CN107652166B - Separation method of mangnolia officinalis bisphenol - Google Patents

Separation method of mangnolia officinalis bisphenol Download PDF

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CN107652166B
CN107652166B CN201710940611.8A CN201710940611A CN107652166B CN 107652166 B CN107652166 B CN 107652166B CN 201710940611 A CN201710940611 A CN 201710940611A CN 107652166 B CN107652166 B CN 107652166B
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extraction
silica gel
petroleum ether
magnolia
leaching
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CN107652166A (en
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王代军
陈松
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Beijing Guokang Herbary Species Biological Science And Technology Research Institute Co ltd
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    • C07C37/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
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    • C07C37/70Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
    • C07C37/82Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by solid-liquid treatment; by chemisorption

Abstract

The invention relates to the field of extraction and separation, in particular to a separation method of mangnolia officinalis bisphenol. The prior magnolia officinalis bisphenol extraction technology is immature, the yield is low, and magnolol and honokiol have similar polarities and are not easy to separate. Resin is used as an adsorbent, methanol and ethanol are used as an eluting agent, bisphenol monomers cannot be obtained, the efficiency is low, and the solvent consumption is large; silica gel is used as a carrier, and petroleum ether and ethyl acetate are used as eluent, so that the solvent is seriously wasted. The inventor finds that magnolol and honokiol can be effectively separated by adopting the mixed solution of petroleum ether and ethanol as a solvent to separate the magnolia officinalis extract, and the effect is excellent.

Description

Separation method of mangnolia officinalis bisphenol
Technical Field
The invention relates to the field of extraction and separation, and particularly relates to a separation method of mangnolia officinalis bisphenol.
Background
The cortex Magnolia officinalis is dry bark, root bark and branch bark of Magnolia officinalis or Magnolia officinalis of Magnoliaceae. Bitter and pungent in flavor and warm in nature. It enters spleen, stomach, lung and large intestine meridians. It can be used for treating damp stagnation, abdominal distention, emesis, diarrhea, dyspepsia, abdominal distention, constipation, phlegm retention, asthma, and cough. According to the literature report, the magnolia officinalis also has the function of relaxing muscles in pharmacology; small dose can excite the smooth muscle of the intestinal canal, and large dose has inhibition effect on the smooth muscle of the intestinal canal; the medicine has the functions of resisting ulcer, reducing blood pressure, resisting pathogenic microorganisms and resisting tumors, and has a remarkable central inhibition function; it also has antiplatelet and intracellular calcium flow inhibiting effects, and neuroprotective and antidiabetic effects. The cortex Magnolia officinalis contains volatile oil, alkaloid, saponin, tannin, and trace amount of nicotinic acid. The main medicinal components are magnolol and honokiol, which account for more than 95 percent of the effective medicinal components of the magnolia officinalis, and the molecular formula is as follows:
Figure BDA0001426945250000011
the extraction method of magnolol mainly comprises the following steps: heating reflux extraction, ultrasonic-assisted extraction, microwave-assisted extraction, and supercritical CO extraction2Fluid extraction, but the conditions of difficult compromise of yield and purity, large solvent consumption in extraction, serious energy waste and the like generally exist. Such as: the microwave-assisted extraction method has high yield but low purity; and supercritical CO2The fluid extraction method can obtain high-purity product, but low yield. The heating reflux extraction method has large solvent consumption and long production period.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a separation method of mangnolia officinalis bisphenol, which combines the processes of extraction of mangnolia officinalis and separation of honokiol to directly obtain a bisphenol monomer, has high monomer purity and extraction rate through high performance liquid phase detection, can recycle a solvent, and is an effective extraction and separation method of mangnolia officinalis.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a method for separating cortex Magnolia officinalis bisphenol comprises separating cortex Magnolia officinalis extract with mixed solution of petroleum ether and ethanol as solvent.
The prior magnolia officinalis bisphenol extraction technology is immature, the yield is low, and magnolol and honokiol have similar polarities and are not easy to separate. Resin is used as an adsorbent, methanol and ethanol are used as an eluting agent, bisphenol monomers cannot be obtained, the efficiency is low, and the solvent consumption is large; silica gel is used as a carrier, and petroleum ether and ethyl acetate are used as eluent, so that the solvent is seriously wasted. The inventor finds that magnolol and honokiol can be effectively separated by adopting the mixed solution of petroleum ether and ethanol as a solvent to separate the magnolia officinalis extract, and the effect is excellent.
Further, the volume ratio of the petroleum ether to the ethanol is 5-100: 1.
Preferably, the volume ratio of the petroleum ether to the ethanol is 5-30: 1.
More preferably, the volume ratio of the petroleum ether to the ethanol is 10-20: 1.
Preferably, the separation is performed by rinsing.
In order to facilitate rinsing to sufficiently separate the target substances from the Magnolia bark extract, the Magnolia bark extract is preferably concentrated and then rinsed with an adsorbent.
Further, the adsorbent is silica gel powder.
Further, the magnolia bark extract is processed into flowable dry powder and then subjected to separation operation, and the flowable dry powder is prepared by the following steps:
extracting cortex Magnolia officinalis with ethanol, and concentrating the obtained ethanol extractive solution to obtain concentrated solution;
and mixing the concentrated solution with silica gel powder, and continuously concentrating to obtain the flowable dry powder.
In the leaching process, firstly, petroleum ether is adopted for leaching, mainly bubbles in the column are removed, so that the flowing dry powder is in a uniform environment, and then solvents with different proportions are used for leaching, so that magnolol and honokiol are separated.
The flowable dry powder leaching can be performed by sequentially adopting the following solvents: petroleum ether, a first mixed solution of petroleum ether and absolute ethyl alcohol in a volume ratio of 30-100:1, and a second mixed solution of petroleum ether and absolute ethyl alcohol in a volume ratio of 10-20: 1.
The second mixed solution of the petroleum ether and the absolute ethyl alcohol in the volume ratio of 10-20:1 can also be leached in the following mode.
In view of the effect of separating the target, the separation efficiency, and the convenience of the operation, it is preferable that the flowable dry powder is rinsed with the following solvents in order: petroleum ether, a first mixed solution of the petroleum ether and absolute ethyl alcohol in a volume ratio of 100:0.8-1.5, and a second mixed solution of the petroleum ether and the absolute ethyl alcohol in a volume ratio of 10: 0.8-1.5;
collecting eluate by stages, and concentrating to obtain magnolol and honokiol monomer.
Through a large number of experiments, the leaching efficiency can be greatly improved by adopting the step for leaching.
The invention combines the processes of extracting honokiol and honokiol from magnolia officinalis, extracts the magnolia officinalis material by alcohol, mixes the product with silica gel after concentration, so that the concentrated solution is uniformly spread on silica gel powder, then gradually leaches the silica gel powder to obtain leacheate which is concentrated to obtain the magnolol and the honokiol, the obtained magnolol and the honokiol comprise the mixture of the magnolol and the honokiol which exist independently and part of the magnolol, the mixture can be used for silica gel powder mixing and leaching independently or together with the concentrated solution of the next batch, and the operation is repeated to obtain the bisphenol monomer. The method can directly obtain bisphenol monomer, and has high monomer purity and yield by high performance liquid detection, and solvent can also be recycled, thus being an effective extraction and separation method for Magnolia officinalis.
In order to more fully extract the effective components in the magnolia bark raw material, further, the magnolia bark raw material is extracted by alcohol in the form of crushed material.
Further, the magnolia bark raw material comprises any one or more of magnolia bark, magnolia root bark and magnolia leaves.
Preferably, the particle size of the pulverized material is 40 to 60 mesh. As in the different embodiments, the particle size of the pulverized material may be 40 mesh, 45 mesh, 50 mesh, 55 mesh, 60 mesh, etc.
In order to fully extract the effective ingredients in the raw materials of the magnolia officinalis, the alcohol extraction is as follows: extracting with 90% +/-2% ethanol water solution.
Further, the extraction is reflux extraction, and the extraction temperature is 50-70 ℃. As in the various embodiments, the temperature of extraction may be 50 deg.C, 52 deg.C, 55 deg.C, 57 deg.C, 60 deg.C, 62 deg.C, 65 deg.C, 68 deg.C, 70 deg.C, etc.
Further, the extraction times are 2-4 times, the extraction time is 1-2h, and the amount of the ethanol water solution added in each extraction is 4-6 times of the weight of the magnolia bark raw material.
For example, the extraction times can be 2 times, 3 times, 4 times, etc., the extraction time can be 60min, 70min, 80min, 90min, 100min, 110min, 120min, etc., and the amount of the ethanol aqueous solution added for extraction can be 40%, 42%, 45%, 48%, 50%, 53%, 55%, 58%, 60%, etc. of the weight of the Magnolia officinalis raw material.
Further, the concentration is carried out to 8-15% of the volume of the alcohol extract. Such as may be 8%, 9%, 10%, 12%, 13%, 15%, etc.
Further, the adding amount of the silica gel powder is 2-3 times of the mass of the concentrated solution.
Further, the particle size of the silica gel powder is 100-200 meshes. For example, in various embodiments, the silica gel powder may have a particle size of 100 mesh, 120 mesh, 150 mesh, 170 mesh, 180 mesh, 200 mesh, and the like.
The silica gel powder used in the invention is A-type silica gel and fine pores, experiments show that the larger the mesh number is, the better the separation effect is, but the slower the leaching speed is, the longer the time consumption is, based on the above, the silica gel powder with the mesh number of 100-200 is preferred, and the good separation effect and the high speed are achieved. The silica gel powder used in the invention can be purchased from Qingdao ocean chemical Co.
The concentrated solution is mixed with the silica gel powder and then further concentrated into the flowable dry powder, mainly because the concentrated solution is viscous and is directly added into a column, and the concentrated solution can be directly stuck on the column, so that the leaching effect is poor. By mixing with the silica gel powder, the silica gel powder spreads the concentrated solution, that is, the concentrated solution is attached to the pores and various surfaces of the silica gel powder, so that the subsequent leaching is facilitated, and the separation efficiency and effect of the target product are improved.
Further, before the elution, the method also comprises a step of filling the flowing dry powder into a column, wherein the step of filling the column comprises the following steps: the petroleum ether and silica gel powder are mixed and packed into column by wet method until no bubble exists, and then the fluidity dry powder is added.
Further, in the leaching process, the leaching time of the petroleum ether is 100-150min, the leaching time of the mixed solution is 50-70min, and the leaching time of the absolute ethyl alcohol is 50-70 min.
The used column is made of unlimited materials, such as common glass column, metal column, etc., a valve is arranged below the column to facilitate sectional access of the leacheate, and the diameter of the column is 10-20 cm. Generally, a 3L column is selected, silica gel powder is 150-250g, petroleum ether is added into the silica gel powder for mixing, the column is packed by a wet method until no air bubbles exist, and then about 600g of the fluidity dry powder is added, namely 0.05-0.08kg of the silica gel powder is added into each liter of the column, and 0.15-0.25kg of the fluidity dry powder is added.
Further, when the leacheate is collected, the step of collecting the leacheate in sections is included, and the leacheate collected in sections is concentrated and dried respectively to obtain the magnolol monomer and the honokiol monomer.
And (3) receiving the leacheate in sections, detecting the leacheate by adopting thin-layer chromatography, and judging whether the magnolol and the honokiol are completely separated or not according to the detection result. Collecting the eluates containing magnolol and honokiol, and concentrating to obtain monomer of magnolol and honokiol.
Further, the leacheate can be recycled.
Compared with the prior art, the invention has the beneficial effects that:
(1) resin is used as an adsorbent, methanol and ethanol are used as an eluting agent, bisphenol monomers cannot be obtained, the efficiency is low, and the solvent consumption is large; silica gel is used as a carrier, petroleum ether and ethyl acetate are used as eluent, and the waste of the solvent is serious; the inventor finds that magnolol and honokiol can be effectively separated by adopting the mixed solution of petroleum ether and ethanol as a solvent to separate the magnolia officinalis extract, and the effect is excellent.
(2) The invention combines the processes of extracting honokiol from magnolia officinalis and separating honokiol, after the magnolia officinalis material is extracted with alcohol, the product is concentrated and then mixed with silica gel powder, thus, the concentrated solution is evenly spread on the silica gel powder, and then the obtained leacheate is concentrated to obtain the honokiol and the honokiol through gradual leaching.
(3) The method for separating the mangnolia officinalis bisphenol can directly obtain the bisphenol monomer, and the purity of the monomer is over 96 percent through detection, the leacheate is concentrated and distilled, and the extraction rate of the bisphenol is over 90 percent; after the filtered mother liquor is concentrated and distilled again, the extraction rate of bisphenol is over 98 percent, and the extraction rate is high.
(4) The solvent used in the leaching can be recycled, and the recycled solvent is easy to treat and recycle.
(5) The method for separating the mangnolia officinalis bisphenol provided by the invention is simple, easy to implement, high in separation efficiency, low in investment cost and easy to popularize and apply in a large range.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a photograph showing the results of the chromatography after leaching in Magnolia bark in example 1 of the present invention;
FIG. 2 is a chromatogram of magnolol isolated in example 2 of the present invention;
FIG. 3 is a chromatogram of honokiol isolated in example 2 of the present invention;
FIG. 4 is a chromatogram of isolated Magnolia bark bisphenol of example 2 of the present invention.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
Processing extractive solution of cortex Magnolia officinalis bisphenol by thin layer chromatography with different solvents respectively, wherein the specific solvents are as follows:
PE: the results of thin-layer plates obtained with mixtures of ETOH at volume ratios of 100:1, 50:1, 40:1, 30:1, 20:1 and 10:1, respectively, are shown in fig. 1. The left side of each plate in FIG. 1 is the control group.
As can be seen from FIG. 1, magnolol and honokiol are well separated when the volume ratio of PE to ETOH is 10-20: 1.
Example 2
A separation method of mangnolia officinalis bisphenol comprises the following steps:
extraction: pulverizing cortex Magnolia officinalis (containing magnolol 2.9% and honokiol 1.9% by HPLC), sieving with 50 mesh sieve, extracting 1000g with 90% ethanol aqueous solution 6000g, 5000g and 4000g at 60 deg.C for 2 hr, 1 hr and 1 hr respectively;
the extracts were combined and concentrated to 10% of their volume, 300g of silica gel powder was added and concentration continued to a flowable dry powder of about 600 g.
Taking a glass column with the volume of about 3000ml, adding 200g of silica gel powder to the glass column, and filling the silica gel powder into the glass column by a wet method, namely mixing the silica gel powder with petroleum ether with the boiling point of 60-90 ℃, filling the silica gel powder into the glass column by a wet method until no bubbles exist, then adding about 600g of flowable dry powder, and finally adding PE (petroleum ether 60-90 ℃) and ETOH (absolute ethyl alcohol) to carry out leaching:
1) PE: 0ml of ETOH (5000 ml), and leaching for 2 h;
2) PE: washing the ETOH (5000 ml) with 50ml for 1 h;
3) PE: 500ml of ETOH (5000 ml) and 1h of leaching.
Classifying the leacheate according to TLC (thin layer chromatography) detection, concentrating (distillation concentration), concentrating without spin drying until the solid and liquid respectively account for half, separating out most of crystals, and filtering to obtain 9.1g (purity 98.9%) of separated magnolol crystals, 7.1g (purity 96.8%) of separated honokiol crystals and 27.3g (purity 98%) of bisphenol mixture powder;
wherein, the result of chromatographic detection of magnolol crystal is shown in figure 2. The specific information in fig. 2 is shown in table 1.
TABLE 1 chromatographic results
Figure BDA0001426945250000081
The results of the chromatographic detection of honokiol crystals are shown in figure 3. The specific information in fig. 3 is shown in table 2.
TABLE 2 chromatographic results
Figure BDA0001426945250000082
The results of the chromatographic measurement of the bisphenol mixture powder are shown in FIG. 4. The specific information in fig. 4 is shown in table 3.
TABLE 3 chromatographic results
Figure BDA0001426945250000083
Figure BDA0001426945250000091
And (3) continuously adding silica gel powder with equal mass into the filtered mother liquor, concentrating to dryness, leaching again, concentrating (distilling and concentrating) respectively, concentrating without spin-drying until most of crystals are separated out, and filtering to obtain 1.2g (98%) of magnolol crystals, 1.0g (98%) of honokiol crystals and 2.3g (98%) of bisphenol mixture powder.
The residual mother liquor contains a small amount of bisphenol, and can be continuously leached and separated by the next batch.
In this embodiment, the silica gel powder used has 150 meshes.
Example 3
A separation method of mangnolia officinalis bisphenol comprises the following steps:
extraction: pulverizing cortex Magnolia officinalis (detecting by HPLC to obtain powder containing magnolol and honokiol), sieving with 40 mesh sieve, extracting 1000g sequentially with 92% ethanol aqueous solution 6000g, 5000g and 4000g at 50 deg.C for 2 hr, 1 hr and 1 hr;
the extract liquid is combined and concentrated to 8 percent of the volume, 300g of silica gel powder is added, and the concentration is continued to be fluid dry powder.
Taking a glass column with the volume of about 3000ml, adding 200g of silica gel powder to the glass column, and filling the silica gel powder into the glass column by a wet method, namely mixing the silica gel powder with petroleum ether with the boiling point of 60-90 ℃, filling the silica gel powder into the glass column by a wet method until no bubbles exist, then adding about 600g of flowable dry powder, and finally adding PE (petroleum ether 60-90 ℃) and ETOH (absolute ethyl alcohol) to carry out leaching:
1) PE: 0ml of ETOH (5000 ml), and leaching for 2 h;
2) PE: washing the ETOH (5000 ml) with 50ml for 1 h;
3) PE: 250ml of ETOH (5000 ml) and 1h of leaching.
Determining the classification of the eluate according to TLC (thin layer chromatography), concentrating (distilling and concentrating), concentrating without spin drying, concentrating until the solid and liquid account for half of each, precipitating most of crystals, and filtering to obtain precipitated magnolol crystals, honokiol crystals and bisphenol mixture powder;
and continuously adding silica gel powder with equal mass into the filtered mother liquor, concentrating to dryness, and leaching again to respectively obtain magnolol crystals, honokiol crystals and bisphenol mixture powder.
The total recovery rate of the magnolol crystal, the honokiol crystal and the bisphenol mixture powder is calculated to reach 98.7%, the purity of the separated magnolol crystal is more than 98%, the purity of the honokiol crystal is more than 97%, and the purity of the bisphenol mixture powder is more than 98%.
In this embodiment, the silica gel powder used has a mesh size of 200 meshes.
Example 4
A separation method of mangnolia officinalis bisphenol comprises the following steps:
extraction: pulverizing Magnolia officinalis leaves (containing magnolol and honokiol by HPLC), sieving with 60 mesh sieve, reflux-extracting 1000g with 88 vol% ethanol water solution 5000g, 5000g and 4000g at 70 deg.C for 2 hr, 1 hr and 1 hr;
the extract liquid is combined and concentrated to 10 percent of the volume, 450g of silica gel powder is added, and the concentration is continued to be fluid dry powder.
Taking a glass column with the volume of about 3000ml, adding 200g of silica gel powder to the glass column, and filling the silica gel powder into the glass column by a wet method, namely mixing the silica gel powder with petroleum ether with the boiling point of 60-90 ℃, filling the silica gel powder into the glass column by a wet method until no bubbles exist, then adding about 600g of flowable dry powder, and finally adding PE (petroleum ether 60-90 ℃) and ETOH (absolute ethyl alcohol) to carry out leaching:
1) PE: 0ml of ETOH (5000 ml), and leaching for 2 h;
2) PE: washing the ETOH (5000 ml) with 50ml for 1 h;
3) PE: 400ml of ETOH (5000 ml) and 1h of leaching.
Determining the classification of the eluate according to TLC (thin layer chromatography), concentrating (distilling and concentrating), concentrating without spin drying, concentrating until the solid and liquid account for half of each, precipitating most of crystals, and filtering to obtain precipitated magnolol crystals, honokiol crystals and bisphenol mixture powder;
and continuously adding silica gel powder with equal mass into the filtered mother liquor, concentrating to dryness, and leaching again to obtain magnolol crystals, honokiol crystals and bisphenol mixture powder.
The total recovery rate of the magnolol crystal, the honokiol crystal and the bisphenol mixture powder reaches 98.5 percent, the purity of the separated magnolol crystal is more than 98 percent, the purity of the honokiol crystal is more than 97 percent, and the purity of the bisphenol mixture powder is more than 98 percent.
In the present example, the mesh number of the silica gel powder used was 100 mesh, and the extraction rate in the present invention is a value obtained by comparing the target substance obtained by extraction with the target substance theoretically contained in the raw material and multiplying the result by 100%.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims (4)

1. A separation method of Magnolia officinalis bisphenol is characterized in that Magnolia officinalis extract is separated with mixed solution of petroleum ether and ethanol as solvent;
the separation is carried out by leaching;
the magnolia bark extract is mixed with an adsorbent after being concentrated for leaching separation;
the adsorbent is silica gel powder;
the magnolia bark extract is processed into flowable dry powder and then subjected to separation operation, and the flowable dry powder is prepared by the following steps:
extracting cortex Magnolia officinalis with ethanol, and concentrating the obtained ethanol extractive solution to obtain concentrated solution; the alcohol extraction comprises the following steps: extracting by using an ethanol water solution with the volume concentration of 90% +/-2%; the extraction is reflux extraction, and the extraction temperature is 50-70 ℃; the extraction times are 2-4 times, the extraction time is 1-2h, and the amount of the ethanol water solution added in each extraction is 4-6 times of the weight of the magnolia bark raw material; the concentration is carried out until the volume of the alcohol extract is 8 to 15 percent;
mixing the concentrated solution with silica gel powder, and continuously concentrating to obtain flowable dry powder;
before leaching, the method also comprises the step of filling the flowing dry powder into columns, wherein the column filling comprises the following steps: firstly, filling petroleum ether and silica gel powder into a column by a mixing wet method until no bubbles exist, and then adding the flowable dry powder;
the mobile dry powder is leached by adopting the following solvents in sequence: petroleum ether, a first mixed solution of the petroleum ether and absolute ethyl alcohol in a volume ratio of 100:0.8-1.5, and a second mixed solution of the petroleum ether and the absolute ethyl alcohol in a volume ratio of 10: 0.8-1.5; in the leaching process, the leaching time of the petroleum ether is 100-150min, the leaching time of the first mixed solution is 50-70min, and the leaching time of the second mixed solution is 50-70 min;
collecting eluate, and concentrating to obtain magnolol and honokiol.
2. The method for separating magnolia biphenol according to claim 1, wherein the magnolia bark raw material is alcohol extracted in the form of a pulverized material;
the cortex Magnolia officinalis raw material comprises one or more of cortex Magnolia officinalis bark, cortex Magnolia officinalis root bark, and cortex Magnolia officinalis leaf; the particle size of the crushed material is 40-60 meshes.
3. The method for separating the magnolia officinalis bisphenols as claimed in claim 1, wherein the amount of the silica gel powder added is 2-3 times of the weight of the concentrated solution;
the particle size of the silica gel powder is 100-200 meshes.
4. The method for separating magnolol as claimed in claim 1, wherein the step of collecting the eluate further comprises collecting the eluate in stages, and the collected eluates are concentrated and dried to obtain magnolol monomer and honokiol monomer.
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CN1446785A (en) * 2003-03-07 2003-10-08 上海大学 Method of producing magnolol and honokiol
KR20080016269A (en) * 2006-08-18 2008-02-21 주식회사 유니젠 Manufacturing process of high purity honokiol, magnolol and extract

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1446785A (en) * 2003-03-07 2003-10-08 上海大学 Method of producing magnolol and honokiol
KR20080016269A (en) * 2006-08-18 2008-02-21 주식회사 유니젠 Manufacturing process of high purity honokiol, magnolol and extract

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