CN1260567C - Surface silanization regenerated cellulose microsphere filling and preparation method and use thereof - Google Patents
Surface silanization regenerated cellulose microsphere filling and preparation method and use thereof Download PDFInfo
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- CN1260567C CN1260567C CN 200410060705 CN200410060705A CN1260567C CN 1260567 C CN1260567 C CN 1260567C CN 200410060705 CN200410060705 CN 200410060705 CN 200410060705 A CN200410060705 A CN 200410060705A CN 1260567 C CN1260567 C CN 1260567C
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Abstract
The present invention relates to surface silanizing regenerated cellulose microsphere filler. The present invention contains 48 to 90 wt% of cellulose, 9 to 50 wt% of konjak glucomannan and 0.5 to 4 wt% of silicane. 4 to 6% of cellulose NaOH/thiourea water solution and 2 to 4% of konjak glucomannan NaOH/thiourea water solution are evenly mixed and deaired to obtain a mixed solution. A Span 80 liquid paraffin solution is added into the mixed solution and then is stirred. 1 to 10 wt% of CacI<2> water solution is added and is stirred, and finally an HCI water solution is added. A microsphere is obtained by filtration and wash. After the microsphere is carried out with freeze drying, N, N-dimethyl acetamide is taken as a medium. A catalytic agent and pyridine are added. At the temperature of 20 to 100 DEG C, chlorosilane is added and stirred for 3 to 5 hours. A filler microsphere of a regenerated cellulose microsphere with a grain size of 30 to 100 mu m is obtained by filtration and wash. Microsphere filler made by the present invention has the advantages of small grain size, high alkali resistance, low adsorption of biological biomacromolecules and the good efficacy of filled chromatographic columns.
Description
Technical field
The present invention relates to a kind of surface silicon alkanisation regenerated cellulose microballoon filler and its production and use.It belongs to technical field of polymer chemistry, also belongs to the chromatographia technical field.
Background technology
Cellulose and konjaku glucomannan are the natural polymers that enriches, and belong to environment-friendly material; And, because they contain abundant hydroxyl, but make its derivatization and prepare many functional materials; Therefore noticeable day by day to their research and development, especially developing high value-added product has become the research focus in nearly ten years.On the other hand, all extremely important in industry and research with the separation of preparation type gel permeation chromatographic column, classification or the big molecule of purifying biological or synthetic polymer.Yet because chromatographic column filler commonly used is crosslinked polystyrene, glucosan, agarose, polyacrylamide and Bio-sil, their complex manufacturing technology, therefore the working condition strictness costs an arm and a leg, and biocompatibility is relatively poor, is difficult to satisfy the requirement of biological products.Utilize inexpensive cellulose and konjaku glucomannan not only can reduce cost, and help developing abundant regenerated resources for raw material production preparation type gel permeation chromatographic column filler.
The new development of relevant cellulose family chromatographic column filler research mainly contains employing cellulose/17.5%NaOH aqueous solution (day disclosure special permission communique, A, flat 2-235944,1990), 9.2% cellulose viscose (day disclosure special permission communique, A, clear 63-92603,1988), cellulose/calcium thiocyanate solution (J.Chromatogr.A, 720,151,1996), cellulose copper ammon solution (Chinese patent, publication number, 98113654.0,1998) and be mixed with the porous cellulose granular filler with other adjuvant, viscose prepares microballoon regenerated cellulose ion exchanger (ion-exchange and absorption, 14 (1), 23,1998), also utilize cellulose and konjaku glucomannan in NaOH/ thiocarbamide dicyandiamide solution, to prepare porous aggregate and be used for classification polysaccharide (Chinese patent, publication number 1424139A, 2003).The weak point of these methods is that the cellosolve system is more expensive or environment had pollution, or range of application is narrower as can not be used for stronger alkali condition, or filler is that irregular sphere and particle diameter cause the general column efficiency of institute's fill color to reduce more greatly, or filler produces absorption to the classification polymkeric substance and cause chromatographic behavior unusual etc.In addition, cellulose derivative gel (J.Chromatogr.A, 919,29,2001), cellulose derivative microballoon (J.Chromatogr.A, 552,389,1991; Sichuan University's journal (engineering science version), 32,48,2000), inorganic filler (J.Chromatogr.A, 904,17,2000 of cellulose coating; J.Chromatogr.Sci., 40,315,2002) also be used for the gel permeation chromatographic column filler, but its complicated process of preparation and instability, thereby limited its application aspect separation classification and purifying macromolecular substances.
Summary of the invention
Problem to be solved by this invention provides a kind of surface silicon alkanisation regenerated cellulose microballoon filler and its production and use, this method technology is simple, easy to operate, the microballoon packing material size that makes is little, alkali resistance is higher, low to the suction-operated of biomacromolecule, and make the usefulness of the chromatographic column of being filled higher.
Technical scheme provided by the invention is: a kind of surface silicon alkanisation regenerated cellulose microballoon filler, and it consists of: 48%～90% cellulose, 9%～50% konjaku glucomannan, 0.5%～4% silane, above number percent are mass percent.
Above-mentioned regenerated cellulose microballoon filler is interweaved with forming by cellulose and konjaku glucomannan and has mesh-structured microballoon, and its particle diameter is that 30～100 μ m, average pore size are 570～1130nm, hydride modified microballoon hole surface.
The present invention also provides the preparation method of above-mentioned regenerated cellulose microballoon filler, by cellulose: konjaku glucomannan is 10: 1 to 48: 50 a mass ratio, cellulose NaOH/ thiourea solution with 4～6% and 2～4% konjaku glucomannan NaOH/ thiourea solution mix and deaeration obtains mixed solution, and used NaOH/ thiourea solution is 4～8%NaOH/4～6% thiourea solution; The Span80 whiteruss solution that will contain 1～10wt% then joins in the above-mentioned mixed solution, and the amount of used Span80 whiteruss solution is 50～200% of an above-mentioned mixed liquor volume, stirs 0.5～6 hour, adds the CaCl of 1～10wt% again
2Aqueous solution stirred 10～120 minutes, the HCl aqueous solution that adds 1～5wt% at last, filter, obtain microballoon with acetone, absolute ethyl alcohol and water washing successively, thus obtained microsphere is after freeze drying, with N, the N-dimethyl acetamide is a medium, adds the catalyzer pyridine, adds the chlorosilane of 100～300wt% microspheres quality and stirs 3～5 hours at 20-100 ℃, filter, obtain the regenerated cellulose microballoon filler microballoon that particle diameter is 30～100 μ m with toluene, acetone and absolute ethanol washing.
Application in regenerated cellulose microballoon filler of the present invention separation in water, buck or organic solvent system, classification or the purified high-molecular material.
The pore size of microballoon filler is by the control of the content of konjaku glucomannan, but it solidify with regenerative process in be not as the pore former stripping, but with the cellulose formation eyed structure that interweaves.Change the porous aggregate that cellulose and the charge ratio of konjaku glucomannan can obtain different apertures, especially large aperture and wide pore diameter distribution.Change the consumption of emulsifying agent Span80 whiteruss solution, can obtain the microballoon of different-grain diameter.Change the consumption of trimethyl chlorosilane, can obtain the different microballoon filler of microsphere surface degree of modification.Because the surface and the inner bore surface of cellulose/konjaku glucomannan mixed microsphere are modified through trimethyl chlorosilane, not only make this filler keep the performances such as biocompatibility of cellulose/konjaku glucomannan mixed microsphere, and make the absorption property to biomacromolecule of this filler reduce raising greatly, also strengthened the alkali resistance of filler simultaneously, therefore can be under-40-100 ℃ with the chromatographic column of this filler filling, under water, buck and organic solvent system, normally use, in particular for separation, classification and purifying molecule amount 50 * 10
4The polymer substance of following various molecular weight.For the preparative scale chromatography post of 500 * 20mm, every day, preparation amount was 6～15 gram polymer substances.
The present invention under NaOH/ thiocarbamide novel solvent system, is a raw material with cotton linter and konjaku glucomannan first, has prepared the regenerated cellulose microballoon with emulsion method, and has modified microsphere surface with chlorosilane, obtains low and the gel permeation chromatographic column filler that alkali resistance is strong of adsorbability.The present invention has substantive different compared to the prior art, and marked improvement is arranged.Technology of the present invention is simple, rapid, easy to operate, with low cost and applied widely, the microballoon packing material size that makes little (30～100 μ m), alkali resistance are higher, low to the suction-operated of biomacromolecule, the usefulness height of the chromatographic column of being filled is applicable to the preparation type gel permeation chromatographic column of production in enormous quantities.Be easy to the suitability for industrialized production preparation.
Description of drawings
The Electronic Speculum figure of the surface silicon alkanisation regenerated cellulose microballoon filler that Fig. 1 makes for the embodiment of the invention 1;
The Electronic Speculum figure of the surface silicon alkanisation regenerated cellulose microballoon filler that Fig. 2 makes for the embodiment of the invention 2.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described further:
Embodiment 1
Cellulose with 3% and 2% konjaku glucomannan NaOH/ thiourea solution are by cellulose: konjaku glucomannan is that 6: 4 proportioning mixes and deaeration, get 40 grams and insert the there-necked flask of 250mL, to contain 2% Span80 whiteruss solution 40mL joins in this system, stirred 2 hours with 200 rev/mins speed, add 5% CaCl then
2Aqueous solution 50mL also stirred 1 hour, added 2% the HCl aqueous solution of 100mL again and stirred half an hour.Stop to stir, filter, gained solids acetone, absolute ethyl alcohol and distilled water are cleaned, and with this product freeze drying.Get dry above-mentioned product 4 grams and put into the there-necked flask of 100mL, add 30mL N, N dimethyl acetamide and 10mL pyridine stirred 1 hour at 20 ℃ of logical nitrogen and with 100 rev/mins speed, added 4 gram trimethyl chlorosilanes then, stirred 2 hours.Products obtained therefrom is used toluene after filtration, and acetone and absolute ethyl alcohol are cleaned and promptly got required filler, and its particle diameter is 50 to 80 μ m, and silane contents is 2.1%, its scanning electron microscope diagram such as Fig. 1.
Embodiment 2
Cellulose with 4% and 2% konjaku glucomannan NaOH/ thiourea solution are by cellulose: konjaku glucomannan is that 7: 3 proportioning mixes and deaeration, get 40 grams and insert the there-necked flask of 250mL, to contain 4% Span80 whiteruss solution 50mL joins in this system, stirred 1 hour with 200 rev/mins speed, add 5% CaCl then
2Aqueous solution 80mL also stirred 1 hour, added 5% the HCl aqueous solution of 80mL again and stirred half an hour.Stop to stir, filter, gained solids acetone, absolute ethyl alcohol and distilled water clean clean, and with this product freeze drying.Get dry product 4 grams and put into the there-necked flask of 100mL, add 30mL N, N dimethyl acetamide and 10mL pyridine stirred 1 hour at the logical nitrogen of 40C and with 100 rev/mins speed, added 8 gram chlorotriethyl silanes then, stirred 2 hours.Products obtained therefrom is used toluene after filtration, and acetone and absolute ethyl alcohol are cleaned required filler promptly, and its particle diameter is 30 to 50 μ m, and silane contents is 2.8%, its scanning electron microscope diagram such as Fig. 2.
Embodiment 3: the surface silicon alkanisation regenerated cellulose microballoon filler that embodiment 1 is made is packed in the glass tube of 550 * 20mm, forms the glue bed of 500 * 20mm, makes preparation type gel permeation chromatographic column thus.The theoretical pedal number of this preparation type gel permeation chromatographic column is 2730.This post is used for classification weight-average molecular weight M
wBe 8.31 * 10
4, dispersity index d is the tetrahydrofuran solution of 1.55 polycaprolactone, and moving phase is tetrahydrofuran, and flow velocity is 1.2mL min-1.This polymkeric substance is divided into 6 fractions, obtains the fraction product of different molecular weight, its molecular weight is respectively 18.4 * 10
4, 13.4 * 10
4, 11.0 * 10
4, 8.48 * 10
4, 6.10 * 10
4With 1.17 * 10
4, dispersity index is 1.2.Each fraction weight accounts for 10～15% of sample size, and overall yield reaches 96.2%.Showing that this surface silicon alkanisation regenerated cellulose microballoon filler is used in is used for the classification polymkeric substance in the organic solvent system.
Embodiment 4: the surface silicon alkanisation regenerated cellulose microballoon filler that embodiment 2 is made is packed in the glass tube of 550 * 20mm, forms the glue bed of 500 * 20mm, makes preparation type gel permeation chromatographic column thus.This post is used for classification weight-average molecular weight M
wBe 12.1 * 10
4, dispersity index d is the NaOH aqueous solution of 1.70 glucosan, and moving phase is the NaOH aqueous solution of 0.05M, and flow velocity is 1.2mL min-1.This polymkeric substance is divided into 6 fractions, obtains the fraction product of different molecular weight, its molecular weight is respectively 21.3 * 10
4, 14.2 * 10
4, 11.6 * 10
4, 10.7 * 10
4, 9.2 * 10
4With 8.5 * 10
4, dispersity index is 1.3, and overall yield reaches 95.1%.Show that this surface silicon alkanisation regenerated cellulose microballoon filler alkali resistance is higher, low to the suction-operated of biomacromolecule, the usefulness height of the chromatographic column of being filled.
Claims (3)
1. surface silicon alkanisation regenerated cellulose microballoon filler, it consists of: 48%～90% cellulose, 9%～50% konjaku glucomannan, 0.5%～4% silane, above number percent are mass percent; Being interweaved with forming by cellulose and konjaku glucomannan has mesh-structured microballoon, and its particle diameter is that 30～100 μ m, average pore size are 570～1130nm, hydride modified microballoon hole surface.
2. the preparation method of the described regenerated cellulose microballoon of claim 1 filler, it is characterized in that: by cellulose: konjaku glucomannan is 10: 1 to 48: 50 a mass ratio, cellulose NaOH/ thiourea solution with 4～6% and 2～4% konjaku glucomannan NaOH/ thiourea solution mix and deaeration obtains mixed solution, and used NaOH/ thiourea solution is 4～8%NaOH/4～6% thiourea solution; The Span80 whiteruss solution that will contain 1～10wt% then joins in the above-mentioned mixed solution, and the amount of used Span80 whiteruss solution is 50～200% of an above-mentioned mixed liquor volume, stirs 0.5～6 hour, adds the CaCl of 1～10wt% again
2Aqueous solution stirred 10～120 minutes, the HCl aqueous solution that adds 1～5wt% at last, filter, obtain microballoon with acetone, absolute ethyl alcohol and water washing successively, thus obtained microsphere is after freeze drying, with N, the N-dimethyl acetamide is a medium, adds the catalyzer pyridine, adds the chlorosilane of 100～300wt% microspheres quality and stirs 3～5 hours at 20-100 ℃, filter, obtain the regenerated cellulose microballoon filler microballoon that particle diameter is 30～100 μ m with toluene, acetone and absolute ethanol washing.
3. the application in the described regenerated cellulose microballoon of claim 1 filler separation in water, buck or organic solvent system, classification or the purified high-molecular material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100371377C (en) * | 2006-06-09 | 2008-02-27 | 牡丹江卷烟材料厂有限责任公司 | Porous color cellulose particle and its preparing method |
| CN101274985B (en) * | 2008-05-12 | 2011-04-20 | 武汉大学 | Magnetic cellulose microsphere, preparation thereof and use thereof |
| CN102513071B (en) * | 2012-01-09 | 2014-09-10 | 江南大学 | Novel high performance liquid chromatography medium and preparation method thereof |
| CN102627779B (en) * | 2012-02-23 | 2014-12-10 | 宁波争光树脂有限公司 | Preparation method of konjac glucomannan gel microspheres |
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