CN1078724A - The preparation method of beadedly cross-linked glucomannan - Google Patents
The preparation method of beadedly cross-linked glucomannan Download PDFInfo
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- CN1078724A CN1078724A CN 93110973 CN93110973A CN1078724A CN 1078724 A CN1078724 A CN 1078724A CN 93110973 CN93110973 CN 93110973 CN 93110973 A CN93110973 A CN 93110973A CN 1078724 A CN1078724 A CN 1078724A
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Abstract
The invention provides a kind of preparation method who can be used as the crosslinked konjac glucomanna of pearl of gel filter medium.It is characterized in that the konjac glucomanna aqueous solution is scattered in the water-insoluble organic compound that contains dispersion agent, evaporate the water in the drop then, make pearl konjac glucomanna particle after, again with linking agent reaction, the crosslinked konjac glucomanna of preparation pearl.Can save esterification of the prior art, two step of hydrolysis operation like this, shorten the production time and reduce production costs.And the crosslinked konjac glucomanna of pearl of preparation has good intensity and hydraulic performance, the granularity of plurality of specifications and turgidity.
Description
The present invention relates to a kind of preparation method of liquid chromatography (LC) medium, particularly about the preparation method of crosslinked konjac glucomanna beaded particles.
Konjac glucomanna is the major ingredient of konjaku, is that glucose and sweet glycan are by β-1,4 glycosidic link bonded polysaccharide.With its pearl gel of making, the same with dextrane gel, can be used as chromatography media, be applicable to technical field of biochemical separation.Present preparation method [the clear 62-236829 of JP, the flat 1-94949 of JP] carries out esterification with konjac glucomanna earlier to become water-insoluble, is the dispersion medium balling-up with water, is hydrolyzed after the balling-up again, and is then crosslinked, obtains the pearl cross linked gel.This method technical process is longer, and the phase needs all left and right sides time weekly, and consumes a large amount of solvents, and not only the cost costliness also is difficult to industrialization.
The objective of the invention is to overcome the shortcoming in the above-mentioned synthesis technique, provide an a kind of step konjac glucomanna can be made the pearl body, and then the crosslinked konjac glucomanna of crosslinked preparation pearl, to save esterification and the hydrolyzing process in the existing method, thereby shorten the production time, reduce cost.
For reaching above-mentioned purpose, the present invention adopts following technical scheme, the sweet glycan of grape is soluble in water, be dispersion medium with water-fast organic compound, be added with dispersion agent in the dispersion medium, the konjac glucomanna aqueous solution is dispersed in the dispersion medium, obtain water-in-oil-type suspension, evaporate the water in the drop then, obtain pearl konjac glucomanna particle, through crosslinked, can obtain the crosslinked portuguese gansu polyose gel of pearl again.
Under agitation make it evenly be dissolved in Yongzhong commercially available konjaku powder (konjac glucomanna that contains molecular weight and be 60-100 about ten thousand is more than 80%), the warp thread net filtration is removed insolubles.Konjac glucomanna concentration is 0.05%-59% (weight), is preferably 0.2%-2%.Konjac glucomanna concentration was greater than 5% o'clock, and viscosity is too big, was difficult in the organic medium disperse, and was lower than at 0.05% o'clock, and the pearl body is too thin, and production efficiency is too low, and is uneconomical.
Dispersion medium is an oil phase, can be that boiling point is higher than 30 ℃, fusing point is lower than 60 ℃ water-insoluble organic compound, as 6 more than the carbon atom saturated alkane and one or more mixtures in the aromatic hydrocarbon that replaces of monohydroxy-alcohol, alkyl or benzene, halohydrocarbon, ether, the ester, the dispersion medium consumption is 1-10 a times of konjac glucomanna aqueous solution volume, is preferably 1.2-5 doubly.Be difficult to obtain the pearl body in the time of little dried 1 times, production efficiency is too low during greater than 10 times.
In order to guarantee to obtain the konjac glucomanna particle of pearl, the use of dispersion agent is necessary.Nonionic surface active agent, anionic emulsifier, modified-cellulose class and water-fast inorganic salt powder all can be used as dispersion agent.As the class's of department class emulsifying agent, tween emulsifier type, high fatty alcohol epoxy adduct, sodium oleate, Walocel MT 20.000PV, Natvosol, methylcellulose gum, ethyl cellulose, magnesiumcarbonate, lime carbonate, wilkinite, talcum powder etc.Can use wherein a kind of, also can several mixing use.Its consumption is the 0.01%-10% of oil phase weight, preferably 0.1%-5%.Be difficult to guarantee to obtain the pearl body less than 0.01% o'clock, thin partially greater than 10% pearl body, and increase cost.The difference of control dispersion agent is arranged in pairs or groups and consumption, can prepare the pearl body of various particle diameters.
Feeding mode can under agitation dynamically drop into the konjac glucomanna aqueous solution, and the back restir that also can static state feeds intake disperses.Vaporization temperature is at 20 ℃～100 ℃.If when organic dispersion medium and water can form azeotrope, vaporization temperature was advisable near azeotropic point.Vaporization temperature is low, and then drop is long set time, and the pearl body that obtains is transparent, the temperature height, and set time is short, but occurs opaque pearl body easily.
To drop curing, leach the pearl body, through organic solvent (as lower ketones, ether, alcohol) washing, drying just obtains pearl konjac glucomanna particle.
With the pearl konjac glucomanna particle of method for preparing in the presence of alkali lye, again with can carry out crosslinking reaction with the polyfunctional compound of hydroxyl reaction, just can make water-insoluble pearl gel.
Used alkali lye can be alkali metal hydroxide or/and one or more in the alkaline earth metal hydroxides aqueous solution in the crosslinking reaction, and its concentration is not limit.Adding alkali number decides on dosage of crosslinking agent and required turgidity.Usually, linking agent reaction finishing institute's alkali needed can be calculated by reaction equation.When linking agent is excessive and when adding alkali number and control the turgidity of gel, turgidity diminishes with the increase of alkali number.Described basic metal, alkaline-earth metal can be Na, K, Li, Ca, Mg.
Used linking agent can be one or more in the polyfunctional compounds such as epoxide oxygen propane, epoxide oxygen propane one polyol derivative, diepoxy butane, 2,4 toluene diisocyanate, hexamethylene two isocyanic acid ketone in the crosslinking reaction.
Crosslinking reaction can directly be carried out in linking agent.Dosage of crosslinking agent is 2-30 a times of konjac glucomanna pearl body weight.Earlier the pearl body is dispersed in the linking agent, again dripping alkali liquid under agitation.
Crosslinking reaction also can be carried out in the water-soluble organic medium aqueous solution.Konjac glucomanna pearl body is dispersed in the dielectric fluid, stirs and drip linking agent and alkali lye down.Also can be earlier with linking agent or/and alkali lye mixes with dielectric fluid, add all the other components again.Organic medium can be one or more in lower alcohol, ether, ketone, the sulfoxide, and its concentration is 1.5-100% (weight), preferably 30-100% (weight).Organic medium liquid and alkali lye weight sum are 2-30 times of pearl body weight, and preferably 3-15 doubly.At this moment, the consumption of linking agent is that per 100 gram pearl bodies are greater than 0.05 mole.By adjusting the consumption of alkali number and linking agent, can prepare the crosslinked portuguese gansu polyose gel of pearl of different turgiditys, to adapt to different service conditions.
Preferably 10 ℃～95 ℃ of crosslinking reaction temperature, the reaction times is 4-48 hour, temperature of reaction is low, long reaction time then, the temperature of reaction height, then the reaction times can shorten.
After crosslinking reaction finishes, leach the pearl body, through water-soluble organic medium washing, washing just obtains the crosslinked portuguese gansu polyose gel of pearl.
The crosslinked portuguese gansu polyose gel of pearl with the present invention's preparation has good intensity and hydraulic performance, granularity of plurality of specifications (5～200 μ m) and turgidity [2.0～10.0ml/g (doing)], can be used as the medium of gel filtration method in the biotechnology isolation technique, can also be as other chromatography medias (as ion-exchange chromatography media, affinity chromatography medium, hydrophobic chromatoghaphy medium etc.) parent.
Preparation method of the present invention has saved esterification, two step of hydrolysis operation than prior art, has both shortened the production time greatly, has saved a large amount of solvents again, and production cost reduces significantly, helps industrialization.
Accompanying drawing 1 is the chromatography spectrogram that the crosslinked konjac glucomanna of pearl of the embodiment of the invention 12 preparations is used for the protein desalination, and wherein the A peak is a protein peak, and the B peak is the salt peak, protein recovery 99.86%, the salt rate of recovery 95.26%.
Be embodiment below.
Embodiment one
In the 500ml there-necked flask of band whipping appts and profit height separator, add the white oil 235ml that is mixed with class of 1.2 gram departments one 80,4.8 gram tween-80s, be warming up to 90 ℃, under agitation dripping concentration is the konjac glucomanna aqueous solution 100ml of 1% (weight), 0.5 hour dropping time.After dropwising, be warming up to 95 ℃, kept 12 o'clock, the pearl body solidifies.Leach the pearl body, divide 5 washings with 500ml methyl alcohol, room temperature is dried.Particle diameter is less than the pearl body circle of 200 μ, and is oval greater than slightly becoming of 200 μ.
Embodiment two
With the same device of embodiment one in add the white oil 350ml that is mixed with 6 gram tween 80s and 15 gram n-Octanols, be warming up to % ℃, stirring and dripping concentration down is the konjac glucomanna aqueous solution 100ml of 1% (weight), 0.5 hour dropping time.Be warming up to 95 ℃ then, kept 9 o'clock, the pearl body solidifies.Leach the pearl body, divide 5 washings, change over to then in the ethanol of 100ml 8.5% (volume), be dissolved with 1 gram NaOH in the ethanol, placed 24 hours with the ethanol of 500ml 8.5% (volume).Leach the pearl body, drop in the 30 gram epoxy chloropropane, room temperature left standstill 24 hours.Leach the pearl body, through 100ml ethanol, the 500ml water washing, the pearl body is insoluble in water.
Embodiment three
With the same device of example one in add and be mixed with 80,7 gram departments class of class of 7 gram departments, 20,0.7 gram lime carbonate, the butylacetate 350ml of 3.5 gram n-Octanols is warming up to 60 ℃, dropping concentration is the konjac glucomanna aqueous solution 70ml of 1% (weight) under stirring.Be warming up to 80 ℃ after dropwising, kept 7.5 hours, the pearl body solidifies.A small amount of slimeball is arranged.
Embodiment four
With the same device of embodiment one in add and be mixed with 3 gram polysorbate40s, the epoxy chloropropane 270ml of class of 6 gram departments 80 is warming up to 85 ℃, stirs the konjac glucomanna aqueous solution 100ml of dropping 1% (weight) concentration down.Kept under 95 ℃ 6 hours then, the pearl body solidifies.Leach the pearl body,, drip the NaOH aqueous solution 8 grams of 30% (weight) under 60 ℃ of vacuum, drip epoxide oxygen propane 6.2 grams then through washing with alcohol.40 ℃ were reacted 10 hours down, and 60 ℃ were reacted 10 hours down.Leach the pearl body, washing, crosslinked pearl body 15.3ml, inhale forever that multiple is 1.00 times, turgidity is a 2.67ml/ gram (doing).
Embodiment ten
In the 250ml there-necked flask, add the isopropanol water solution 50ml of 50% (weight), 5 grams are pressed the pearl body of embodiment seven preparations, stir the NaOH aqueous solution 2 grams that drip 30% (weight) down, drip epoxide oxygen propane 6.2 grams then.40 ℃ were reacted 20 hours down, and 60 ℃ were reacted 5 hours down.Leach the pearl body, washing gets crosslinked pearl body 26ml, and its suction multiple is 2.64 times, and turgidity is a 4.86ml/ gram (doing).
Embodiment 11
In the 250ml there-necked flask, add the dioxane aqueous solution 60ml of 30% (weight), 10 grams are pressed the pearl body of embodiment seven preparations, stir NaOH 16.4 grams that drip 30% (weight) down, epoxy chloropropane 9.5 grams.40 ℃ were reacted 4 hours down, and 60 ℃ were reacted 2 hours down.Get crosslinked pearl body 72.5ml, its suction multiple is 3.45, and turgidity is a 6.82ml/ gram (doing).
Embodiment 12
In 2 liters of there-necked flasks, add the dioxane aqueous solution 810ml of 40% (weight), press pearl body 162 grams of embodiment seven preparations, stir the NaOH aqueous solution 200 grams that drip 30% (weight) down, epoxy chloropropane 138.7 grams.40 ℃ were reacted 2 hours down, and 60 ℃ were reacted 4 hours down.Get crosslinked pearl body 450ml, its suction multiple is 1.1 times, and turgidity is a 2.58ml/ gram (doing).
Dry; The external mass color circle of the pearl that obtains, particle diameter is at 5～30 μ.
Embodiment five
With the same device of embodiment one in add and be mixed with 3 gram polysorbate40s, the n-Octanol 300ml of class of 6 gram departments 60,70 ℃ of stirrings drip the konjac glucomanna aqueous solution 100ml of 1% (weight) down, keep the curing of pearl body 4 hours under 95 ℃.Filter, the external mass color circle of the pearl that obtains after the washing with alcohol, particle diameter is in 80～200 μ.
Embodiment six
With the same device of embodiment one in add and be mixed with 3 gram polysorbate40s, the epoxy chloropropane 270ml of class of 6 gram departments 60,75 ℃ of konjac glucomanna aqueous solution 100ml of input 1% (weight) down, the back restir dispersion that finishes feeds intake, heat up after disperseing to finish, kept under 95 ℃ 6 hours, the pearl body solidifies.Filter, washing with alcohol, the external mass color circle of pearl, particle diameter is 50～180 μ.
Embodiment seven
In 5 liters of there-necked flasks of band water-and-oil separator, add and to be mixed with 12 gram polysorbate40s, the epoxy chloropropane 2280ml of class of 20 gram departments 60,70 ℃ of stirrings drip the konjac glucomanna aqueous solution 1900ml of 0.7% (weight) down, keep the curing of pearl body 12 hours under 94 ℃.Filter, washing with alcohol, oven dry, the pearl body is transparent, and outer mass color circle is most of at 20～60 μ.Through screen cloth screening, pearl body size distribution is as follows: greater than 200 μ: 0.1 gram, and 220～135 μ: 0.2 gram, 135～75 μ: 0.4 gram, less than 75 μ: 11.4 grams.
Embodiment eight
Press pearl konjac glucomanna particle 5 grams of embodiment seven preparations, drop in the 250ml there-necked flask, add epoxy chloropropane 50ml, stirring drips the NaOH aqueous solution 8 grams of 30% (weight) down, and 40 ℃ were reacted 8 hours down.Leach the pearl body, respectively through ethanol, water washing gets the crosslinked pearl body of 15ml, and its suction multiple is 1.04, and turgidity is a 2.78ml/ gram (doing).
Embodiment nine
In the 250ml there-necked flask, add the 50ml Virahol, 5 grams are pressed the pearl body of embodiment seven preparations, stir
Claims (9)
1. the preparation method of the crosslinked konjac glucomanna of pearl is characterized in that:
(a) the konjac glucomanna aqueous solution is scattered in the water-insoluble organic compound, becomes water-in-oil-type suspension;
(b) add in the water-insoluble organic compound dispersion agent is arranged;
(c) 20 ℃～100 ℃ down in the evaporation drops forever, be solidified into the pearl konjac glucomanna to drop;
(d) with can with the polyfunctional compound of hydroxyl reaction as linking agent, at alkali metal hydroxide or/and alkaline earth metal hydroxides in the presence of, carry out crosslinking reaction with the pearl konjac glucomanna that obtains, promptly make the crosslinked konjac glucomanna of pearl.
2. the preparation method of the crosslinked konjac glucomanna of pearl according to claim 1, the concentration that it is characterized in that the konjac glucomanna aqueous solution are 0.05～5% (weight).
3. the preparation method of the crosslinked konjac glucomanna of pearl according to claim 1, it is characterized in that the water-insoluble organic compound is that boiling point is higher than 30 ℃, fusing point is lower than 60 ℃ organic compound, can be above saturated alkane and monohydroxy-alcohols of 6 carbon atoms, aromatic hydrocarbon or benzene that alkyl replaces, haloalkane, ether, the mixture of one or more in the organic acid acetic.
4. according to the preparation method of claim 1 or the crosslinked konjac glucomanna of 3 described pearls, it is characterized in that the dispersion agent that adds in the water-insoluble organic compound can be a nonionic surface active agent, anionic emulsifier, the mixture of one or more in modified-cellulose class and the water-fast inorganic salt powder, its consumption are 0.01～10% (weight).
5. according to the preparation method of claim 1 or the crosslinked konjac glucomanna of 3 described pearls, the volume ratio that it is characterized in that the water-insoluble organic compound and the konjac glucomanna aqueous solution is 1～10.
6. the preparation method of the crosslinked konjac glucomanna of pearl according to claim 1, it is characterized in that linking agent used in the crosslinking reaction can be an epoxy chloropropane, the polyol derivative of epoxy chloropropane, the diepoxy butane, 2, the 4-tolylene diisocyanate, one or more in the polyfunctional compounds such as HDI.
7. according to the preparation method of claim 1 or the crosslinked konjac glucomanna of 6 described pearls, it is characterized in that the alkali metal hydroxide that crosslinking reaction is used or/and alkaline earth metal hydroxides can be sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide.
8. according to the preparation method of claim 1 or the crosslinked konjac glucomanna of 6 described pearls, it is characterized in that crosslinking reaction can carry out in 2～30 times of linking agents of pearl body weight; Also can carry out in concentration is the water-soluble organic medium aqueous solution of 15～100% (weight), the organic medium aqueous solution and alkali lye sum are 2～30 times of pearl body weight.
9. the preparation method of the crosslinked konjac glucomanna of pearl according to claim 8 is characterized in that water-soluble organic medium can be one or more mixtures in low and slow alcohol, ether, ketone, the sulfoxide, and its concentration is 30%～100% (weight) preferably.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93110973 CN1031194C (en) | 1993-04-20 | 1993-04-20 | Preparation method of beadedly cross-linked glucomannan |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 93110973 CN1031194C (en) | 1993-04-20 | 1993-04-20 | Preparation method of beadedly cross-linked glucomannan |
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| CN1078724A true CN1078724A (en) | 1993-11-24 |
| CN1031194C CN1031194C (en) | 1996-03-06 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101113180B (en) * | 2006-07-26 | 2010-12-08 | 中国科学院过程工程研究所 | Konjak portuguese gansu polyose gel microsphere and method for preparing same |
| WO2016193163A1 (en) * | 2015-06-04 | 2016-12-08 | Ge Healthcare Bioprocess R&D Ab | Manufacturing process for polysaccharide beads |
| CN108478875A (en) * | 2018-03-16 | 2018-09-04 | 浙江科技学院 | A kind of preparation method and applications of cross-linked hyaluronic acid gel microballoon |
-
1993
- 1993-04-20 CN CN 93110973 patent/CN1031194C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101113180B (en) * | 2006-07-26 | 2010-12-08 | 中国科学院过程工程研究所 | Konjak portuguese gansu polyose gel microsphere and method for preparing same |
| WO2016193163A1 (en) * | 2015-06-04 | 2016-12-08 | Ge Healthcare Bioprocess R&D Ab | Manufacturing process for polysaccharide beads |
| CN107667135A (en) * | 2015-06-04 | 2018-02-06 | 通用电气医疗集团生物工艺研发股份公司 | The preparation method of polysaccharide bead |
| US11236216B2 (en) | 2015-06-04 | 2022-02-01 | Cytiva Bioprocess R & D Ab | Manufacturing process for polysaccharide beads |
| CN108478875A (en) * | 2018-03-16 | 2018-09-04 | 浙江科技学院 | A kind of preparation method and applications of cross-linked hyaluronic acid gel microballoon |
| CN108478875B (en) * | 2018-03-16 | 2021-06-04 | 浙江科技学院 | Preparation method and application of crosslinked hyaluronic acid gel microspheres |
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| CN1031194C (en) | 1996-03-06 |
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