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113654A CN1089618C (en) | 1998-07-30 | 1998-07-30 | Process for preparing porous filler of regenerated cellulose for gel permeation chromatographic column |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1243761A CN1243761A (en) | 2000-02-09 |
| CN1089618C true CN1089618C (en) | 2002-08-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98113654A Expired - Fee Related CN1089618C (en) | 1998-07-30 | 1998-07-30 | Process for preparing porous filler of regenerated cellulose for gel permeation chromatographic column |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101776668B (en) * | 2010-03-13 | 2012-06-27 | 兰州中科安泰分析科技有限责任公司 | Filling method of C18 HPLC (High Performance Liquid Chromatography) column |
| CN105880271B (en) * | 2016-07-02 | 2019-04-09 | 江苏省山水生态环境建设工程有限公司 | A kind of restorative procedure of mine chromium heavy-metal contaminated soil |
| CN111220745B (en) * | 2018-11-26 | 2023-05-09 | 江苏集萃智能液晶科技有限公司 | Chromatographic column and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02235944A (en) * | 1989-03-09 | 1990-09-18 | Nisshinbo Ind Inc | Preparation of porous particles of both cellulose and cellulose derivative |
| CN1072419A (en) * | 1991-11-20 | 1993-05-26 | 中国科学院大连化学物理研究所 | Synthesizing of ion-exchange medium for radial chromato bar |
| CN1091144A (en) * | 1993-02-19 | 1994-08-24 | 武汉大学 | Method for preparation of high waterproof high strength regenerative cellulose membrane |
| CN1104647A (en) * | 1994-09-16 | 1995-07-05 | 中国科学院广州化学研究所 | Manufacture of nm avicel powder by solvent process |
-
1998
- 1998-07-30 CN CN98113654A patent/CN1089618C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02235944A (en) * | 1989-03-09 | 1990-09-18 | Nisshinbo Ind Inc | Preparation of porous particles of both cellulose and cellulose derivative |
| CN1072419A (en) * | 1991-11-20 | 1993-05-26 | 中国科学院大连化学物理研究所 | Synthesizing of ion-exchange medium for radial chromato bar |
| CN1091144A (en) * | 1993-02-19 | 1994-08-24 | 武汉大学 | Method for preparation of high waterproof high strength regenerative cellulose membrane |
| CN1104647A (en) * | 1994-09-16 | 1995-07-05 | 中国科学院广州化学研究所 | Manufacture of nm avicel powder by solvent process |
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| CN1243761A (en) | 2000-02-09 |
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