CN106008811A - Past-crosslinking macroporous resin and application thereof to purification of effective ingredient of peucedanum praeruptorum dunn - Google Patents

Past-crosslinking macroporous resin and application thereof to purification of effective ingredient of peucedanum praeruptorum dunn Download PDF

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CN106008811A
CN106008811A CN201610481818.9A CN201610481818A CN106008811A CN 106008811 A CN106008811 A CN 106008811A CN 201610481818 A CN201610481818 A CN 201610481818A CN 106008811 A CN106008811 A CN 106008811A
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macroporous resin
peucedanum praeruptorum
praeruptorum dunn
effective ingredient
resin
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聂小忠
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Shenzhen Polytechnic
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Shenzhen Polytechnic
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
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    • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28076—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being more than 1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
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    • C08F2/00—Processes of polymerisation
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
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    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
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Abstract

The invention discloses past-crosslinking macroporous resin and application thereof to purification of an effective ingredient of peucedanum praeruptorum dunn. Polar monomer methylacrylic acid glycol ester (EGDMA) is adopted to modify suspended double-bond past-crosslinking divinylbenzene (DVB) macroporous resin, a high specific surface and polarity are achieved at the same time, and the past-crosslinking macroporous resin can be widely applied to separation and purification of the coumarin effective ingredient in the peucedanum praeruptorum dunn. Adopted raw materials are easy to obtain, the preparation method is simple, product cost is low, and pollution to the environment is small. The past-crosslinking macroporous resin can be used repeatedly, and the concentration of the coumarin effective ingredient in the peucedanum praeruptorum dunn can be raised to 50% or above.

Description

Rear Crosslinked Macroporous resin and the application in Active Ingredient of Peucedanum Praeruptorum Dunn purification thereof
Technical field
The present invention relates to the separating and purifying technology field of a kind of Peucedanum praeruptorum DUNN Coumarins effective ingredient, particularly a kind of outstanding Hang Crosslinked Macroporous resin after double bond and preparation thereof and Peucedanum praeruptorum DUNN Coumarins effective ingredient isolated and purified in application.
Background technology
Peucedanum praeruptorum DUNN is the one of Chinese medicine Radix Peucedani, another name: Radix Peucedani (Mingyi Bielu), chicken foot Radix Peucedani, official's Radix Peucedani (medical material name), RADIX ANGELICAE PUBESCENTISs (Jiangsu) etc. are for perennial vertical herbage, high 60～90 centimetres or little over it；Root is thick, coniform, long 3～ 15 centimetres, there are branch, sepia or yellowish-brown；Stem is cylindric, the most sturdy, light green color, has lira, and base portion has most sepia Sheath fiber.Peucedanum praeruptorum DUNN mainly originates in the ground such as Anhui, Jiangxi, Zhejiang, Fujian, Guangxi, Hunan, Hubei, Sichuan, and Anhui Province is peaceful City of state Peucedanum praeruptorum DUNN yield occupies national best.Radix Peucedani is conventional Chinese medicine, has dispelling wind-heat, and effect of lowering the adverse-rising QI to resolve phlegm is used for controlling Treating anemopyretic cold, cough with copious phlegm, the yellow disease such as thick of coughing up phlegm, its main pharmacological action includes: 1, calcium knot anti-agent effect, 2, little to blood The effect of plate coagulation, 3, phlegm-dispelling functions, 4, Dilation of coronary artery.
Coumarin, also known as tonkabean lactone, adjacent chomene ketone, bifuran and cumarin, has benzene α-pyranone parent nucleus The general name of a class native compound, there is 6C-3C basic framework, coumarin ring often have the substituent group such as hydroxyl, methoxyl group.In vain Spend front HUGEN containing coumarin kind compound, mainly raceme praeruptorin (praeruptorin) the A i.e. Pd-of i.e. Pd, Ia, B II dextrorotation praeruptorin C, D and E, the white Ib of dextrorotation (Pd-Ib), III (Pd-III), the former is dextrorotation-3 ' (R)-Radix Angelicae Sinensis acyl-oxygen Base-4 '-one base-3 ', 4 '-dihydro seselin [3 ' (R)-angeloyloxy-4 '-keto-3 ', 4 '-dihydroseselin], The latter be dextrorotation-3 (S)-Radix Angelicae Sinensis acyloxy-4 '-(S)-isovaleryl epoxide-3 ', 4 '-dihydroseselin), pteryxin (pteryxin), Peucedanum praeruptorum DUNN coumarin (peucedanocoumarin) I, II, III, Radix Peucedani coumarin (qianhucoumarin) A, psoralen (Psoralen), 5-MOP (5-methoxy psoralen), 8- Methoxypsoralen (8-methoxy pso-ralen) [6], left-handed Peucedanum praeruptorum DUNN alcohol (peucedanol)；Coumarin glucoside Compounds: decuroside (nodakenin), India's glycoside (marmesinin), skimmin (skimmin), target perfume (or spice) furan Mutter tonquinol glycoside (rutarin), different Folium Symplocoris Caudatae furan tonquinol glycoside (isorutarin), scopolin (scoploin), Peucedanum praeruptorum DUNN glycoside (praeroside) I, II, III, IV and V, RADIX PEUCEDANI kind glycoside (decuroside) IV, splendid achnatherum Splendid achnatherum celery glycosyl skimmin (apiosylskimmin)；Other: PEARLITOL 25C (D-mannitol), cupreol (β Sitosterol), galactitol (galactitol), Radix Dauci Sativae sweet (daucosterol) and RADIX PEUCEDANI Saponin V (Pd- Saponin V i.e. 3-O-α-L-arabopyranose base-hederagenin-28-O-β-gentiobioside (3-O-α-L- arabinopyranosyl hederagenin-28-O-β-gentiobioside)。
In Peucedanum praeruptorum DUNN in the separating and purifying technology of Coumarins effective ingredient, it is generally required to by several extraction separation means Combine, individually use any method to be all relatively inaccessible to extraction, the purpose of purification Peucedanum praeruptorum DUNN coumarin.Crystallization is The method generally used to certain composition sterling of Peucedanum praeruptorum DUNN coumarin, but often require that in crystallization raw material, monomer effective content is not Can be the lowest, and column chromatography is to improve the effective ways of subject component content in natural product.At present, also there is more column chromatography Separation, the report of purification Peucedanum praeruptorum DUNN coumarin.
Complicated in Peucedanum praeruptorum DUNN, Peucedanum praeruptorum DUNN coumarin content are low, and it is unrealistic directly to carry out column chromatography, need be from vain In flower Radix Peucedani, preliminary extraction obtains Peucedanum praeruptorum DUNN coumarin extract.Preliminary extraction process generally uses organic solvent extraction, Also it is that the method that used of Peucedanum praeruptorum DUNN coumarin is extracted in current industrialization.But organic solvent extraction need to be dense through repeatedly extracting Contracting, not only energy consumption is big, the time is long, and Peucedanum praeruptorum DUNN coumarin is easily heated and is destroyed.And organic solvent is fragrant to Peucedanum praeruptorum DUNN The dissolving poor selectivity of legumin, extract impurity (wax) content is high, causes follow-up refined difficulty to strengthen.Supercritical extraction is then Can significantly improve extraction ratio, extraction yield is typically more than 90%, and less demanding to raw material, but CO2 supercritical fluid Abstraction technique process costs is higher, and condition requires harshness.These extracting method cut both ways, and are not that extraction ratio is low, it is simply that produce Cycle is long, and uses substantial amounts of solvent, unsafe.Peucedanum praeruptorum DUNN coumarin extraction ratio is low is to cause the Peucedanum praeruptorum DUNN wasting of resources, So, the extracting method of research Peucedanum praeruptorum DUNN coumarin has caused international great attention.
Resin adsorption method is as a kind of Solid phase extraction separation method of low energy consumption, and macroporous resin has mechanical strength High, production cost is low, physicochemical properties are stable, acid and alkali-resistance, reproducible utilization, the advantage such as simple to operation are increasingly subject to weight Depending on and have been widely used in industry.Flavonoids by Macroporous Adsorption Resin is low due to production cost, simple to operate, and extraction ratio is high, environmental protection It is with a wide range of applications extracting effective medicinal ingredient from Peucedanum praeruptorum DUNN etc. advantage.But macroporous resin is for from Radix Peucedani In the research of isolated and purified peucedanocoumarin effective constituents have no report temporarily.
Summary of the invention
It is that isolated and purified peucedanocoumarin effective constituents technique of the prior art is multiple to this end, to be solved by this invention Miscellaneous, that DNA purity is the highest technical problem.
The present invention provides Crosslinked Macroporous resin after one, it is adaptable to the legumin class in isolated and purified Peucedanum praeruptorum DUNN perfume (or spice) effectively becomes Point, cross-link divinylbenzene (DVB) macropore tree after modifying suspended double bond for polar monomer methacrylic acid glycol ester (EGDMA) Fat, its average pore size is 3-15nm, and specific surface area is 800-1500m2/ g, pore volume is 1.2-2.5ml/g.
Described polar monomer methacrylic acid glycol ester (EGDMA) cross-links divinylbenzene after modifying suspended double bond (DVB) macroporous resin, prepares by the following method:
(1) suspension polymerisation:
Divinylbenzene (DVB) and polar monomer methacrylic acid glycol ester (EGDMA) occur outstanding under initiator causes Floating polymerization, obtains having the initial copolymer of suspended double bond that polar group is modified；Its chemical equation is:
(2) post-crosslinking reaction:
After the initial copolymer of above-mentioned suspended double bond is the most swelling, add Friedel-Craft catalyst, Post-crosslinking reaction is there is at 60-100 DEG C, i.e. prepared legumin effective constituents be applicable to isolated and purified Peucedanum praeruptorum DUNN perfume (or spice) Rear Crosslinked Macroporous resin；Its chemical equation is:
The present invention provides the preparation method of a kind of above-mentioned rear Crosslinked Macroporous resin, comprises the steps:
(1) suspension polymerisation:
Divinylbenzene (DVB) and polar monomer methacrylic acid glycol ester (EGDMA) occur outstanding under initiator causes Floating polymerization, obtains having the initial copolymer of suspended double bond that polar group is modified；Its chemical equation is:
(2) post-crosslinking reaction:
After the initial copolymer of above-mentioned suspended double bond is the most swelling, add Friedel-Craft catalyst, Post-crosslinking reaction is there is, after i.e. preparing the legumin effective constituents be applicable to isolated and purified Peucedanum praeruptorum DUNN perfume (or spice) at 60-100 DEG C Crosslinked Macroporous resin；Its chemical equation is:
(3) eluting:
After post-crosslinking reaction completes, it is cooled to room temperature, after soak with ethanol, dilute acid soln soak, is washed to neutrality, dries, Standby.
It is also preferred that the left described organic solvent is dichloromethane, chloroform, acetone, oxolane, acetonitrile, toluene, normal heptane Or petroleum ether.
It is also preferred that the left described Friedel-Crafts catalyst is ferric chloride, ferrous chloride, zinc chloride, stannic chloride, chlorination Magnesium, manganese chloride, Chlorizate chromium, Nickel dichloride., cobaltous chloride.
It is also preferred that the left described diluted acid is dilute hydrochloric acid, phosphoric acid, nitric acid, aqueous sulfuric acid, concentration is 0.1-10mol/L.
The present invention also provides for the separation at Peucedanum praeruptorum DUNN Coumarins effective ingredient of a kind of above-mentioned rear Crosslinked Macroporous resin Application in purification.
The present invention also provides for a kind of isolated and purified method of Peucedanum praeruptorum DUNN Coumarins effective ingredient, including walking as follows Rapid:
(1) Peucedanum praeruptorum DUNN extract is prepared:
Using 70%-90% ethanol as extracting solution, using Peucedanum praeruptorum DUNN medicated powder end as extracting material, both liquid ratios For 10ml～100ml (70% ethanol): 1g (Peucedanum praeruptorum DUNN medicated powder), sonication treatment time 20～50 minutes, extracting solution is through vacuum Sucking filtration；Extracting 1～3 time the most altogether, all solution of extraction merge, and through being concentrated in vacuo, water-bath are evaporated, before spending in vain Extract 105 DEG C is dried to constant weight recklessly；
(2) Crosslinked Macroporous resin absorption afterwards:
Peucedanum praeruptorum DUNN extract dissolves the ethanol water with volumn concentration 6-10%, under room temperature, uses above-mentioned Rear Crosslinked Macroporous resin chromatography, adsorption column diameter and adsorption column length are than for 1:5 to 1:20, and flow velocity is 0.5-1.0BV/hr, in vain On the rear Crosslinked Macroporous resin that in flower Radix Peucedani, Coumarins effective ingredient is attracted in adsorption column；
(3) zeolite regeneration:
With the ethanol solution eluting adsorption column of volumn concentration 80-95%, rear Crosslinked Macroporous resin is regenerated, eluting Liquid recycling design final vacuum is dried, and obtaining Peucedanum praeruptorum DUNN Coumarins effective ingredient purity is the sample of 55-60%.
The technique scheme of the present invention has the advantage that compared to existing technology
1, the rear Crosslinked Macroporous resin of the present invention, has high-ratio surface and polarity concurrently, solves tradition non-polar resin and compares table Face is high and hydrophilic difference or polar resin hydrophilic is strong and contradiction that specific surface is low；This is reasonable in design, is widely portable to white In flower Radix Peucedani, Coumarins effective ingredient is isolated and purified.
2, its raw material used is easy to get；Preparation method is simple, only just can be obtained by a step post-crosslinking reaction, cross-link afterwards During need not use strong carcinogen chloromethyl ether, environmental friendliness.After suspended double bond, cross-linking method prepares high-ratio surface absorption tree Fat is avoided using strong volatility carcinogen chloromethyl ether, and experimental procedure is simple, and production cost is low, and environmental pollution is little.
3, the rear Crosslinked Macroporous resin of the present invention can repeatedly use, and actually used by more than 2 years, it is possible to The concentration making Peucedanum praeruptorum DUNN Coumarins effective ingredient brings up to more than 50%.
Accompanying drawing explanation
In order to make present disclosure be more likely to be clearly understood, below according to the specific embodiment of the present invention, to this Invention is described in further detail.
Fig. 1 is the contrast IR spectrogram before and after the post-crosslinking reaction of the rear Crosslinked Macroporous resin of the present invention.
Fig. 2 is the contrast aperture scattergram before and after the post-crosslinking reaction of the rear Crosslinked Macroporous resin of the present invention.
Fig. 3 be the rear Crosslinked Macroporous resin of the present invention post-crosslinking reaction before and after to praeruptorin A PA in aqueous solution Static adsorption isothermal line.
Detailed description of the invention
In order to make the object, technical solutions and advantages of the present invention clearer, below embodiments of the present invention are made into One step ground describes in detail.
Embodiment 1
Incorporated by reference to referring to table 1, utilize suspension polymerization to industry divinylbenzene (DVB) and polar monomer methacrylic acid Glycol ester (EGDMA) carries out copolymerization and prepares initial copolymer suspended double bond series plastics；Polymerization gained initial macroporous absorption tree Fat PDVB-EGDMA, after the most swelling in the organic solvent of 3-10 times, adds Friedel-Crafts catalyst (such as, nothing Aqueous ferric chloride etc.) effect under, at temperature 60-100 DEG C, carry out suspended double bond post-crosslinking reaction, generate high-ratio surface Rear Crosslinked Macroporous adsorbent resin.It is down to room temperature, filters, washing with alcohol soaked overnight, add appropriate HCl/water solution soaking, greatly Amount water washing is neutral to flowing out water, and washing with alcohol is dried final vacuum and dried, standby.
Cross-linked adsorbing resin after this high-ratio surface polarity is applied to isolated and purified effective medicinal ingredient from Peucedanum praeruptorum DUNN Peucedanum praeruptorum DUNN coumarin.
Concrete, using 70%-90% ethanol as extracting solution, using Peucedanum praeruptorum DUNN medicated powder end (crossing 60 mesh sieves) as extracting Material, both liquid ratios are 10ml～100ml (70% ethanol): 1g (Peucedanum praeruptorum DUNN medicated powder), sonication treatment time 20～50 Minute, extracting solution is through vacuum filtration；Extracting 1～3 time the most altogether, all solution of extraction merge, through being concentrated in vacuo, and water Being evaporated on bath, Peucedanum praeruptorum DUNN extract 105 DEG C is dried to constant weight.
Above-mentioned Peucedanum praeruptorum DUNN extract is dissolved in the ethanol water that volumn concentration is 6-10%, prepares upper prop Liquid；Above-mentioned rear Crosslinked Macroporous resin loads in adsorption column, and the ratio of adsorption column diameter and column length is 1:5-1:20；Under room temperature, will Upper prop liquid passes through resin absorbing column with the flow velocity of 0.5-1.0BV/ hour, and in Radix Peucedani therein, Coumarins effective ingredient is adsorbed On resin column；It is regenerated with volumn concentration for 80-95% ethanol solution eluting resin column, rear Crosslinked Macroporous resin, Eluent recycling design final vacuum is dried, and obtains the Peucedanum praeruptorum DUNN Coumarins effective ingredient sample that purity is 55-60%.
Refer to accompanying drawing 1 to 3, Fig. 1 is the infrared spectrum before and after macroporous adsorbent resin post-crosslinking reaction, and spectral detection is initial Copolymer polar resin contains suspended double bond, and the characteristic absorption peak of its suspended double bond is 1630,995 and 902cm-1, through catalyst The most substantially disappear after anhydrous ferric trichloride post-crosslinking reaction, illustrate the generation of post-crosslinking reaction and react completely.1609cm-1 It it is the C=C stretching vibration absorption of vinyl on X-5 resin phenyl ring.
Fig. 2 is the pore size distribution curve before and after BJH method makes macroporous adsorbent resin post-crosslinking reaction, it can be seen that macropore Adsorbent resin is after post-crosslinking reaction, and the specific surface area of resin and pore volume have had obvious increase.Anti-relative to rear crosslinking Macroporous resin before Ying, after post-crosslinking reaction, macroporous resin has more micropore, illustrates after post-crosslinking reaction, resin institute shape The hole become is mainly based on micropore.Rear Crosslinked Macroporous resin swelling ratio in water and organic solvent toluene is less than rear crosslinking Reaction front large hole resin, illustrates that initial copolymer is more stable in rear crosslinking back skeleton structure.
Fig. 3 be the rear Crosslinked Macroporous resin of the present invention post-crosslinking reaction before and after to praeruptorin A PA in aqueous solution Static adsorption isothermal line, adsorption isotherm is fitted with Freundlich equation and Langmuir equation respectively. Shown in Freundlich model and Langmuir model equation are expressed as follows:
Freundlich model:
l o g Q e = l o g K F + 1 n l o g C e
Langmuir model:
C e Q e = 1 K L Q m + C e Q m
K in formulaF((mg/g)/(mg/L)1/n) it is the characteristic parameter of resin absorption amount, n describes isothermal change and becomes Gesture, as n ＞ 1, adsorbent/adsorbate system is preferential absorption；KL(L/g) it is adsorption coefficient, Qm(mg/g) it is that monolayer is satisfied And adsorbance.Fitting result is as it is shown on figure 3, therefrom result is it will be seen that saturated to praeruptorin A PA of rear crosslinked resin Adsorbance all increased.This is because macroporous resin specific surface area after post-crosslinking reaction increases, under certain condition The adsorbance of adsorbate is directly proportional by resin, and specific surface area is the highest, and adsorbance is the biggest.It can also be seen that the suction of resin from Fig. 3 Attached isothermal line all meets Langmuir Adsorption Model, coefficient R2More than 0.99, before and after cross-linking after explanation, resin is at water body System adsorbs praeruptorin A PA and belongs to monolayer adsorption.The adsorption isotherm result of Freundlich Adsorption Model matching Also preferably, and n value is all higher than 1, and after explanation, before and after crosslinking, resin is preferential absorption to the absorption of praeruptorin A PA.
Table 1 preparation technology parameter and isolated and purified purity
The physical parameter contrast table of table 2 macroporous resin
PDVB-EGDMA resin PDVB-EGDMApc resin X-5 resin AB-8 resin
Average pore size (nm) 11.7 9.75 7.54 8.93
Pore volume (ml/g) 1.46 1.66 1.04 0.92
Specific surface area (m2/g) 805.1 1018.5 648.6 458.5
Appearance color White is spherical Brown is spherical White is spherical White is spherical
Particle diameter (mm) 0.1-1 0.1-1 0.1-1 0.1-1
Embodiment 2
The present embodiment experimental technique step is the most same as in Example 1, its recipe ingredient and the difference of preparation method technique It is not shown in Table 1.
Embodiment 3
The present embodiment experimental technique step is the most same as in Example 1, its recipe ingredient and the difference of preparation method technique It is not shown in Table 1.
Embodiment 4
The present embodiment experimental technique step is the most same as in Example 1, its recipe ingredient and the difference of preparation method technique It is not shown in Table 1.
Embodiment 5
The present embodiment experimental technique step is the most same as in Example 1, its recipe ingredient and the difference of preparation method technique It is not shown in Table 1.
Embodiment 6
The present embodiment experimental technique step is the most same as in Example 1, its recipe ingredient and the difference of preparation method technique It is not shown in Table 1.
Comparative example 1
Commercially available Peucedanum praeruptorum DUNN extract is dissolved in the ethanol water that volumn concentration is 6-10%, prepares Post liquid；Commercialization Resin A DS-17 being loaded in adsorption column, the ratio of adsorption column diameter and column length is 1:20；Under room temperature, by upper prop Liquid passes through resin absorbing column with the flow velocity of 1.0BV/ hour, and in Radix Peucedani therein, Coumarins effective ingredient is attracted to resin column On；Being 80% ethanol solution eluting resin column with volumn concentration, rear Crosslinked Macroporous resin is regenerated, and eluent reclaims molten Agent final vacuum is dried, and obtains the Peucedanum praeruptorum DUNN Coumarins effective ingredient sample that purity is 40%.
Comparative example 2
Commercially available Peucedanum praeruptorum DUNN extract is dissolved in the ethanol water that volumn concentration is 6-10%, prepares Post liquid；Being loaded in adsorption column by commercialization resin X-5, the ratio of adsorption column diameter and column length is 1:20；Under room temperature, by upper prop liquid with The flow velocity of 1.0BV/ hour passes through resin absorbing column, and in Radix Peucedani therein, Coumarins effective ingredient is attracted on resin column； Being 80% ethanol solution eluting resin column with volumn concentration, rear Crosslinked Macroporous resin is regenerated, eluent recycling design Final vacuum is dried, and obtains the Peucedanum praeruptorum DUNN Coumarins effective ingredient sample that purity is 36%.
Comparative example 3
Commercially available Peucedanum praeruptorum DUNN extract is dissolved in the ethanol water that volumn concentration is 6-10%, prepares Post liquid；Commercialization Resin A B-8 being loaded in adsorption column, the ratio of adsorption column diameter and column length is 1:20；Under room temperature, by upper prop liquid With the flow velocity of 1.0BV/ hour by resin absorbing column, in Radix Peucedani therein, Coumarins effective ingredient is attracted to resin column On；Being 80% ethanol solution eluting resin column with volumn concentration, rear Crosslinked Macroporous resin is regenerated, and eluent reclaims molten Agent final vacuum is dried, and obtains the Peucedanum praeruptorum DUNN Coumarins effective ingredient sample that purity is 38%.
Obviously, above-described embodiment is only for clearly demonstrating example, and not restriction to embodiment.Right For those of ordinary skill in the field, can also make on the basis of the above description other multi-form change or Variation.Here without also cannot all of embodiment be given exhaustive.And the obvious change thus extended out or Change among still in protection scope of the present invention.

Claims (9)

1. Crosslinked Macroporous resin after a kind, it is adaptable to the legumin effective constituents in isolated and purified Peucedanum praeruptorum DUNN perfume (or spice), for polarity list Body methacrylic acid glycol ester (EGDMA) cross-links divinylbenzene (DVB) macroporous resin, its average pore size after modifying suspended double bond For 3-15nm, specific surface area is 800-1500m2/ g, pore volume is 1.2-2.5ml/g.
Rear Crosslinked Macroporous resin the most according to claim 1, it is characterised in that: described polar monomer methacrylic acid second Diol ester (EGDMA) cross-links divinylbenzene (DVB) macroporous resin after modifying suspended double bond, prepares by the following method:
(1) suspension polymerisation:
Divinylbenzene (DVB) and polar monomer methacrylic acid glycol ester (EGDMA) occur to suspend to gather under initiator causes Close, obtain that there is the initial copolymer of suspended double bond that polar group is modified；Its chemical equation is:
(2) post-crosslinking reaction:
After the initial copolymer of above-mentioned suspended double bond is the most swelling, add Friedel-Craft catalyst, at 60- Post-crosslinking reaction, the rear friendship of i.e. prepared legumin effective constituents be applicable to isolated and purified Peucedanum praeruptorum DUNN perfume (or spice) is there is at 100 DEG C Connection macroporous resin；Its chemical equation is:
3. a preparation method for rear Crosslinked Macroporous resin according to claim 1 and 2, comprises the steps:
(1) suspension polymerisation:
Divinylbenzene (DVB) and polar monomer methacrylic acid glycol ester (EGDMA) occur to suspend to gather under initiator causes Close, obtain that there is the initial copolymer of suspended double bond that polar group is modified；Its chemical equation is:
(2) post-crosslinking reaction:
After the initial copolymer of above-mentioned suspended double bond is the most swelling, add Friedel-Craft catalyst, at 60- Post-crosslinking reaction, the rear friendship of i.e. prepared legumin effective constituents be applicable to isolated and purified Peucedanum praeruptorum DUNN perfume (or spice) is there is at 100 DEG C Connection macroporous resin；Its chemical equation is:
(3) eluting:
After post-crosslinking reaction completes, it is cooled to room temperature, after soak with ethanol, dilute acid soln soak, is washed to neutrality, dries, standby With.
The preparation method of rear Crosslinked Macroporous resin the most according to claim 3, it is characterised in that: described organic solvent is two Chloromethanes, chloroform, acetone, oxolane, acetonitrile, toluene, normal heptane or petroleum ether.
The preparation method of rear Crosslinked Macroporous resin the most according to claim 3, it is characterised in that: described Friedel- Crafts catalyst is ferric chloride, ferrous chloride, zinc chloride, stannic chloride, magnesium chloride, manganese chloride, Chlorizate chromium, Nickel dichloride., chlorine Change cobalt.
The preparation method of rear Crosslinked Macroporous resin the most according to claim 3, it is characterised in that: described diluted acid is dilute salt Acid, phosphoric acid, nitric acid, aqueous sulfuric acid, concentration is 0.1-10mol/L.
7. a rear Crosslinked Macroporous resin according to claim 1 and 2 dividing at Peucedanum praeruptorum DUNN Coumarins effective ingredient Application in purification.
8. an isolation and purification method for Peucedanum praeruptorum DUNN Coumarins effective ingredient, comprises the steps:
(1) Peucedanum praeruptorum DUNN extract is prepared:
Using ethanol as extract solution, using Peucedanum praeruptorum DUNN medicated powder end as extract material, both liquid ratios be 10ml～ 100ml:1g, sonication treatment time 20～50 minutes, extracting solution sucking filtration, concentrate, be dried to constant weight；
(2) Crosslinked Macroporous resin absorption afterwards:
Peucedanum praeruptorum DUNN extract is dissolved in the ethanol water of volumn concentration 6-10%, under room temperature, uses above-mentioned rear friendship The United Nations General Assembly's hole resin chromatography, adsorption column diameter and adsorption column length are than for 1:5 to 1:20, and flow velocity is 0.5-1.0BV/hr, before spending in vain On the rear Crosslinked Macroporous resin that in Hu, Coumarins effective ingredient is attracted in adsorption column；
(3) zeolite regeneration:
With the ethanol solution eluting adsorption column of volumn concentration 80-95%, rear Crosslinked Macroporous resin is regenerated, and eluent returns Receiving solvent final vacuum to be dried, obtaining Peucedanum praeruptorum DUNN Coumarins effective ingredient purity is the sample of 55-60%.
The isolation and purification method of Peucedanum praeruptorum DUNN Coumarins effective ingredient the most according to claim 8, it is characterised in that: system Standby Peucedanum praeruptorum DUNN extract particularly as follows:
Using 70%-90% ethanol as extracting solution, using Peucedanum praeruptorum DUNN medicated powder end as extracting material, both liquid ratios are 10ml～100ml (70% ethanol): 1g (Peucedanum praeruptorum DUNN medicated powder), sonication treatment time 20～50 minutes, extracting solution is taken out through vacuum Filter；Extracting 1～3 time the most altogether, all solution of extraction merge, and through being concentrated in vacuo, water-bath are evaporated, Peucedanum praeruptorum DUNN Extract 105 DEG C is dried to constant weight.
CN201610481818.9A 2016-06-27 2016-06-27 Past-crosslinking macroporous resin and application thereof to purification of effective ingredient of peucedanum praeruptorum dunn Pending CN106008811A (en)

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CN110256624A (en) * 2019-05-23 2019-09-20 广东工业大学 A kind of hypercrosslinked polymeric resin and its application in adsorbing separation 5 hydroxymethyl furfural
CN112358563A (en) * 2020-12-01 2021-02-12 西安蓝深环保科技有限公司 Macroporous adsorption resin for lincomycin extraction and synthetic method thereof

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Publication number Priority date Publication date Assignee Title
CN110256624A (en) * 2019-05-23 2019-09-20 广东工业大学 A kind of hypercrosslinked polymeric resin and its application in adsorbing separation 5 hydroxymethyl furfural
CN112358563A (en) * 2020-12-01 2021-02-12 西安蓝深环保科技有限公司 Macroporous adsorption resin for lincomycin extraction and synthetic method thereof
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