CN1243761A - 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 PDF

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Publication number
CN1243761A
CN1243761A CN 98113654 CN98113654A CN1243761A CN 1243761 A CN1243761 A CN 1243761A CN 98113654 CN98113654 CN 98113654 CN 98113654 A CN98113654 A CN 98113654A CN 1243761 A CN1243761 A CN 1243761A
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China
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cellulose
chromatographic column
filler
aqueous solution
regenerated cellulose
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CN 98113654
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CN1089618C (en
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张俐娜
杨光
周金平
陈敬华
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Wuhan University WHU
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Wuhan University WHU
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Publication of CN1089618C publication Critical patent/CN1089618C/en
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  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

A process for preparing porous cylindrical filler of regenerated cellulose for permeating gel chromatographic column includes such steps as uniformly and proportionally mixing cellulose cuprammonia solution (6-10%) with high-molecular pore-forming agent, extruding out to obtain filament, solidifying in 0-10% aqueous solution of NaOH at 20-40 deg.C, regenerating in aqueous solution of H2SO4 and cutting as will. The chromatographic column made up of said filler can be used to classify, separate and purify the high-molecular biopolymer or synthetic polymer in water or organic solvent. Its advantages are simple process, high speed and low cost.

Description

The preparation method of porous filler of regenerated cellulose for gel permeation chromatographic column
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.
Cellulose/17.5%NaOH aqueous solution (day disclosure special permission communique is mainly adopted in the new development of relevant in recent years cellulose family chromatographic column filler research, A, flat 2~235944,1990), 9.2% cellulose viscose solution (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 made from this filler 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 0~1 times macromolecule pore former of content of cellulose evenly mixes with 6~10% cellulose cuprammonia and weight, injection is extruded and is formed the filamentous with certain diameter and enter in 0~20%NaOH aqueous solution and solidify under 20~40 ℃ then, again at 4~10%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 polyvinyl alcohol 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 η=4.2 * 10 -4) when making pore former, the cellulose cuprammonia solidifies in 40 ℃ of hot water and at 10%H 2SO 4Its surface apertures of regeneration back reaches 360mm in the aqueous solution, and cross-sectional aperture is 1400mm.Solidify in the 10%NaOH aqueous solution for the cellulose cuprammonia of pore former and at 4%H with polyethylene glycol (M=2000) 2SO 4Garden its surface apertures of cylindricality 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 550mm * 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 konjaku-mannosan 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
Method (patent publication No. CN1091144A) preparation 6% cellulose copper ammon solution (I) by former disposes 20% 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 10%NaOH aqueous solution, again at 4%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 6% 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 12%.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 10%H 2SO 4Regenerate in the aqueous solution, rinse well with flowing water at last.Below operation is same as embodiment 1.

Claims (3)

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 times macromolecule pore former of content of cellulose evenly mixes with 6~10% cellulose cuprammonia and weight, injection is extruded and is formed the filamentous with certain diameter and enter in 0~10%NaOH aqueous solution and solidify under 20~40 ℃ then, again at 4~10%H 2SO 4Regenerate in the aqueous solution, final rinse water is cut into silk the Cylinder particle of Len req.
2. by the described method of claim 1, it is characterized in that described macromolecule pore former is polyethylene glycol, konjacmannan or gelatin.
By claim 1 or 2 described methods 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.
CN98113654A 1998-07-30 1998-07-30 Process for preparing porous filler of regenerated cellulose for gel permeation chromatographic column Expired - Fee Related CN1089618C (en)

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CN98113654A 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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CN1089618C CN1089618C (en) 2002-08-28

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101776668A (en) * 2010-03-13 2010-07-14 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
CN105880271A (en) * 2016-07-02 2016-08-24 李康 Method for repairing mine chrome heavy metal pollution soil
CN111220745A (en) * 2018-11-26 2020-06-02 江苏集萃智能液晶科技有限公司 Chromatographic column and preparation method thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
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
CN1053935C (en) * 1993-02-19 2000-06-28 武汉大学 Method for preparation of high waterproof high strength regenerative cellulose membrane
CN1051093C (en) * 1994-09-16 2000-04-05 中国科学院广州化学研究所 Manufacture of nm avicel powder by solvent process

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101776668A (en) * 2010-03-13 2010-07-14 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
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
CN105880271A (en) * 2016-07-02 2016-08-24 李康 Method for repairing mine chrome heavy metal pollution soil
CN111220745A (en) * 2018-11-26 2020-06-02 江苏集萃智能液晶科技有限公司 Chromatographic column and preparation method thereof

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