CN101264442A - Preparation of adsorption resin containing polar group and its application in purifying total alkaloids of rhizoma corydalis - Google Patents
Preparation of adsorption resin containing polar group and its application in purifying total alkaloids of rhizoma corydalis Download PDFInfo
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- CN101264442A CN101264442A CNA200810052877XA CN200810052877A CN101264442A CN 101264442 A CN101264442 A CN 101264442A CN A200810052877X A CNA200810052877X A CN A200810052877XA CN 200810052877 A CN200810052877 A CN 200810052877A CN 101264442 A CN101264442 A CN 101264442A
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Abstract
The invention discloses a preparation method of adsorption resin with polarity group and an application thereof in the purification of rhizoma corydalis total alkaloid, which comprises the following steps: (1) gelatin or polyvinyl alcohol are dissolved in the water to make aqueous phase solution, (2) methacrylate, styrene and divinylbenzene are made monomer phase, and long chain alkane is added as pore-foaming agent and made oil phase with the monomer phase, (3) the aqueous phase and the oil phase are mixed together with the volume ratio 3:1, 2'-azobisisobutyronitrile is adopted as the initiator, and the adsorption resin with polarity group is acquired by polymerization reaction, and (4) the application is that the rhizoma corydalis is crushed, extracted by ethanol and transferred to water, the acquired clear aqueous solution is pumped in the resin column of the adsorption resin for absorption, washed by water and ethanol water in sequence, and eluted by acetic acid-ethanol aqueous solution, the eluent is vacuum-distilled and vacuum-dried, and the solid tetrahydropalmatine with purity 15 to 20% is acquired. The adsorption resin with polarity group has the advantages of simple technology, no use of toxic organic solvent, and low investment cost, thus being suitable for industrialized mass production.
Description
[technical field]:
The extracting method of the extraction and the separation technology field, particularly tetrahydropalmatine of pharmaceutically active ingredient in the present invention relates to reaches the preparation of employed polymeric adsorbent in this method.
[background technology]:
Corydalis tuber (Corydalis yanhusuo W.T.Wang.) is the dry tuber of papaveraceae plant corydalis, and its flavor is hot, bitter, warm in nature, have activate blood circulation and disperse blood clots, the effect of regulating qi-flowing for relieving pain.Clinical chest abdomen pain, limbs pain, colic, the dysmenorrhoea of being used for the treatment of.But single uses, but also compatibility other medicines decoction.Modern pharmacology studies show that corydalis tuber has antiulcer, gastric acid inhibitory secretion, spasmolysis and increases coronary blood flow, effects such as anti-arrhythmia.Main active is an isoquinoline alkaloid in the corydalis tuber, comprises corydalis tuber first element, tetrahydropalmatine, Biflorine, Tetrahydrocoptisine etc., and wherein tetrahydropalmatine (Tetrahydropalmatine) is main active ingredient, and its structure is as shown below.Investigate the purity of TA among the present invention with the content of tetrahydropalmatine in extract.
Studies show that tetrahydropalmatine has the effect of analgesia, calmness.The analgesic activity of tetrahydropalmatine is stronger than analgesic-antipyretic.Effect to chronic rest pain and internal organ dull pain is better.At the performance analgesic activity simultaneously, also has sedative-hypnotic effect.Discovered in recent years also has pharmacological actions such as step-down, anti-arrhythmia cordis, antithrombotic, calcium antagonism, gastric acid inhibitory secretion (Xu Ting, gold former times land, Cao Huiming, tetrahydropalmatine Pharmacological action study progress, Chinese clinical pharmacy magazine, 2001,10 (1): 58-60).
In current research, often adopt methods such as Soxhlet extraction, refluxing extraction, supercritical extract and Microwave Extraction to carry out the extraction of tetrahydropalmatine.Wrap employing supercritical COs such as valuable mandarin duck
2The fluid extraction method extracts tetrahydropalmatine from corydalis tuber, and experimental condition has been carried out optimizing (wrapped valuable mandarin duck, Wu Licheng, what loyal equality, supercritical CO
2The fluid extraction method is extracted tetrahydropalmatine, Chinese medicine, 2004,27 (7): 501-503).Cheng Jianming etc. are index with the rate of extract of extract and the content of tetrahydropalmatine, investigated the extraction effect of methods such as Soxhlet extraction, supercritical fluid, Microwave Extraction, think that supercritical fluid is suitable for the extraction of tetrahydropalmatine (Cheng Jianming most, the well mountain forest, the comparative studies of tetrahydropalmatine Different Extraction Method in the corydalis tuber, the time precious traditional Chinese medical science traditional Chinese medicines, 2006,17 (7): 1236-1237).But the supercritical fluid extraction cost is higher, and disposable apparatus is bigger, is not suitable for large-scale industrial production.Zhang Li builds etc. and studies show that to extract corydalis tuber alkaloid medicinal extract rate with the macroporous absorbent resin method higher, do not use toxic solvent, pollute for a short time, and resin is renewable, easy to use, be a kind of method that is worthy to be popularized (Zhang Lizhu, Zhu Zhu, Hao Xiaoyan, the comparison of two kinds of extracting methods of corydalis tuber biology total alkali, the Guiyang Medical College journal, 2006,31 (3): 280-282).Be used for the polymeric adsorbent mostly resin that Chinese herbal medicine effective ingredients extracts is full polystyrene type or contains a spot of low pole group at present.The hydrophobic effect power of this resinoid is very strong, and is relatively poor to the selectivity of active ingredient and impurity.We expect synthetic a kind of polystyrene type polymeric adsorbent that contains polar group, and are applied to prepare from corydalis tuber tetrahydropalmatine.
[summary of the invention]:
The objective of the invention is to solve that the tetrahydropalmatine extracting method is relatively poor to the selectivity of active ingredient and impurity in the existing corydalis tuber, cost is high and be not suitable for the problem of large-scale industrial production, a kind of adsorbent resin preparation method thereof and the application of this resin in purifying total alkaloids of rhizoma corydalis of polar functionalities are provided.
The preparation method of the polymeric adsorbent of polar functionalities provided by the invention, realize by following steps:
The first, at normal temperatures, gelatin or polyvinyl alcohol are dissolved in the water, are made into the quality percentage composition and are 0.5%～5% aqueous phase solution;
The second, be divinylbenzene compositing monomer phase with the methyl acrylate of quality percentage composition 3%～10%, 30%～60% styrene and surplus, add long chain alkane as pore-foaming agent to monomer in mutually, its quality is 80～100% of a monomer phase quality, forms oil phase mutually jointly with monomer; Aqueous phase solution in the first step is heated to 30～50 ℃, adds above-mentioned oil phase, water and oil phase volume ratio are 3: 1;
Three, go on foot upwards in the mixed liquor that to add consumption be that 1～3% azo-bis-isobutyl cyanide of total monomer phase quality is as initator; In the suspension polymerisation process, be warming up to 60～80 ℃ of reactions 2～6 hours earlier, continue to be warming up to 85～90 ℃ of reactions 3 hours again; Obtain at last after filtration, the polymeric adsorbent of polar functionalities after the carrying out washing treatment.
The application of the polymeric adsorbent of method for preparing is used for preparing tetrahydropalmatine from corydalis tuber, and concrete steps are as follows:
The first step, corydalis tuber is pulverized,, repeated to extract 1～3 time with 70～85% alcohol heating reflux 1～2 hour;
Second step, will go up the step extract and change in the aqueous solution, transfer pH value to 3～4, filter clear aqueous solution;
The 3rd step, the polymeric adsorbent of claim 1 preparation is packed in the adsorption column, the fineness ratio of adsorption column is 1: 5～1: 20;
The 4th step, with second step change into solution behind the water with the flow velocity of 0.5～3.0BV/h by the resin adsorption post, wherein tetrahydropalmatine is adsorbed on the resin column effectively;
The 5th step, with 2～3BV water cleaning resin bed, use the acetic acid-ethanol water stepwise elution of ethanol water, 2～5BV acetic acid volumn concentration 3～8% and the ethanol volumn concentration 75～90% of the volumn concentration 50～60% of 2～4BV then successively, flow velocity is 0.5～3BV/h;
The 6th step, with acetic acid-ethanol eluate through vacuum distillation recovered solvent, concentrate, vacuum drying, promptly get the tetrahydropalmatine extract.
The purity of tetrahydropalmatine is 15～20% in the above tetrahydropalmatine extract.
Advantage of the present invention and good effect:
The present invention is raw material with the corydalis tuber, is to extract solvent with ethanol, only goes on foot simple process by " absorption-wash-out ", can be from the corydalis tuber extract separation and purification obtain the extract of tetrahydropalmatine, detect through HPLC, the purity of tetrahydropalmatine is 15～20% in the product.Technology of the present invention simply, is not used toxic organic solvent, and cost of investment is low, be easy to industrialized production.
[specific embodiment]:
Embodiment 1:
The preparation method of the polymeric adsorbent of polar functionalities, realize by following steps:
At normal temperatures, the 1.5g polyvinyl alcohol is dissolved in the 298.5g water, is made into 0.5% the aqueous solution, be heated to 40 ℃, adding adds the 50g long chain alkane and makes pore-foaming agent, with monomer phase composition oil phase with 1.5g methyl acrylate, 15g styrene and 33.5g divinylbenzene compositing monomer phase.Adding 0.5g azo-bis-isobutyl cyanide (AIBN) be initator, slowly is warming up to 65 ℃ of reactions more than 4 hours, slowly is warming up to 90 ℃ again and reacts more than 3 hours, after filtration, after the carrying out washing treatment, prepare required polymeric adsorbent.
Embodiment 2:
At normal temperatures, the 18g gelatin is dissolved in the 582g water, is made into 3% the aqueous solution, be heated to 40 ℃, adding adds the 89g long chain alkane and makes pore-foaming agent, with monomer phase composition oil phase with 5.6g methyl acrylate, 66.6g styrene and 38.8g divinylbenzene compositing monomer phase.Adding 1.7gAIBN is an initator, slowly is warming up to 80 ℃ of reactions more than 3 hours, slowly is warming up to 90 ℃ of reactions again more than 3 hours, after filtration, after the carrying out washing treatment, prepare required polymeric adsorbent.
Embodiment 3:
Above-mentioned polymeric adsorbent is in the application of preparation tetrahydropalmatine from corydalis tuber
5 gram corydalis tubers are pulverized, and 70% ethanol water added hot reflux 1 hour for 60 ℃, repeated 1 time, and extract changes in the 30mL water, accent PH to 3.0, filter clear aqueous solution.The aqueous solution that obtains is fed resin column (the post footpath 15mm that above-mentioned resin is housed, the 30mL resin is housed), the absorption flow velocity is 2.5BV/h, use water and the washing of 2BV 50% ethanol water of 2BV (bed volume) successively, use the aqueous solution wash-out of 2BV acetic acid volumn concentration 3% and ethanol volumn concentration 90% again, elution flow rate is 2.0BV/h.Divide eluent to get solids through decompression distillation, vacuum drying respectively, detect through the Waters484 high performance liquid chromatograph, tetrahydropalmatine content is 19.1%.
Embodiment 4:
10 gram corydalis tubers are pulverized, and 80% ethanol water added hot reflux 2 hours for 60 ℃, and extract changes in the 50mL water, transfers pH value to 3.5, filter clear aqueous solution.The aqueous solution that obtains is fed resin column (the post footpath 15mm that above-mentioned resin is housed, the 30mL resin is housed), the absorption flow velocity is 1.0BV/h, successively with 3BV water and the washing of 4BV 50% ethanol water, contain 75% ethanol water wash-out of 8% acetic acid again with 2BV, elution flow rate is 0.5BV/h.Divide eluent to get solids through decompression distillation, vacuum drying respectively, detect through the Waters484 high performance liquid chromatograph, tetrahydropalmatine content is 20.8%.
Embodiment 5:
25 gram corydalis tubers are pulverized, and 80% ethanol water added hot reflux 1 hour for 60 ℃, repeated 2 times, and extract changes in the 80mL water, accent pH value to 4.0, filter clear aqueous solution.The aqueous solution that obtains is fed resin column (the post footpath 20mm that commentaries on classics has above-mentioned resin, the 25mL resin is housed), the absorption flow velocity is 2.0BV/h, successively with 3BV water and the washing of 3BV 50% ethanol water, contain 80% ethanol water wash-out of 5% acetic acid again with 2BV, elution flow rate is 1.0BV/h.Divide eluent to get solids through decompression distillation, vacuum drying respectively, detect through the Waters484 high performance liquid chromatograph, tetrahydropalmatine content is 18.3%.
Embodiment 6:
150 gram corydalis tubers are pulverized, and 75% ethanol water added hot reflux 1 hour for 60 ℃, and extract changes in the 350mL water, transfers pH value to 3.5, filter clear aqueous solution.The aqueous solution that obtains is fed resin column (the post footpath 5.5cm that above-mentioned resin is housed, the 500mL resin is housed), the absorption flow velocity is 2.0BV/h, successively with 2BV water and the washing of 3BV 60% ethanol water, contain 75% ethanol water wash-out of 5% acetic acid again with 3BV, elution flow rate is 2.0BV/h.Divide eluent to get solids through decompression distillation, vacuum drying respectively, detect through the Waters484 high performance liquid chromatograph, tetrahydropalmatine content is 16.9%.
Claims (3)
1, a kind of preparation method of polymeric adsorbent of polar functionalities is characterized in that, realizes by following steps:
The first, at normal temperatures, gelatin or polyvinyl alcohol are dissolved in the water, are made into the quality percentage composition and are 0.5%～5% aqueous phase solution;
The second, be divinylbenzene compositing monomer phase with the methyl acrylate of quality percentage composition 3%～10%, 30%～60% styrene and surplus, add long chain alkane as pore-foaming agent to monomer in mutually, its quality is 80～100% of a monomer phase quality, forms oil phase mutually jointly with monomer; Aqueous phase solution in the first step is heated to 30～50 ℃, adds above-mentioned oil phase, water and oil phase volume ratio are 3: 1;
Three, go on foot upwards in the mixed liquor that to add consumption be that 1～3% azo-bis-isobutyl cyanide of monomer phase gross mass is as initator; In the suspension polymerisation process, be warming up to 60～80 ℃ of reactions 2～6 hours earlier, continue to be warming up to 85～90 ℃ of reactions 3 hours again; Obtain at last after filtration, the polymeric adsorbent of polar functionalities after the carrying out washing treatment.
2, according to the application of the polymeric adsorbent of the described method of claim 1 preparation, be used for preparing tetrahydropalmatine from corydalis tuber, concrete steps are as follows:
The first step, corydalis tuber is pulverized,, repeated to extract 1～3 time with 70～85% alcohol heating reflux 1～2 hour;
Second step, will go up the step extract and change over to and become water in the aqueous solution, transfer pH value to 3～4, filter clear aqueous solution;
The 3rd step, the polymeric adsorbent of claim 1 preparation is packed in the adsorption column, the fineness ratio of adsorption column is 1: 5～1: 20;
The 4th step, with second step change into solution behind the water with the flow velocity of 0.5～3.0BV/h by the resin adsorption post, wherein tetrahydropalmatine is adsorbed on the resin column effectively;
The 5th step, with 2～3BV water cleaning resin bed, use the acetic acid-ethanol water stepwise elution of ethanol water, 2～5BV acetic acid volumn concentration 3～8% and the ethanol volumn concentration 75～90% of the volumn concentration 50～60% of 2～4BV then successively, flow velocity is 0.5～3BV/h;
The 6th step, with acetic acid-ethanol eluate through vacuum distillation recovered solvent, concentrate, vacuum drying, promptly get the tetrahydropalmatine extract.
3, application according to claim 2, the purity that it is characterized in that tetrahydropalmatine in the tetrahydropalmatine extract is 15～20%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102319585A (en) * | 2011-05-18 | 2012-01-18 | 凯瑞化工股份有限公司 | High-temperature-resistant maleic anhydride (MAH) resin catalyst and preparation method thereof |
| CN102641754A (en) * | 2012-05-11 | 2012-08-22 | 南开大学 | Preparation method for weak-base anion-exchange resin of novel acrylate skeleton |
| CN110404522A (en) * | 2019-08-13 | 2019-11-05 | 包头稀土研究院 | Adsorb the regeneration method of the resin column of organic impurities in rare-earth chloride solution |
| CN118005506A (en) * | 2024-04-10 | 2024-05-10 | 安徽先材科技有限公司 | Preparation method of trimesic acid chloride |
-
2008
- 2008-04-25 CN CNA200810052877XA patent/CN101264442A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102319585A (en) * | 2011-05-18 | 2012-01-18 | 凯瑞化工股份有限公司 | High-temperature-resistant maleic anhydride (MAH) resin catalyst and preparation method thereof |
| CN102319585B (en) * | 2011-05-18 | 2012-10-17 | 凯瑞化工股份有限公司 | High-temperature-resistant maleic anhydride (MAH) resin catalyst and preparation method thereof |
| CN102641754A (en) * | 2012-05-11 | 2012-08-22 | 南开大学 | Preparation method for weak-base anion-exchange resin of novel acrylate skeleton |
| CN102641754B (en) * | 2012-05-11 | 2013-11-20 | 南开大学 | Preparation method for weak-base anion-exchange resin of novel acrylate skeleton |
| CN110404522A (en) * | 2019-08-13 | 2019-11-05 | 包头稀土研究院 | Adsorb the regeneration method of the resin column of organic impurities in rare-earth chloride solution |
| CN110404522B (en) * | 2019-08-13 | 2022-08-02 | 包头稀土研究院 | Regeneration method of resin column for adsorbing organic impurities in rare earth chloride solution |
| CN118005506A (en) * | 2024-04-10 | 2024-05-10 | 安徽先材科技有限公司 | Preparation method of trimesic acid chloride |
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Open date: 20080917 |