CN111875650A - Preparation and application of boric acid functionalized resin - Google Patents
Preparation and application of boric acid functionalized resin Download PDFInfo
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- CN111875650A CN111875650A CN202010797366.1A CN202010797366A CN111875650A CN 111875650 A CN111875650 A CN 111875650A CN 202010797366 A CN202010797366 A CN 202010797366A CN 111875650 A CN111875650 A CN 111875650A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H17/00—Compounds containing heterocyclic radicals directly attached to hetero atoms of saccharide radicals
- C07H17/04—Heterocyclic radicals containing only oxygen as ring hetero atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/20—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the sorbent material
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
- C07H1/08—Separation; Purification from natural products
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- C—CHEMISTRY; METALLURGY
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/24—Haloalkylation
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- C—CHEMISTRY; METALLURGY
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Abstract
The invention provides a preparation method of boric acid functionalized resin and application of the boric acid functionalized resin in separation and purification of high-purity oleuropein, thereby overcoming the defects of high target solvent usage amount, complex process, low oleuropein purity and low yield in the prior art. The m-aminobenzene boric acid resin has the advantages of simple preparation process, simple and convenient operation and no use of corrosive chemical reagents; the process route for purifying the oleuropein is simple, the purity can reach more than 60 percent, the yield can reach more than 60 percent, the cost is low, the efficiency is high, and the method is suitable for large-scale industrial production. The m-aminophenylboronic acid functionalized resin can be regenerated and reused, and the adsorption capacity is reduced by about 5% after five times of recycling.
Description
Technical Field
The invention belongs to the technical field of preparation and application of natural product separation materials, and particularly relates to preparation of boric acid functionalized resin and application of the boric acid functionalized resin in separation and purification of high-purity oleuropein.
Background
Olea europaea L is used as an economic crop, is mainly planted in Greece, Italy and other countries along the coast of the Mediterranean at first and is introduced into China later. At present, the seeds are mainly cultured in Yunnan, Sichuan, Gansu, Guizhou and other places.
Olive leaves are the main by-products of olive growing industry, which are discarded every year when fruits are pruned and harvested, but olive leaves contain various active substances such as polyphenols, flavonoids, seco-iridoids, biflavones, etc., and the waste materials generated in the olive oil production process, such as olive pomace and olive waste water, also contain abundant Oleuropein (OL), which is an important polyphenol compound, and OL has antioxidant, antifungal, antiviral, anticancer and hypoglycemic effects. Therefore, it is necessary to comprehensively utilize and develop olive waste.
Chinese patent 201010549802.X discloses a method for extracting oleuropein from olive leaves, which comprises the steps of extracting the olive leaves with ethanol, decolorizing with activated carbon, extracting with n-butanol, and separating with a high-speed countercurrent chromatograph to obtain oleuropein with purity of more than 90%, but the method has the disadvantages of complicated operation process, large solvent consumption, low oleuropein yield of the whole process, only about 1%, high production cost and no contribution to industrial production; chinese patent CN102228514B utilizes macroporous resin to extract oleuropein from olive leaves, can produce the oleuropein with the content of more than 40 percent, and the method needs to be absorbed by macroporous resin and eluted by an alcohol-water solvent, absorbed by decolorizing resin and extracted by an organic solvent, and has the defects of needing to be subjected to two times of resin and one time of extraction, complex operation, loss of a large amount of oleuropein, low yield and increased production cost; chinese patent CN102451235B discloses a preparation method of olive leaf extract, olive leaves are subjected to polar solvent extraction, grease adsorption by diatomite, macroporous resin adsorption/desorption, concentration and drying of desorption solution to obtain the olive leaf extract, wherein the purity of oleuropein can reach more than 55 percent, the method needs the steps of olive leaf impurity removal, crushing, water precipitation and the like, and the process is time-consuming.
Disclosure of Invention
The invention provides a preparation method of boric acid functionalized resin and application of the boric acid functionalized resin in separation and purification of high-purity oleuropein, thereby overcoming the defects of high target solvent usage amount, complex process, low oleuropein purity and low yield in the prior art.
The method for separating and purifying high-purity oleuropein provided by the invention comprises the following steps:
1) soaking the nonpolar polystyrene-divinyl phenyl macroporous resin in an organic solvent, and swelling overnight;
wherein the macroporous resin is XAD-4, D101, HPD-100, X-5, H103, D4020 or H107; the organic solvent is dichloromethane, 1, 2-dichloroethane or N, N-dimethylformamide;
2) adding a chloromethylation reagent and a catalyst into the organic solvent in the step 1) for reaction, and after the reaction is finished, sequentially washing with water and ethanol until AgNO is added3After no white precipitate exists, performing vacuum drying to obtain chloromethylated resin;
the chloromethylation reagent is chloracetyl chloride or chloromethyl ether, the catalyst is Lewis acid,
wherein the mass ratio of the chloromethylation reagent to the resin is 0.1-5: 1;
the mass ratio of the catalyst to the resin is 0.1-5: 1,
the reaction conditions are that the reaction time is 4-24 hours and the reaction temperature is 40-80 ℃; stirring at a speed of 50-200 rpm;
3) adding chloromethylated resin into a solvent to swell overnight, adding m-aminobenzoic acid to react, washing with water and ethanol in sequence after the reaction is finished, and drying in vacuum to obtain m-aminobenzoic acid modified resin;
the solvent is dichloromethane, 1, 2-dichloroethane or N, N-dimethylformamide;
the mass ratio of the resin to the solvent to the m-aminobenzoic acid is 1: 10-50: 0.1 to 1;
the reaction conditions comprise 6-24 h of reaction time, 40-80 ℃ of reaction temperature and 50-200 rpm of mechanical stirring speed;
4) filling the m-aminobenzoic acid modified resin into a chromatographic column, and loading the extracting solution of the olive leaves, wherein the loading volume is 1-10 BV, and the loading flow rate is 1-10 BV/h;
5) eluting the resin chromatographic column modified by m-aminophenylboronic acid by using a mixed solvent consisting of n-hexane, ethyl acetate, ethanol and water, taking the upper phase as an eluent, and drying the eluent to obtain high-purity oleuropein;
wherein the volume ratio of n-hexane, ethyl acetate, ethanol and water is (0.1-2): (8-10): (8-10):
(0.1-2) the sample loading volume is 1-10 BV, and the elution flow rate is 1-10 BV/h.
The method greatly improves the purity and yield of the oleuropein separated and purified by resin, and is simple and convenient to operate.
Compared with the prior art, the invention has the following advantages:
1. the m-aminophenylboronic acid resin has simple preparation process, simple and convenient operation and no use of corrosive chemical reagents;
2. the process route for purifying the oleuropein is simple, the purity can reach more than 60 percent, the yield can reach more than 60 percent, the cost is low, the efficiency is high, and the method is suitable for large-scale industrial production;
3. the m-aminophenylboronic acid functionalized resin can be regenerated and reused, and the adsorption capacity is reduced by about 5% after five times of recycling.
Drawings
FIG. 1: XPS spectrum of boric acid functional resin;
FIG. 2: nitrogen absorption/desorption curve diagram;
FIG. 3: HPLC spectra before and after the treatment of the extract with boric acid functionalized resin.
Detailed Description
The invention is described in detail below with reference to specific examples and the accompanying drawings.
Example 1
(1) Weighing 10g D101 resin in a three-neck round-bottom flask, adding 150mL of 1, 2-dichloroethane, and swelling overnight;
(2) 20g of chloroacetyl chloride is weighed and added into the mixture in the step (1), and 30g of AlCl is added3Reacting at 40 ℃ for 12h, after the reaction is finished, filtering the resin, washing the resin for a plurality of times by using ethanol and water respectively until no precipitate is formed after the AgNO3 solution is added, and finally drying in vacuum to obtain the chloromethylated treeLipid D101-Cl;
(3) adding 4g D101-Cl into a three-neck round-bottom flask, adding 100mL of 1, 2-dichloroethane for swelling overnight, adding 2g of m-aminophenylboronic acid, reacting for 12h at 60 ℃, removing filtrate after the reaction is finished, repeatedly washing the obtained resin with ethanol, HCl aqueous solution and distilled water, and finally drying for 12h at 60 ℃ in vacuum to obtain m-aminophenylboronic acid functionalized resin D101-BA, wherein an XPS spectrogram (figure 1) shows that nitrogen and boron elements exist on the resin, which indicates that the m-aminophenylboronic acid is successfully modified, and a nitrogen absorption/desorption spectrogram (figure 2) shows that the contrast surface area is almost not influenced before and after modification;
(4) extracting olive leaves with water, concentrating to obtain extract containing 0.1g leaves per ml, adjusting pH to 8.0 to obtain sample solution, weighing 2g D101-BA ethanol, swelling overnight, loading into chromatographic column, washing the column with distilled water, collecting 3BV sample solution, loading at flow rate of 2BV/h, and washing the column with distilled water;
(5) mixing n-hexane: ethyl acetate: ethanol: preparing an eluent according to the ratio of 0:10:1:9(V/V), taking an upper phase solution, adjusting the pH to 3.5 by using an HCl ethanol solution to obtain the eluent, taking 3BV of the eluent, eluting at the flow rate of 2BV/h, carrying out rotary evaporation on the eluent, fixing the volume by using distilled water, and measuring the purity by using HPLC, wherein a figure 3 shows an HPLC map before and after the extracting solution is treated by boric acid functionalized resin, so that the impurities are obviously reduced, the purity of oleuropein is 93.25%, the yield is 73.1%, and the adsorption capacity of the resin is reduced by 4.3% after five times of recycling.
Example 2
(1) Weighing 10g of XAD-4 resin in a three-neck round-bottom flask, adding 150mL of 1, 2-dichloroethane, and swelling overnight;
(2) 20g of chloroacetyl chloride is weighed and added into the mixture in the step (1), and 30g of AlCl is added3Reacting for 12h at 40 ℃, filtering the resin after the reaction is finished, respectively washing the resin for a plurality of times by using ethanol and water until no precipitate is formed after AgNO3 solution is added, and finally drying in vacuum to obtain chloromethyl resin XAD-4-Cl;
(3) adding 4g of XAD-4-Cl into a three-mouth round-bottom flask, adding 100mL of 1, swelling with 2-dichloroethane overnight, adding 2g of m-aminophenylboronic acid, reacting at 60 ℃ for 12 hours, removing filtrate after the reaction is finished, repeatedly washing the obtained resin with ethanol, HCl aqueous solution and distilled water, and finally drying at 60 ℃ in vacuum for 12 hours to obtain m-aminophenylboronic acid functionalized resin XAD-4-BA, wherein the XPS spectrogram shows that the resin contains nitrogen and boron elements, which indicates that m-aminophenylboronic acid is successfully modified, and the nitrogen absorption/desorption spectrogram indicates that the contrast surface area is almost unaffected before and after modification;
(4) extracting olive leaves with water, concentrating to obtain extract containing 0.1g leaves per ml, adjusting pH to 8.0 to obtain sample solution, weighing 2g D101-BA ethanol, swelling overnight, loading into chromatographic column, washing the column with distilled water, collecting 3BV sample solution, loading at flow rate of 2BV/h, and washing the column with distilled water;
(5) mixing n-hexane: ethyl acetate: ethanol: preparing an eluent according to the ratio of 0:10:1:9(V/V), taking an upper phase solution, adjusting the pH to 3.5 by using an HCl ethanol solution to obtain the eluent, taking 3BV of the eluent, eluting at the flow rate of 2BV/h, carrying out rotary evaporation on the eluent, fixing the volume by using distilled water, measuring the purity by using HPLC, and carrying out HPLC (high performance liquid chromatography) on an extracting solution before and after treatment by using boric acid functionalized resin, wherein the impurities are obviously reduced, the purity of oleuropein is 94.51 percent, the yield is 78.2 percent, and the adsorption capacity of the resin is only reduced by 4.2 percent after five times of cyclic use.
Claims (10)
1. A method for separating and purifying high-purity oleuropein, which is characterized by comprising the following steps:
1) soaking the nonpolar polystyrene-divinyl phenyl macroporous resin in an organic solvent, and swelling overnight;
2) adding a chloromethylation reagent and a catalyst into the organic solvent in the step 1) for reaction, and after the reaction is finished, sequentially washing with water and ethanol until AgNO is added3After no white precipitate exists, performing vacuum drying to obtain chloromethylated resin;
3) adding chloromethylated resin into a solvent to swell overnight, adding m-aminobenzoic acid to react, washing with water and ethanol in sequence after the reaction is finished, and drying in vacuum to obtain m-aminobenzoic acid modified resin;
4) filling the m-aminobenzoic acid modified resin into a chromatographic column, and loading the extracting solution of the olive leaves, wherein the loading volume is 1-10 BV, and the loading flow rate is 1-10 BV/h;
5) using a mixed solvent composed of n-hexane, ethyl acetate, ethanol and water, taking the upper phase as an eluent, eluting the m-aminobenzoic acid modified resin chromatographic column, and drying the eluent to obtain the high-purity oleuropein.
2. The method of claim 1, wherein the macroporous resin in 1) is XAD-4, D101, HPD-100, X-5, H103, D4020 or H107.
3. The method of claim 1, wherein the organic solvent of 1) is dichloromethane, 1, 2-dichloroethane, or N, N-dimethylformamide.
4. The method of claim 1, wherein the chloromethylating reagent in 2) is chloroacetyl chloride or chloromethyl ether, and the catalyst is a Lewis acid.
5. The method according to claim 1, wherein the mass ratio of the chloromethylation reagent to the resin in 2) is 0.1-5: 1; the mass ratio of the catalyst to the resin is 0.1-5: 1.
6. The method of claim 1, wherein the reaction time in 2) is 4-24 h, and the reaction temperature is 40-80 ℃; the stirring speed is 50-200 rpm.
7. The method of claim 1, wherein the solvent of 3) is dichloromethane, 1, 2-dichloroethane, or N, N-dimethylformamide.
8. The method of claim 1, wherein the mass ratio of the resin to the solvent and the m-aminobenzoic acid in 3) is 1: 10-50: 0.1 to 1.
9. The method of claim 1, wherein the reaction conditions in 3) are a reaction time of 6 to 24 hours, a reaction temperature of 40 to 80 ℃ and a mechanical stirring speed of 50 to 200 rpm.
10. The method according to claim 1, wherein the volume ratio of n-hexane, ethyl acetate, ethanol and water in the step 4) is 0.1-2: 8-10: 8-10: 0.1 to 2.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112552431A (en) * | 2020-12-10 | 2021-03-26 | 中国科学院青岛生物能源与过程研究所 | Preparation method of pinacol ester protected boric acid functional base material |
| CN112724455A (en) * | 2020-12-10 | 2021-04-30 | 中国科学院青岛生物能源与过程研究所 | Preparation method of efficient high-selectivity polyol adsorption material |
| CN114031694A (en) * | 2021-12-23 | 2022-02-11 | 云南三七科技有限公司 | Extraction method of pseudo-ginseng polysaccharide |
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| CN102228514A (en) * | 2011-05-05 | 2011-11-02 | 陕西禾博天然产物有限公司 | Method for extracting oleuropein from olive leaves |
| CN106967137A (en) * | 2017-04-12 | 2017-07-21 | 中国科学院兰州化学物理研究所 | A kind of method that macroreticular resin is combined preparative liquid chromatography separating high-purity oleuropein |
| CN109400658A (en) * | 2018-11-26 | 2019-03-01 | 中国科学院兰州化学物理研究所 | The method of separated in synchronization purifying oleuropein and hydroxytyrosol from olive growing leaves |
-
2020
- 2020-08-10 CN CN202010797366.1A patent/CN111875650B/en active Active
Patent Citations (3)
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| CN102228514A (en) * | 2011-05-05 | 2011-11-02 | 陕西禾博天然产物有限公司 | Method for extracting oleuropein from olive leaves |
| CN106967137A (en) * | 2017-04-12 | 2017-07-21 | 中国科学院兰州化学物理研究所 | A kind of method that macroreticular resin is combined preparative liquid chromatography separating high-purity oleuropein |
| CN109400658A (en) * | 2018-11-26 | 2019-03-01 | 中国科学院兰州化学物理研究所 | The method of separated in synchronization purifying oleuropein and hydroxytyrosol from olive growing leaves |
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| Title |
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| BAOQIAN LIU 等: "Isolation and purification of oleuropein from olive leaves using boric acid affinity resin and a novel solvent system", 《COLLOIDS AND SURFACES A: PHYSICOCHEMICAL AND ENGINEERING ASPECTS》 * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112552431A (en) * | 2020-12-10 | 2021-03-26 | 中国科学院青岛生物能源与过程研究所 | Preparation method of pinacol ester protected boric acid functional base material |
| CN112724455A (en) * | 2020-12-10 | 2021-04-30 | 中国科学院青岛生物能源与过程研究所 | Preparation method of efficient high-selectivity polyol adsorption material |
| CN112724455B (en) * | 2020-12-10 | 2022-12-23 | 中国科学院青岛生物能源与过程研究所 | Preparation method of efficient high-selectivity polyol adsorption material |
| CN114031694A (en) * | 2021-12-23 | 2022-02-11 | 云南三七科技有限公司 | Extraction method of pseudo-ginseng polysaccharide |
| CN114031694B (en) * | 2021-12-23 | 2023-02-03 | 云南三七科技有限公司 | Extraction method of pseudo-ginseng polysaccharide |
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