CN100494231C - Preparation of screening type adsorption resin and application thereof in separating panaxoside monomer Rb1 - Google Patents
Preparation of screening type adsorption resin and application thereof in separating panaxoside monomer Rb1 Download PDFInfo
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Abstract
The invention discloses a making method of screening-typed adsorbing resin and application to separate panaxoside monomer Rb1, which is characterized by the following: adsorbing in the resin channel; eluting; separating Rb1 from other monomer panaxoside completely; obtaining the panaxoside Rb1 with purity over 50%.
Description
[technical field] the present invention relates to the separation technology field of the synthetic and middle pharmaceutically active ingredient of polymeric adsorbent, the highly selective polystyrene adsorption resin of the little and even aperture distribution of particularly synthetic mean pore size, make it have the synergy of screening and absorption, can accurately sieve according to the difference of molecular dimension, use it for the saponin monomer Rb1 that separates in Radix Ginseng total saponins, the Radix Notoginseng total arasaponins extract at last.
The Chinese medicinal materials that [background technology] contains the ginsenoside effective constituents all shows significant biological activity in folk tradition medication and modern medicines development research, for example genseng, Radix Panacis Quinquefolii, pseudo-ginseng etc.Practice for many years shows that they all have good pharmacologically active for cardiovascular systems, blood and hemopoietic system, central nervous system, immunity system, can delaying human body caducity.Pharmaceutical component in the ginsenoside mainly contains the close saponin monomer composition of several structures, as the ginsenoside Rb1, and the ginsenoside Rg1, ginsenoside Re also contains a kind of special saponin monomer arasaponin R1 in addition in the pseudo-ginseng.Their structure is as follows:
General, saponin monomer almost can reproduce all biological of total saponin and learn active, but along with going deep into of research, it is found that some saponin monomer has unique pharmacological action, even find that some saponin monomer has opposite pharmacologically active, and as Rg1 stronger hemolytic action being arranged, Rb1 then has antih(a)emolysin, Rb1 promotes platelet aggregation, and Rg1, Re anticoagulant.In the influence research of cholesterol metabolic, someone thinks that protopanoxadiol is that ginsenoside Rb1 of glucoside unit etc. stimulates the effect of cholesterol synthetic stronger, be a little less than ginsenoside Rg1, the Re of glucoside unit then acts on Protopanaxatriol, so the different proportionings of saponin monomer can realize different drug effects.
The pharmacological research of saponin monomer Rb1 causes people's very big concern in Radix Ginseng total saponins; people's such as Jiang Pei result of study confirms; it is obvious that the ischemia-reperfusion lung injury action effect is transplanted in the anti-simulation of Rb1; and Rg1 does not have obvious restraining effect [Jiang Pei to ischemia-reperfusion lung injury; Deng. ginsenoside Rb1 and Rg1 transplant the provide protection of lung to simulation; Zhongshan Medical Univ.'s journal; 1997; 18 (2): 85～88]; so Rb1 is the medicine that lung is transplanted in a kind of up-and-coming protection, be worth further research.What is more important Rb1 can obtain the pure product of some secondary glucoside through chemical conversion process to its modification transformation of carrying out chemical structure in addition.Secondary glucoside generally has tangible pharmacologically active, as Rh2 is a kind of natural plant composition of antitumor, the anti-metastasis of finding recently, the choice drug of chemotherapeutic sensitivity attenuation [national herbal medicine is write group. national herbal medicine compilation: the first volume [M], Beijing: People's Health Publisher, 1992.20.]; Secondary glucoside Rg3 has the effect [1 that tumor neogenetic blood vessels forms that suppresses, Pan Zimin, the leaf strong wind is thanked emerging, etc. the research [J] of the antineoplastic vascular nucleus formation of the Reconstruction in Sever Combined Immunodeciency mouse of 3 pairs of lotus knurls of panaxoside Rg ovarian cancer. Chinese journal of obstetrics and gynecology, 2002,37 (4): 227-230; 2, Gao Yong, Wang Jiejun, Xu Qing. panaxoside Rg 3 suppresses the research [J] that tumor neogenetic blood vessels forms. The 2nd Army Medical College journal, 2001,22 (1): 40-42].Therefore, secondary glucoside has high pharmaceutical use and application prospect.Twentieth century eighties, a lot of in the world scholars make great efforts to develop secondary glucoside product.But the general content of these secondary glucosides is very little or plant in do not contain, it is a kind of meta-bolites, so limited its application and development greatly, therefore if can obtain required secondary glucoside from the modification or the transformation of the higher panaxoside monomer of content by chemical structure, (for example from genseng, extract panoxadiol class saponin Rb1, hydrolysis method changes glycols saponin glycosyl and prepares low-polar [Zhang Chunfang, the preparation research of low-polar, the Anhui chemical industry, 2005, (3): 25]), will go deep into more for the medicinal research of ginsenoside.At present the main source of saponin monomer remains extraction separation from natural phant, generally is solvent extration, crosses silicagel column and Sephadex post repeatedly, and complex steps expends a large amount of solvents and the product that obtains only limits to quantitative analysis and uses.It is poor to separating the little compound separation of difference, and the operating time is long, and the solvent amount of expending is big.What have comes saponin monomer is separated with positive or anti-phase HPLC, though the product purity that obtains is higher, the amount that generally obtains also is fewer, use only for being used for analyzing, and cost is than higher, so and the moving phase of HPLC acetonitrile is generally arranged, toxicity also is very big.Therefore set up that a kind of process is simple, lower, the eco-friendly separation method of cost is very significant to prepare highly purified saponin monomer.It is high that macroporous adsorbent resin has stability, loading capacity is big, advantages such as the good and easy regeneration of selectivity, many Effective Components of Chinese Herb extract with separate in obtained good effect, become the indispensable isolation technique of the propelling modernization of Chinese medicine, the research that separates the saponin monomer Rb1 in total saponin with resin method yet there are no report.Because the structural similitude of several principal monomer saponins in total saponin, molecular weight and polarity difference are little, are difficult to separate with general macroporous adsorbent resin.
[summary of the invention] order of the present invention ground is to solve the above-mentioned problems in the prior art, a kind of preparation method of polystyrene type polymeric adsorbent of highly selective is provided, and use it for the separation of saponin monomer Rb1 in Radix Ginseng total saponins, the Radix Notoginseng total arasaponins extract, with commercially available extract is raw material, only through " adsorbing a desorption " step simple process, can reach separating fully of ginsenoside Rb1 and other saponin monomers.
The present invention addresses the above problem the scheme that is adopted to be, change traditional macroporous adsorbent resin by the method for poor solvent through the pore that is separated, adopt the polymeric adsorbent of the novel pore structure of the less and even aperture distribution of the synthetic a kind of mean pore size of cross-linking method after the Fu Shi alkylation, this resinoid has screening and adsorption dual function concurrently, can realize the separation of the saponin monomer Rb1 that molecular dimension is bigger in total saponin.
The concrete preparation method of screening type polystyrene adsorption resin provided by the invention, realize by following steps:
(1) preparation of low cross-linking polystyrene adsorption resin:
At normal temperatures, gelatin or polyvinyl alcohol are dissolved in the water, be made into the water of 0.5%-5%, be heated to 30-50 ℃, with the mix monomer of vinylbenzene and divinylbenzene is reaction oil phase (divinylbenzene account for mix monomer total mass 0.5-1.5%), wherein water and oil phase volume ratio are 3: 1, with the benzoyl peroxide is initiator, consumption is the 1-3% of mix monomer total mass, through suspension polymerization, slowly is warming up to 70-80 ℃ of reaction and slowly is warming up to 85 ℃ of reactions 3 hours more than 3 hours again, slowly be warming up to again more than 95 ℃ and reacted 3 hours, after filtration, after the carrying out washing treatment, prepare low cross-linking gel type polystyrene resin, be called for short Archon.
(2) preparation of the polystyrene resin of low cross-linking chloromethylation:
Add Archon under the normal temperature in there-necked flask, with the abundant swelling of the mixing solutions of chloromethyl ether and ethylene dichloride, the mixing solutions consumption is 6-8 a times of Archon quality, and the volume ratio of chloromethyl ether and ethylene dichloride is 1: 2.Add ZnCl
2Make catalyzer, consumption is the 40-80% of low cross-linking polystyrene quality, and fully mixing is warmed up to 30-40 ℃ then, react 8-12 hour, after filtration, after the carrying out washing treatment, prepare the styrene resin of low cross-linking chloromethylation, abbreviation chlorine ball.
(3) preparation of screening type polystyrene adsorption resin:
In there-necked flask, add the chlorine ball under the normal temperature, with the abundant swelling of ethylene dichloride, consumption is 8-10 a times of chlorine ball quality, under agitation drip tin tetrachloride and ethylene dichloride mixing solutions, consumption is the 50-70% of low cross-linking chloromethylation styrene resin quality, and the volume ratio of tin tetrachloride and ethylene dichloride is 1: 1-2: 1, speed with 0.5-2.0 ℃/min rises to 80-100 ℃ with temperature, reacts stopped reaction 8-10 hour, filter, dehydrated alcohol extraction 6-8 hours are used in washing, the resin that obtains in apparatus,Soxhlet's, resin is taken out dry, vacuum-drying obtains required screening type polystyrene adsorption resin.
Its external appearance characteristic and structural parameter are: resin is the translucent spheroidal particle of reddish-brown, particle diameter 0.3-1.0mm, and specific surface area is 1200-1600m
2/ g dried resin, water content are 50-70%, and mean pore size is 2-3nm, porosity 50-80%.
The monomer ginsenoside Rb1 of above-mentioned screening type polystyrene adsorption resin in separating arasaponin or ginsenoside extract application:
(1) with commercially available ginsenoside or arasaponin extract water dissolution, makes adsorbent solution.
(2) polymeric adsorbent of above preparation is packed in the adsorption column, the specification of adsorption column is: column diameter/column length is 1/8-1/20.
(3) under the room temperature, with adsorbent solution with 0.3-1.0BV/ hour flow velocity by resin column, wherein the ginsenoside Rb1 can't diffuse in the resin hole and be flowed out from resin column with adsorbent solution by active adsorption, other saponin monomer is adsorbed on the resin column fully.
When (4) adsorbing, the treatment capacity of every milliliter of resin is that 8-19mg ginsenoside is carried thing thing or arasaponin extract at every turn, and total saponin content is 60%-75% in the extract, and wherein ginsenoside Rb1's content is 20%-35%.
(5) after absorption is finished, collect the absorption effluent liquid, resin column is collected elutriant with 70% aqueous ethanolic solution wash-out, and effluent liquid and elutriant are respectively through vacuum distillation recovered solvent, concentrated, vacuum-drying, obtain two kinds of solid phase prods, detect through the Waters484 high performance liquid chromatograph respectively, only contain the ginsenoside Rb1 in the solid phase prod behind the effluent liquid evaporate to dryness, substantially do not contain all the other saponin monomers, and do not contain the ginsenoside Rb1 in the solid phase prod behind the elutriant evaporate to dryness and only contain all the other saponin monomers.
Advantage of the present invention and positively effect: the present invention is according to the constitutional features and the size difference of saponin monomer, synthesized the little and polystyrene type polymeric adsorbent even and the novel pore structure that the aperture is adjustable within the specific limits in a kind of aperture, screening and the adsorption dual function of utilizing this resin to have, can realize that the molecular polarity difference is little, structural similitude, but the separation of differentiated molecule on molecular dimension.Can't enter the resin duct because the size of Rb1 is big is adsorbed, thereby in adsorption process, from resin column, flow out with adsorbent solution, all the other saponin monomers are because size is less, can enter the resin duct is adsorbed, after absorption is finished, the certain density alcohol desorption of resin column, these several saponin monomers flow out with elutriant, therefore we are only by " absorption-wash-out " step simple process, both can realize separating fully of Rb1 and other saponin monomer, a large amount of strong toxicity have been avoided using in the existing separating technology, volatile, the defective that inflammable organic solvent and separating technology are loaded down with trivial details, technology of the present invention is simple, do not use toxic organic solvent, environmental friendliness, the renewable use of resin, production cost is low, ginsenoside Rb1's purity is higher than 50%, and does not contain other saponin monomer, can be further medicinal exploitation a large amount of test samples are provided.
[embodiment]
Embodiment 1:
The preparation method of screening type adsorption resin, realize by following steps:
At normal temperatures, polyvinyl alcohol is dissolved in the water, is made into the aqueous solution 450ml of concentration 1.0%, heating in water bath to 45 ℃ in the 1000ml there-necked flask; 148.5g vinylbenzene, 1.5g divinylbenzene, 1.5g benzoyl peroxide are mixed the back to add in the there-necked flask; start stirring; regulate the oil droplet suitable size, through suspension polymerization, 78 ℃ of reactions are more than 3 hours; slowly be warming up to 85 ℃ of reactions 3 hours again; slowly be warming up to more than 95 ℃ reaction 3 hours again, stopped reaction, after filtration, after the carrying out washing treatment; prepare low cross-linking gel type polystyrene resin, be called for short Archon.
In the 1000ml there-necked flask, add the Archon of 40g, make swelling agent with the mixed solvent of 240g chloromethyl ether and 480g ethylene dichloride, after the abundant swelling of Archon, the anhydrous ZnCl of 25g
2, after mixing, be warming up to 35 ℃, reacted 10 hours, after filtration, after the carrying out washing treatment, prepare low cross-linking chloromethylation styrene resin, be called for short the chlorine ball.
The chlorine ball that in the 1000ml there-necked flask, adds 50g, after making its abundant swelling with the 500g ethylene dichloride, under agitation drip the mixing solutions of 15g tin tetrachloride and 15g ethylene dichloride, speed with 1.0 ℃/min rises to 80 ℃ with temperature, reacted 10 hours, after filtration, washing, in apparatus,Soxhlet's, use dehydrated alcohol extraction 8 hours, take out resin, dry the final vacuum drying, obtain required screening type adsorption resin, its external appearance characteristic and structural parameter are: the tree resin is the translucent spheroidal particle of reddish-brown, particle diameter 0.4-0.8mm, and specific surface area is 1255m
2/ g dried resin, water content are 59%, and mean pore size is 2.17nm, porosity 56.5%.
Embodiment 2:
The preparation method of screening type adsorption resin, realize by following steps:
At normal temperatures, polyvinyl alcohol is dissolved in the water, is made into 4.5 liters of the aqueous solution of concentration 1.0%, heating in water bath to 45 ℃ in 10 liters of there-necked flasks; 1.5Kg vinylbenzene, 0.15Kg divinylbenzene, 30g benzoyl peroxide are mixed the back to add in the there-necked flask; start stirring; regulate the oil droplet suitable size, through suspension polymerization, 78 ℃ of reactions are more than 3 hours; slowly be warming up to 85 ℃ of reactions 3 hours again; slowly be warming up to more than 95 ℃ reaction 3 hours again, stopped reaction, after filtration, after the carrying out washing treatment; prepare low cross-linking gel type polystyrene resin, be called for short Archon.
In 10 liters of there-necked flasks, add the Archon of 400g, make swelling agent with the mixed solvent of 2.8Kg chloromethyl ether and 5.6Kg ethylene dichloride, after the abundant swelling of Archon, the anhydrous ZnCl of 300g
2, after mixing, be warming up to 30 ℃, reacted 12 hours, after filtration, after the carrying out washing treatment, prepare low cross-linking chloromethylation styrene resin, be called for short the chlorine ball.
The low cross-linking chloromethylation styrene resin that in there-necked flask, adds 50g, after making its abundant swelling with the ethylene dichloride of 10 times of low cross-linking chloromethylation styrene resin amounts, under agitation drip tin tetrachloride and ethylene dichloride mixing solutions, consumption is 55% of low cross-linking chloromethylation styrene resin amount, and temperature is risen to 90 ℃ with certain speed, reacted 8.5 hours, after filtration, washing was extracted 7 hours in apparatus,Soxhlet's, take out resin, dry the final vacuum drying, obtain required screening type adsorption resin, its external appearance characteristic and structural parameter are: the tree resin is the translucent spheroidal particle of reddish-brown, particle diameter 0.3-1.0mm, specific surface area is 1128m
2/ g dried resin, water content are 65%, and mean pore size is 2.21nm, porosity 58.2%.
Embodiment 3:
The application of above-mentioned screening type adsorption resin saponin monomer Rb1 in separating Radix Notoginseng total arasaponins
With purity is that (wherein ginsenoside Rb1's content is 20.6% for 66.3% commercially available Radix Notoginseng total arasaponins extract 165.0mg, the ginsenoside Rg1, the total content of Re and arasaponin R1 is 45.7%), be dissolved in the 40ml water, be made into adsorbent solution, by resin column (the column length 20cm that above-mentioned screening type adsorption resin is housed, internal diameter 1.5cm, the 20ml wet resin is housed), rate of adsorption is 1BV/h, after absorption was finished, with 70% aqueous ethanolic solution wash-out, flow velocity was 1BV/h, effluent liquid and elutriant are respectively through underpressure distillation, vacuum-drying gets solids, detect through the Waters484 high performance liquid chromatograph, ginsenoside Rb1's content is 53.6% in the absorption effluent liquid, and other three kinds of saponin monomers do not detect, the content of three kinds of saponin monomers is 87.4% in the elutriant, and Rb1 does not detect.
Embodiment 4:
With purity is that (wherein ginsenoside Rb1's content is 20.6% for 66.3% commercially available Radix Notoginseng total arasaponins extract 357.6mg, the ginsenoside Rg1, the total content of Re and arasaponin R1 is 45.7%), be dissolved in the 40ml water, be made into adsorbent solution, by resin column (the column length 20cm that above-mentioned screening type adsorption resin is housed, internal diameter 1.5cm, the 20ml wet resin is housed), rate of adsorption is 1BV/h, after absorption was finished, with 70% aqueous ethanolic solution wash-out, flow velocity was 1BV/h, absorption effluent liquid and elutriant are respectively through underpressure distillation, vacuum-drying gets solids, detect through the Waters484 high performance liquid chromatograph, ginsenoside Rb1's content is 50.1% in the absorption effluent liquid, and other three kinds of saponin monomers do not detect, the content of three kinds of saponin monomers is 81.2% in the elutriant, and the content of Rb1 is 0.8%.
Embodiment 5:
With purity is that (wherein ginsenoside Rb1's content is 20.6% for 66.3% commercially available Radix Notoginseng total arasaponins extract 362.0mg, the ginsenoside Rg1, the total content of Re and arasaponin R1 is 45.7%), be dissolved in the 40ml water, making Radix Notoginseng total arasaponins solution adsorbs waiting, by resin column (the column length 20cm that above-mentioned screening type adsorption resin is housed, internal diameter 1.5cm, the 20ml wet resin is housed), rate of adsorption is 0.5BV/h, after absorption was finished, with 70% aqueous ethanolic solution wash-out, flow velocity was 0.5BV/h, absorption effluent liquid and elutriant are respectively through underpressure distillation, vacuum-drying gets solids, detect through the Waters484 high performance liquid chromatograph, ginsenoside Rb1's content is 55.8% in the absorption effluent liquid, and other three kinds of saponin monomers do not detect, the content of three kinds of saponin monomers is 88.6% in the elutriant, and Rb1 does not detect.
Embodiment 6:
With purity is that (wherein ginsenoside Rb1's content is 31.2% for 68.5% commercially available Radix Ginseng total saponins extract 357.3mg, the total content of ginsenoside Rg1 and Re is 37.3%), be dissolved in the 40ml water, be made into adsorbent solution, by resin column (the column length 20cm that above-mentioned screening type adsorption resin is housed, internal diameter 1.5cm, the 20ml wet resin is housed), rate of adsorption is 0.5BV/h, after absorption was finished, with 70% aqueous ethanolic solution wash-out, flow velocity was 0.5BV/h, absorption effluent liquid and elutriant are respectively through underpressure distillation, vacuum-drying gets solids, detect through the Waters484 high performance liquid chromatograph, ginsenoside Rb1's content is 62.5% in the absorption effluent liquid, and Rg1 and Re do not detect, the total content of Rg1 and Re is 89.3% in the elutriant, and Rb1 does not detect.
Embodiment 7:
With purity is that (wherein ginsenoside Rb1's content is 20.6% for 66.3% commercially available Radix Notoginseng total arasaponins extract 801.2mg, the ginsenoside Rg1, the total content of Re and arasaponin R1 is 45.7%), be dissolved in the 100ml water, be made into adsorbent solution, by resin column (the column length 50cm that above-mentioned screening type adsorption resin is housed, internal diameter 2.5cm, the 100ml wet resin is housed), rate of adsorption is 0.45BV/h, after absorption was finished, with 70% aqueous ethanolic solution wash-out, flow velocity was 0.45BV/h, absorption effluent liquid and elutriant are respectively through underpressure distillation, vacuum-drying gets solids, detect through the Waters484 high performance liquid chromatograph, ginsenoside Rb1's content is 58.9% in the absorption effluent liquid, and other three kinds of saponin monomers do not detect, the content of three kinds of saponin monomers is 90.1% in the elutriant, and Rb1 does not detect.
Embodiment 8:
With purity is that (wherein ginsenoside Rb1's content is 20.6% for 66.3% commercially available Radix Notoginseng total arasaponins extract 1588.4mg, the ginsenoside Rg1, the total content of Re and arasaponin R1 is 45.7%), be dissolved in the 100ml water, be made into adsorbent solution, by resin column (the column length 50cm that above-mentioned screening type adsorption resin is housed, internal diameter 2.5cm, the 100ml wet resin is housed), rate of adsorption is 0.3BV/h, after absorption was finished, with 70% aqueous ethanolic solution wash-out, flow velocity was 0.3BV/h, absorption effluent liquid and elutriant are respectively through underpressure distillation, vacuum-drying gets solids, detect through the Waters484 high performance liquid chromatograph, ginsenoside Rb1's content is 54.3% in the absorption effluent liquid, and other three kinds of saponin monomers do not detect, the content of three kinds of saponin monomers is 87.2% in the elutriant, and Rb1 does not detect.
Embodiment 9:
With purity is that (wherein ginsenoside Rb1's content is 31.2% for 68.5% commercially available Radix Ginseng total saponins extract 40.0g, the total content of ginsenoside Rg1 and Re is 37.3%), be dissolved in 4 premium on currency, be made into adsorbent solution, by resin column (the column length 150cm that above-mentioned screening type adsorption resin is housed, internal diameter 25cm, the 2Kg wet resin is housed), rate of adsorption is 0.5BV/h, after absorption was finished, with 70% aqueous ethanolic solution wash-out, flow velocity was 0.5BV/h, absorption effluent liquid and elutriant are respectively through underpressure distillation, vacuum-drying gets solids, detect through the Waters484 high performance liquid chromatograph, ginsenoside Rb1's content is 59.3% in the absorption effluent liquid, and Rg1 and Re do not detect, the total content of Rg1 and Re is 91.3% in the elutriant, and Rb1 does not detect.
Claims (3)
1, a kind of preparation method of screening type polystyrene adsorption resin is characterized in that realizing by following steps:
(1) preparation of low cross-linking polystyrene adsorption resin:
At normal temperatures, gelatin or polyvinyl alcohol are dissolved in the water, be made into the reaction water of 0.5%-5%, be heated to 30-50 ℃, mix monomer with vinylbenzene and divinylbenzene is the reaction oil phase, divinylbenzene accounts for 0.5-1.5% of mix monomer total mass, and wherein water and oil phase volume ratio are 3: 1, is initiator with the benzoyl peroxide, consumption is the 1-3% of mix monomer total mass, through suspension polymerization, slowly be warming up to 70-80 ℃ of reaction more than 3 hours, slowly be warming up to 85 ℃ of reactions 3 hours again, slowly be warming up to again more than 95 ℃ and reacted 3 hours, after filtration, after the carrying out washing treatment, prepare low cross-linking gel type polystyrene resin, be called for short Archon;
(2) preparation of the polystyrene resin of low cross-linking chloromethylation:
Add Archon under the normal temperature in there-necked flask, with the abundant swelling of the mixing solutions of chloromethyl ether and ethylene dichloride, the mixing solutions consumption is 6-8 a times of Archon quality, and the volume ratio of chloromethyl ether and ethylene dichloride is 1: 2, adds ZnCl
2Make catalyzer, consumption is the 40-80% of low cross-linking polystyrene quality, and fully mixing is warmed up to 30-40 ℃ then, react 8-12 hour, after filtration, after the carrying out washing treatment, prepare the styrene resin of low cross-linking chloromethylation, abbreviation chlorine ball;
(3) preparation of screening type polystyrene adsorption resin:
In there-necked flask, add the chlorine ball under the normal temperature, with the abundant swelling of ethylene dichloride, consumption is 8-10 a times of chlorine ball quality, under agitation drip tin tetrachloride and ethylene dichloride mixing solutions, consumption is the 50-70% of low cross-linking chloromethylation styrene resin quality, and the volume ratio of tin tetrachloride and ethylene dichloride is 1: 1-2: 1, speed with 0.5-2.0 ℃/min rises to 80-100 ℃ with temperature, reacts stopped reaction 8-10 hour, filter, dehydrated alcohol extraction 6-8 hour used in washing, the resin that obtains in apparatus,Soxhlet's, resin is taken out dry, vacuum-drying obtains required screening type polystyrene adsorption resin.
2, the preparation method of screening type polystyrene adsorption resin according to claim 1, the external appearance characteristic and the structural parameter that it is characterized in that described polymeric adsorbent are: resin is the translucent spheroidal particle of reddish-brown, particle diameter 0.3-1.0mm, specific surface area is 1200-1600m
2/ g dried resin, water content are 50-70%, and mean pore size is 2-3nm, porosity 50-80%.
3, the monomer ginsenoside Rb1 of screening type polystyrene adsorption resin in separating arasaponin or ginsenoside extract of the described method preparation of a kind of claim 1 application is characterized in that:
(1) with commercially available ginsenoside or arasaponin extract water dissolution, makes adsorbent solution;
(2) the screening type polystyrene adsorption resin of above preparation is packed in the adsorption column, the specification of adsorption column is: column internal diameter/column length is 1/5-1/20;
(3) under the room temperature, adsorbent solution is passed through resin column with 0.3-1.0BV/ hour flow velocity, wherein the ginsenoside Rb1 can't diffuse in the resin hole and be flowed out from resin column with adsorbent solution by active adsorption, and other saponin monomer is adsorbed on the resin column fully;
When (4) adsorbing, the treatment capacity of every milliliter of resin is 8-19mg ginsenoside extract or arasaponin extract at every turn, and total saponin content is 60%-75% in the extract, and wherein ginsenoside Rb1's content is 20%-35%;
(5) after absorption is finished, collect the absorption effluent liquid; Resin column is collected elutriant with 70% aqueous ethanolic solution wash-out; Effluent liquid and elutriant are respectively through vacuum distillation recovered solvent, concentrated, vacuum-drying, obtain two kinds of solid phase prods, detect through the Waters484 high performance liquid chromatograph respectively, only contain the ginsenoside Rb1 in the solid phase prod behind the effluent liquid evaporate to dryness, do not contain all the other saponin monomers, and do not contain the ginsenoside Rb1 in the solid phase prod behind the elutriant evaporate to dryness, only contain all the other saponin monomers.
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| CN101912770B (en) * | 2010-09-03 | 2012-07-04 | 中国科学院长春应用化学研究所 | Polymeric adsorbent and preparation method thereof |
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| CN103304836A (en) * | 2013-06-28 | 2013-09-18 | 天津欧瑞生物科技有限公司 | Preparation of imprinting type sieving adsorbent resin and method for removing pesticide residue in traditional Chinese medicine extract by using imprinting type sieved adsorbing resin |
| CN107759812B (en) * | 2017-10-10 | 2020-12-15 | 深圳大学 | Crosslinked polymer based on waste polystyrene, and preparation method and application thereof |
| CN109833854B (en) * | 2019-03-04 | 2019-12-20 | 蚌埠市天星树脂有限责任公司 | Macroporous adsorption resin and preparation method thereof |
| CN112742356B (en) * | 2020-12-15 | 2021-08-10 | 蚌埠市天星树脂有限责任公司 | Adsorption resin for treating waste water and gas and preparation method thereof |
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