CN100404125C - Kernel-containing boracic acid group absorptive and its preparing method - Google Patents
Kernel-containing boracic acid group absorptive and its preparing method Download PDFInfo
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- CN100404125C CN100404125C CNB2006100367571A CN200610036757A CN100404125C CN 100404125 C CN100404125 C CN 100404125C CN B2006100367571 A CNB2006100367571 A CN B2006100367571A CN 200610036757 A CN200610036757 A CN 200610036757A CN 100404125 C CN100404125 C CN 100404125C
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Abstract
The invention discloses a boracic base core adsorbent and preparing method, which is characterized by the following: adopting glass, quartz or polystyrene inert ball to prepare the absorbent without adsorbing ability, possessing certain thickness for case and high-degree coordination selection adsorbing ability and active porous dielectric structure for carbohydrate with cis-form dihydroxy, nitrating crosslinking polystyrene ball of glass or quartz core through reducing and after-disposing, or nitrating crosslinking polystyrene ball of glass or quartz core incompletely through reducing and after-disposing.
Description
Technical field
The invention belongs to the adsorption and separation material synthesis technical field, relate to and be used for the adsorbent that preparing chromatograph in industry separates the carbohydrate that contains cis-form dihydroxy, especially relate to a kind of kernel-containing boracic acid group absorptive and this preparation of adsorbent method.
Background technology
Functional oligose is as a class of basic living matter sugar, have the effect that suppresses growth of cancer cells, antidepression, raising body immunity and memory and improve the human body micro-ecological environment, on diseases such as prevention and treatment cancer, depression and senile dementia, demonstrate great potential.Since the hydrophilicity of the special construction of monose and compound sugar and height, the feasible separating high-purity compound sugar technology from monose and oligosaccharide mixture that does not still find a kind of economy so far.In modern separation science and technical field, preparative chromatography technology (comprising adsorption chromatography, ion-exchange chromatography and coordinate chromatograph etc.) has the high-resolution separating power, and can under gentle relatively condition, operate, be the effective means that is widely used in from multicomponent mixture, separating biochemical preparation, chirality body or isomer etc. now, also demonstrate great potential from the field at sugar.The adsorbent of research and development high selectivity and high pass characteristic is to realize that chromatographic separation technology is in compound sugar separation field key in application.
Develop compound sugar chromatographic separation technology efficiently, the problem that at first needs to solve is exactly the exploitation of high selectivity adsorbent.The structure of existing industrial solid adsorbent all is the homogeneous solid phase, and their selectivity is determined by the chemistry and the physical property of adsorbent surface usually.Therefore, surface modification is to improve optionally one of main means of adsorbent.For example, (J.Padin and R.T.Yang such as J.Padin, New Sorbents forOlefin-Paraffin Separations by Adsorption via-Complexation:Synthesis and Effects ofSubstrates, Chem.Eng.Sci.55,2607 (2000)) use Ag
+To γ-Al
2O
3, SiO
2Carry out surface modification with MCM-41, utilize carbon-carbon double bond and Ag
+Between complexing π key, form selection absorption property to alkene, application separates with alkene and the mixed gas of alkane.(Li Zhong such as Li Zhong, Huang Peiquan, Luo Wenxian etc., large-scale liquid chromatogram is separated the thermodynamics and the kinetic parameter identification of sweet mellow wine and sorbierite, ion-exchange and absorption, 11,109 (1995)), obtain a kind of sweet mellow wine sorbierite isomer being had the Ca type adsorbent of separative efficiency preferably by using different metal ion exchanged gel-type and large pores cation exchange resin.Have research (money Guoqiang, woods snow, what handle woods, the reaction of boric acid and polyol and boron selective resin, ion-exchange and absorption, 10,375 (1994)) show boric acid can with the polyalcohol network and the thing of the polyalcohol formation with cis-form dihydroxy 1: 1 and 1: 2.Sugar also is a class of polyalcohol, if boric acid is solidificated on the adsorbing agent carrier surface, just might form a kind of adsorbent to carbohydrate high selectivity with cis-form dihydroxy.Yet except the adsorptive selectivity energy, the mass-transfer performance of adsorbent is another key factor that influences the preparative chromatography separative efficiency.If the mass tranfer coefficient of adsorbent is very little, the chromatogram eluting peak is not only wide but also short, and lock out operation is long cycle time, causes its separative efficiency low, is difficult to satisfy the requirement of industrial separation.In general, the mass tranfer coefficient of adsorbent side and absorbent particles radius square is inversely proportional to.But, if attempt to use the very little granule adsorbent of diameter, can cause the adsorbent bed stressor layer to fall rapid increase to improve the mass tranfer coefficient of adsorbent side, make the power consumption of separation process sharply rise.In addition, separate for multicomponent, the adsorption capacity of adsorbent is not to be the bigger the better, and the adsorbents adsorb capacity is bigger than normal, will cause that the time of staying of adsorbate in chromatographic column grown partially and chromatographic peak broadens, and causes the reduction of adsorbent separative efficiency.
Summary of the invention
The object of the present invention is to provide and a kind ofly not only had high selectivity, but also had the higher mass-transfer performance and the suitable adsorbent of adsorption capacity for the carbohydrate that contains cis-form dihydroxy, can be used for coordination absorption or prepare the separation of liquid phase coordinate chromatograph containing the carbohydrate of cis-form dihydroxy, thereby make the efficient production chromatographic separation process of compound sugar become possibility.
Kernel-containing boracic acid group absorptive of the present invention is a kind of spherical coordination adsorbent with inert core, the inertia bead of its kernel for not having adsorption capacity; Outside, the boronate active porous medium shell mechanism that band cis-form dihydroxy carbohydrate had high coordinating selective adsorption ability certain thickness for having.If the diameter of this coordination absorbent particles is dp, when kernel inertia sphere diameter was do, the thickness of coordination adsorption activity layer was (d so
p-d
o)/2, effective adsorption volume are π (d
p 3-d
o 3)/6.Therefore, work as d
o/ d
pAt 0.2＜d
o/ d
pRegulate in＜0.9 scope, with homogeneous phase adsorbent (whole spheroid all is the porous media with adsorption activity) ratio, the theoretical adsorption capacity of this adsorbent is 99.2%～27.1% of a homogeneous phase adsorbents adsorb amount; As if the calculating that is inversely proportional to mass tranfer coefficient and radius squared, the solid phase mass tranfer coefficient is 1.5～100 times of homogeneous phase adsorbent mass tranfer coefficient.
The present invention also provides the preparation method of described kernel-containing boracic acid group absorptive.
The preparation method of kernel-containing boracic acid group absorptive of the present invention may further comprise the steps:
A) preparation of tool nuclear matrix:
Benzoyl peroxide is made initator and toluene is dissolved in styrene monomer and the divinylbenzene mixed liquor as pore-foaming agent, add the deionized water of molten 0.5% polyvinyl alcohol of 7 times of volumes, stir fast and heat up and carry out the copolymerzation with cross-linking reaction; Spheroid is leached, use hot wash, the gained mixture is filtered, the solid phase centrifugation, vacuum drying is carried out in washing under 65 ℃, obtain not having the even bead of polystyrene matrix of adsorption activity, and particle diameter is distributed in about 1.2-1.5mm;
B) tool nuclear matrix is aminated:
It is 6: 7 HNO that the tool nuclear matrix that steps A is made places the volume ratio that is chilled in advance below 10 ℃
3-H
2SO
4In the nitration mixture, stir under the ice bath environment, the control reaction temperature is no more than 10 ℃, carries out nitration reaction or part nitration reaction by controlling the reaction time, nitration product is taken out clean to pH＞5.5, joins the SnCl of 0.2g/mL
2Hydrochloric acid solution in, under agitation be heated to backflow, reaction is no less than 2.5 hours, temperature is 115 ℃, and product is taken out, and is washed till pH＞5.5 with deionized water;
C) boronate tool caryogamy position preparation of adsorbent:
Take by weighing the aminated tool nuclear matrix that step B makes, soak jolting, the 5%NaNO of the isopyknic same precooling of dropping in 30 minutes with 0 ℃ the 1mol/LHCl solution of being chilled in advance of 10 times of volumes
2, entire reaction is lower than 5 ℃ with ice bath control temperature; Dropwise the distilled water cleaning carrier of back with precooling, then this carrier is joined in the excessive saturated amido phenyl boric acid aqueous solution, jolting 30 minutes was reacted 12 hours, used washed with de-ionized water again, was drying to obtain in vacuum drying chamber.
The present invention compares with existing solid absorbent, has the following advantages:
(1) kernel-containing boracic acid group absorptive of the present invention has high selectivity energy and high mass-transfer performance to the carbohydrate that contains cis-form dihydroxy; Can control the rational adsorption capacity of adsorbent by changing synthetic technological condition.
(2) adsorbent of the present invention is a kind of tool nuclear adsorbent, and kernel is not for to have adsorption function inertia solid phase to separation component, and shell is for having the coordination adsorbent solid phase of high selectivity energy to the carbohydrate that contains cis-form dihydroxy; By adjusting the size of shell, in the solid phase resistance to mass tranfer that can reduce the adsorbent side significantly, when improving the absorption mass transfer rate, can adjust the adsorption capacity of adsorbent again in right amount, combine improving mass transfer rate and adjustment and controlling the adsorbents adsorb capacity.The theoretical value of solid phase mass tranfer coefficient is compared with common homogeneous adsorbent can increase by 1.5 times to 100 times.
(3) boronate tool caryogamy of the present invention position adsorbent for solving the equilibrium problem between adsorption capacity and the separative efficiency, provides better solution, thereby has been better than the homogeneous phase adsorbent.
(4) boronate tool caryogamy of the present invention position adsorbent, its preparation method technology path is reasonable, and technology is simpler, and is easy to operate, is easy to industrialization.
In sum, kernel-containing boracic acid group absorptive of the present invention is used for the coordination preparative chromatography separates the carbohydrate process, can solve and use the homogeneous phase adsorbent because of the less industrial applications problem that is difficult to of its solid phase mass tranfer coefficient, and in the adsorbent used of chromatography because of the little problem that can't industrial applications of adsorbents adsorb capacity, separate the productive rate of carbohydrate admixture with improving the coordination preparative chromatography greatly, impurity monose provides possibility in the functional oligose in particular for removing on the solution industrially scalable.
Description of drawings
Fig. 1 separates elution curve for using homogeneous phase boronate resin isolation glucose/maltotriose; Abscissa t is the delivery time, min; Ordinate C is the exit concentration of glucose and maltotriose, gmL
-1Experiment condition is as follows: L=30cm is the chromatogram column length, and u=0.4cm/min is the fluid linear speed, Q
In=24ml is an inlet amount, and the separation cycle time is about 300min.
Fig. 2 is for using boronate tool nuclear polymeric adsorbent separating glucose of the present invention/maltotriose chromatographic isolation elution curve; Abscissa t is the delivery time, min; Ordinate C is the exit concentration of glucose and maltotriose, gmL
-1Experiment condition is as follows: L=30cm is the chromatogram column length, and u=0.4cm/min is the fluid linear speed, Q
In=24ml is an inlet amount, and the separation cycle time is about 200min.
Fig. 3 separates elution curve for using homogeneous phase boronate resin isolation fructose/maltotriose; Abscissa t is the delivery time, min; Ordinate C is the exit concentration of fructose and maltotriose, gmL
-1Experiment condition is as follows: L=30cm is the chromatogram column length, and u=0.4cm/min is the fluid linear speed, Q
In=24ml is an inlet amount, and the separation cycle time is about 300min.
Fig. 4 is for using the boronate tool nuclear polymeric adsorbent separating levulose/maltotriose chromatographic isolation elution curve of the invention process preparation.Abscissa t is the delivery time, min; Ordinate C is the exit concentration of fructose and maltotriose, gmL
-1Experiment condition is as follows: L=30cm is the chromatogram column length, and u=0.4cm/min is the fluid linear speed, Q
In=24ml is an inlet amount, and the separation cycle time is about 225min.
The specific embodiment
Embodiment one: preparation of adsorbent of the present invention
Preparation of adsorbent method of the present invention may further comprise the steps:
A) preparation of polystyrene matrix
The toluene of the 0.6g benzoyl peroxide being made initator and 100ml is dissolved in 99g styrene monomer and 45g divinylbenzene (as crosslinking agent as pore-foaming agent, its content is 55%) in the mixed liquor, the deionized water that adds the polyvinyl alcohol of 700ml molten 0.5% stirs fast and heats up and carries out the copolymerzation with cross-linking reaction.In 1 hour, temperature is risen to 80 ℃, and kept 2 hours; Rise to 90 ℃ then, kept 2 hours; Reacted again 5 hours at 96 ℃ at last.Spheroid is leached, use hot wash, the gained mixture is filtered, the solid phase centrifugation, vacuum drying is carried out in washing under 65 ℃, obtain not having the even bead of polystyrene matrix of adsorption activity, and particle diameter is distributed in about 1.2-1.5mm.
B) the polystyrene body portion is aminated
Polystyrene matrix 10g that the adding steps A makes in the 500mL three-necked bottle and 250mL are chilled to the HNO below 10 ℃ in advance
3-H
2SO
4Nitration mixture (volume ratio 6: 7) stirs under the ice bath environment, and the control reaction temperature is no more than 10 ℃, carry out the part nitration reaction, make the polystyrene sphere exterior section nitrated, kernel remains the polystyrene kernel (the nitrated time can not be long, otherwise polystyrene sphere is all by nitrated) of inertia.The control nitration reaction time changes at 0-360min, can get the nitration product of tool different size polystyrene inert core.The nitration product taking-up is cleaned to pH＞5.5, be reentered in the three-necked bottle, and add SnCl
2Hydrochloric acid solution (40g SnCl
2Be dissolved among the dense HCl of 200mL), under mechanical agitation, be heated to backflow, to react 3.5 hours, temperature is about 115 ℃, and discharging is washed till pH＞5.5.
C) boronate tool caryogamy position preparation of adsorbent:
Take by weighing the about 10g of aminated tool nuclear matrix that step B makes, the 1mol/LHCl solution that is chilled to 0 ℃ with 100mL in advance soaks jolting, drips the 5%NaNO of the same precooling of 100mL in 30min
2, entire reaction is lower than 5 ℃ with ice bath control temperature.Dropwise the distilled water cleaning carrier of back with precooling, then this carrier is joined in the excessive saturated amido phenyl boric acid aqueous solution, jolting 30min reacted 12 hours, used washed with de-ionized water again, was drying to obtain in vacuum drying chamber.
Embodiment two: preparation of adsorbent of the present invention
Preparation of adsorbent method of the present invention may further comprise the steps:
A) preparation of tool nuclear matrix:
The toluene of the 0.6g benzoyl peroxide being made initator and 100ml is dissolved in 99g styrene monomer and 45g divinylbenzene (as crosslinking agent as pore-foaming agent, its content is 55%) in the mixed liquor, the deionized water that adds the polyvinyl alcohol of 700ml molten 0.5%, and then add glass or the quartzy bead (50g) that diameter is about 1.0-1.5mm, surface process roughening treatment, stir fast and heat up and carry out the copolymerzation with cross-linking reaction.In 1 hour, temperature is risen to 80 ℃, and kept 2 hours; Rise to 90 ℃ then, kept 2 hours; React 5 hours (by adjusting reaction time, can on the inert ball surface, obtain the polystyrene of different-thickness,, can obtain the tool nuclear adsorbent of different-thickness activated adoption layer) again at 96 ℃ at last through subsequent treatment.Spheroid is leached, use hot wash, the gained mixture is filtered, the solid phase centrifugation, vacuum drying is carried out in washing under 65 ℃, and gained tool nuclear matrix particle diameter is distributed in about 1.2-1.5mm.
B) tool nuclear matrix is aminated:
Tool nuclear matrix 15g that the adding steps A makes in the 500mL three-necked bottle and 250mL are chilled to the HNO below 10 ℃ in advance
3-H
2SO
4Nitration mixture (volume ratio 6: 7) stirs under the ice bath environment, and the control reaction temperature is no more than 10 ℃, and nitration reaction after 4.5 hours is cleaned the nitration product taking-up to pH＞5.5, is reentered in the three-necked bottle, and adds SnCl
2Hydrochloric acid solution (40g SnCl
2Be dissolved among the dense HCl of 200mL), under mechanical agitation, be heated to backflow, to react 2.5 hours, temperature is about 115 ℃, and discharging is washed till pH＞5.5.
C) boronate tool caryogamy position preparation of adsorbent
Identical with the step C of embodiment one.
Embodiment three: glucose/maltotriose, fructose/maltotriose preparative chromatography separating experiment
(1) experiment material:
1, boronate tool caryogamy position adsorbent: make by embodiment one and embodiment two described preparation methods;
2, boronate homogeneous phase coordination adsorbent: in embodiment one described step B, nitrated time long enough, polystyrene sphere through the subsequent treatment of step C, obtain boronate homogeneous phase coordination adsorbent all by nitrated;
3, analyze pure glucose: Hua Kai Industrial Co., Ltd. (Shanghai);
4, fructose: Hua Kai Industrial Co., Ltd. (Shanghai);
5, maltotriose: Sigma company (U.S.)
(2) experimentation:
Get above-mentioned boronate tool caryogamy position adsorbent or boronate homogeneous phase, wet method fills in the adsorption column that internal diameter is 1cm, and loading height is 30cm.Get analyze pure glucose, fructose and maltotriose respectively compound concentration be glucose, fructose and the maltotriose solution of 0.3g/mL, 0.3g/mL and 0.2g/mL.With post interior lines flow velocity is 0.4cm/min, distinguishes charging 24mL separately, with the diluted acid flushing of certain pH value, adopts liquid chromatogram differential refraction detection method to detect outflow concentration then.
(3) interpretation of result:
Experimental result as shown in Figures 1 to 4.Fig. 1, Fig. 2 are respectively glucose and the chromatogram elution curve of maltotriose on homogeneous phase and tool nuclear adsorbent packed column.Fig. 3, Fig. 4 are respectively fructose and the chromatogram elution curve of maltotriose on homogeneous phase and tool nuclear adsorbent packed column.
Fig. 1 compares with Fig. 2, and the maltotriose elution curve does not change, and this is because do not have cis-form dihydroxy in the maltotriose molecule, so it does not all have adsorption capacity on homogeneous phase boronate resin and tool nuclear boronate adsorbent.And the peak shape of the glucose elution curve among Fig. 2 is higher relatively and narrower, show that glucose outflow concentration is higher, the chromatographic isolation operation cycle is lacked (shortening about 100 minutes), the mass-transfer performance that tool nuclear adsorbent is described is better than the homogeneous phase adsorbent, and this makes that the isolated yield of tool nuclear adsorbent of the present invention improves about more than 30% than homogeneous solid-phase adsorbent isolated yield under the same operation condition.
Fig. 3 compares with Fig. 4, and the maltotriose elution curve does not change equally.And the fructose elution curve is high and narrow among relative Fig. 3 of peak shape of the fructose elution curve among Fig. 4, show that Fig. 4 process fructose outflow concentration is higher, the chromatographic isolation operation cycle is lacked (shortening about 75 minutes), and this makes that the isolated yield of tool nuclear adsorbent of the present invention improves about more than 25% than homogeneous solid-phase adsorbent isolated yield under the same operation condition.
Conclusion: kernel-containing boracic acid group absorptive of the present invention has good adsorption to select performance to the carbohydrate (as glucose and fructose) with cis-form dihydroxy, and does not select adsorption capacity substantially to not having a compound sugar (as maltotriose) of cis-form dihydroxy.Kernel-containing boracic acid group absorptive of the present invention is compared with boronate homogeneous phase adsorbent, has higher absorption mass-transfer performance and suitable adsorption capacity, can improve the production capacity that preparative chromatography is separated tool cis-form dihydroxy carbohydrate greatly.
Claims (4)
1. kernel-containing boracic acid group absorptive is characterized in that: be a kind of spherical coordination adsorbent with inert core, and the inertia bead of its kernel for not having adsorption capacity, described inertia bead is the crosslinked polystyrene spheroid; Outside certain thickness for having, band cis-form dihydroxy carbohydrate is had the active porous medium shell mechanism of boronate of high coordinating selective adsorption ability, the active porous medium of described boronate is the active porous medium of boronate polystyrene.
2. kernel-containing boracic acid group absorptive according to claim 1 is characterized in that: described crosslinked polystyrene spheroid is the crosslinked polystyrene spheroid with glass or quartzy kernel.
3. the preparation method of kernel-containing boracic acid group absorptive as claimed in claim 1 is characterized in that, may further comprise the steps:
A) preparation of tool nuclear matrix:
Benzoyl peroxide is made initator and toluene is dissolved in styrene monomer and the divinylbenzene mixed liquor as pore-foaming agent, add the deionized water of molten 0.5% polyvinyl alcohol of 7 times of volumes, stir fast and heat up and carry out the copolymerzation with cross-linking reaction; Spheroid is leached, use hot wash, the gained mixture is filtered, the solid phase centrifugation, vacuum drying is carried out in washing under 65 ℃, obtain not having the even bead of polystyrene matrix of adsorption activity, and particle diameter is distributed in 1.2-1.5mm;
B) tool nuclear matrix is aminated:
It is 6: 7 HNO that the tool nuclear matrix that steps A is made places the volume ratio that is chilled in advance below 10 ℃
3-H
2SO
4In the nitration mixture, stir under the ice bath environment, the control reaction temperature is no more than 10 ℃, carries out nitration reaction or part nitration reaction by controlling the reaction time, nitration product is taken out clean to pH＞5.5, joins the SnCl of 0.2g/mL
2Hydrochloric acid solution in, under agitation be heated to backflow, reaction is no less than 2.5 hours, temperature is 115 ℃, and product is taken out, and is washed till pH＞5.5 with deionized water;
C) boronate tool caryogamy position preparation of adsorbent:
Take by weighing the aminated tool nuclear matrix that step B makes, soak jolting, the 5%NaNO of the isopyknic same precooling of dropping in 30 minutes with 0 ℃ the 1mol/LHCl solution of being chilled in advance of 10 times of volumes
2, entire reaction is lower than 5 ℃ with ice bath control temperature; Dropwise the distilled water cleaning carrier of back with precooling, then this carrier is joined in the excessive saturated amido phenyl boric acid aqueous solution, jolting 30 minutes was reacted 12 hours, used washed with de-ionized water again, was drying to obtain in vacuum drying chamber.
4. the preparation method of kernel-containing boracic acid group absorptive according to claim 3, it is characterized in that: in the copolymerzation with cross-linking reaction of steps A, adding diameter is glass or the quartzy bead of the surface of 1.0-1.5mm through roughening treatment, obtains having the crosslinked polystyrene spheroid of glass or quartzy kernel.
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| CN104324704B (en) * | 2014-09-18 | 2016-08-17 | 宁波检验检疫科学技术研究院 | A kind of removing method of vikane |
| CN106693909B (en) * | 2017-01-19 | 2019-06-28 | 江苏大学 | A kind of magnetic nano-particle and its preparation method and application of phenyl boric acid modification |
| CN111272911A (en) * | 2020-03-19 | 2020-06-12 | 中国烟草总公司郑州烟草研究院 | Sample pretreatment method for determining Amadori compound in food |
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| CN1380133A (en) * | 2002-03-13 | 2002-11-20 | 华东理工大学 | Silicone dioxide magnetic microsphere and its preparation method |
| WO2004004749A1 (en) * | 2002-07-03 | 2004-01-15 | Charite - Universitätsmedizin Berlin | Proteaseome inhibitors for the treatment of herpesviridae infected individuals |
| CN1751828A (en) * | 2005-10-24 | 2006-03-29 | 南京大学 | Method for preparing micron/submicron bimetal nano ball shell |
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| CN1380133A (en) * | 2002-03-13 | 2002-11-20 | 华东理工大学 | Silicone dioxide magnetic microsphere and its preparation method |
| WO2004004749A1 (en) * | 2002-07-03 | 2004-01-15 | Charite - Universitätsmedizin Berlin | Proteaseome inhibitors for the treatment of herpesviridae infected individuals |
| CN1751828A (en) * | 2005-10-24 | 2006-03-29 | 南京大学 | Method for preparing micron/submicron bimetal nano ball shell |
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Assignee: Zhaoqing general gas liquid component Co., Ltd. Assignor: Zhaoqing University Contract fulfillment period: 2008.9.3 to 2013.9.3 contract change Contract record no.: 2009440001471 Denomination of invention: Kernel-containing boracic acid group absorptive and its preparing method Granted publication date: 20080723 License type: Exclusive license Record date: 2009.9.24 |
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