CN104744625A - Preparation method of polyacrylic acid adsorption resin for purification of flavonoid compounds - Google Patents
Preparation method of polyacrylic acid adsorption resin for purification of flavonoid compounds Download PDFInfo
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- CN104744625A CN104744625A CN201310756129.0A CN201310756129A CN104744625A CN 104744625 A CN104744625 A CN 104744625A CN 201310756129 A CN201310756129 A CN 201310756129A CN 104744625 A CN104744625 A CN 104744625A
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Abstract
The invention provides a preparation method of a polyacrylic acid adsorption resin for purification of flavonoid compounds, which comprises the following steps: in a reaction kettle, feeding pure water and a polymerization inhibitor, and adding a certain amount of a dispersant, an initiator, a methyl acrylate/crosslinking agent monomer/perfluorinated (alkyl vinyl ether) mixture, a pore-foaming agent, and the like; heating up to the reaction temperature; after the reaction is completed, drying the obtained object, and extracting the pore-foaming agent; and drying and packaging the obtained product. According to the invention, a small amount of double-bonded perfluorinated (alkyl vinyl ether) as a third monomer is introduced in polymerization so as to improve the compatibility of the monomer, as well as the high temperature resistance and acid and alkali corrosion resistance of a resin matrix, thereby improving the strength of polymer particles. The polyacrylate adsorption resin prepared by using the method disclosed by the invention, in the process of separating flavonoids, has the advantages of high yield, low cost, simple operation, and the like, and can be applied to mass production. Due to the introduction of fluorine-containing groups, the corrosion resistance of the resin matrix is enhanced, and the surfaces of spheres are protected, thereby prolonging the service lives of the spheres.
Description
Technical field
The present invention relates to a kind of preparation method of resin sorbent, particularly a kind of polyacrylic adsorbent resin preparation method thereof being applied to flavonoid compound purifying.
Background technology
Middle polarity macroporous adsorbent resin is the polymeric adsorbent containing ester group, and the methacrylic ester of more function group is as linking agent.Its surface has hydrophobic and hydrophilic two portions concurrently.Both apolar substance can be adsorbed in polar solvent, again can by adsorb polar substances in non-polar solvent, such as, also referred to as aliphatics sorbent material, polyacrylate type polymer.
Polarity (function base) and the space structure (aperture, specific surface, pore volume) of resin are the important factors affecting absorption property.Polystyrene type resin is generally suitable for the compound of nonpolar and low-pole material as flavonoid, flavanone etc., polyacrylics is generally with ester group or amido, better to the absorption of the flavonoid compounds such as the cinnamophenone of middle polarity and polar compound (as flavones sterol, flavonoid glycoside) and phenolic hydroxy group.Flavonoid compound generally more has phenolic hydroxyl group and glycosidic linkage, has certain polarity and wetting ability, and the ability generating hydrogen bond is comparatively strong, is conducive to the absorption of low-pole and polar resin.
CN101200517 nonpolar macroporous adsorption resin and synthetic method thereof disclose a kind of nonpolar macroporous adsorption resin and the synthetic method thereof of extracting Chinese medicinal plant effective constituent, by the nonpolar macroporous adsorption resin that the inventive method is synthesized, overcome current commercial resins owing to all can not be directly used in the extraction and isolation of Chinese medicine containing multiple organic residue, and it is easily broken, light specific gravity, granularity is uneven, the shortcomings such as the inconsistent unstable properties of quality of lot, in building-up process, special disposal removal has been carried out to organic residue simultaneously, avoid the secondary pollution problem that may occur when extracting effective ingredients in plant.
In the research and development of new Chinese medicine with in producing, adopt special macroporous adsorbent resin to be optionally separated effective ingredients in plant or to remove invalid components and achieve good effect, but the acrylic acid series polymeric adsorbent intensity prepared by existing known technology is low, easy fragmentation, unstable properties, the organic residues such as the pore-creating agent in resin are removed without special disposal, thus when extraction and isolation, fragment or the organic residue of resin are mixed into liquid, cause secondary pollution.
Summary of the invention
For the deficiencies in the prior art, invent a kind of polyacrylic adsorbent resin preparation method thereof being applied to flavonoid compound purifying, there is following structure:
The integer of N=1-3000
In a kettle., squeeze into pure water, stopper, add a certain amount of dispersion agent, initiator, methyl acrylate/crosslinkers monomers/perfluor (alkyl vinyl ether) mixture, pore-creating agents etc., are warming up to temperature of reaction, and question response terminates. dry, extracting pore-creating agent, dry closing bag. the present invention introduces the perfluor (alkyl vinyl ether) of a small amount of band double bond as Third monomer in polymerization, and to improve the consistency of monomer, and resin matrix ground is high temperature resistant, the ability of acid and alkali corrosion, thus the intensity that improve polymer beads.
Perfluor (alkyl vinyl ether) structural formula is as follows:
CF
3O(CF
2O)nCF
2CF
2OCF＝CF
2n＝1-5.
The invention provides a kind of polyacrylic adsorbent resin preparation method thereof being applied to flavonoid compound and refining, realized by following steps:
The preparation of step 1. aqueous phase
By weight, add 100 parts of pure water 0.5-2 part organic chemistry dispersion agent (preferably 0.5 part) in pressure reaction still, stir;
Described chemical dispersant is selected from polyvinyl alcohol, gelatin or Walocel MT 20.000PV etc.
The preparation of step 2. oil phase
By weight, by 100 parts of methyl acrylates, 50-100 part (preferably 70 parts) linking agent, 0.5-2 part (preferably 1 part) perfluor (alkyl vinyl ether) mixing, add 0.5-3 part peroxide initiator (preferably 2 parts), 10-40 part pore-creating agent again, stir;
Step 3. suspension polymerization
Being added in step 1 to be equipped with by the oil-phase solution prepared in step 2 beaker prepares in the pressure reaction still of aqueous phase, at 70-100 DEG C of staged temperature reaction 10-20h, reaction terminates rear blowing, and washing microballoon is limpid to water, after oven dry, pore-creating agent extracting is clean, obtain product.
Linking agent described in step 2 is preferably from N,N methylene bis acrylamide (MBA).
Perfluor (alkyl vinyl ether) structural formula described in step 2 is as follows:
CF
3O(CF
2O)nCF
2CF
2OCF＝CF
2n＝1-5.
Comprise: CF
3oCF
2oCF
2cF
2oCF=CF
2, CF
3o (CF
2o)
2cF
2cF
2oCF=CF
2,
CF
3O(CF
2O)
4CF
2CF
2OCF＝CF
2、CF
3O(CF
2O)
3CF
2CF
2OCF＝CF
2、CF
3O(CF
2O)
5CF
2CF
2OCF＝CF
2
The preferred benzoyl peroxide of peroxide initiator described in step 2.
Pore-creating agent described in step 2 is good solvent or poor solvent or mixed solvent, as white oil, and solvent oil, toluene etc., preferred toluene.
Beneficial effect of the present invention:
1): by the polyacrylic polymeric adsorbent separating flavone that the inventive method is obtained, there is yield high, the advantages such as cost is low, easy and simple to handle, can select for large production.
2) introducing of fluoro-containing group, resin matrix erosion resistance is strong, spherome surface arrives, thus use.
Concrete real mode
Following instance is further bright the present invention, is not that system is of the present invention.
The preparation of step 1. aqueous phase
By weight, add 100 parts of pure water in pressure reaction still, 0.5 part of gelatin, stirs.
The preparation of step 2. oil phase
The oil phase of following ratio is divided and mixes in beaker, stir;
Step 3. suspension polymerization
Being added in step 1 to be equipped with by the oil-phase solution prepared in step 2 beaker prepares in the pressure reaction still of aqueous phase, after carrying out stir, after 90 DEG C reaction 16h, reaction terminates rear blowing, washing microballoon is limpid to water, after oven dry, pore-creating agent extracting is clean, obtains product. and be SX-1
Example 2
The preparation of step 1. aqueous phase
By weight, add 100 parts of pure water in pressure reaction still, 2 parts of polyvinyl alcohol, stir.
The preparation of step 2. oil phase
The oil phase of following ratio is divided and mixes in beaker, stir;
Step 3. suspension polymerization
Being added in step 1 to be equipped with by the oil-phase solution prepared in step 2 beaker prepares in the pressure reaction still of aqueous phase, and at 70 DEG C of reaction 20h, reaction terminates rear blowing, and washing microballoon is limpid to water, after oven dry, pore-creating agent extracting is clean, obtains product. and be SX-2
Example 3
The preparation of step 1. aqueous phase
By weight, add 100 parts of pure water in pressure reaction still, 1 part of Walocel MT 20.000PV, stirs.
The preparation of step 2. oil phase
The oil phase of following ratio is divided and mixes in beaker, stir;
Step 3. suspension polymerization
Being added in step 1 to be equipped with by the oil-phase solution prepared in step 2 beaker prepares in the pressure reaction still of aqueous phase, and at 70 DEG C of reaction 20h, reaction terminates rear blowing, and washing microballoon is limpid to water, after oven dry, pore-creating agent extracting is clean, obtains product. be numbered SX-3
Embodiment 4
CF in step 2
3oCF
2oCF
2cF
2oCF=CF
2ether weight part is 0.5, the other the same as in Example 1.Products obtained therefrom is numbered SX-4.
Embodiment 5
CF in step 2
3oCF
2oCF
2cF
2oCF=CF
2ether weight part is 2, the other the same as in Example 1.Products obtained therefrom is numbered SX-5.
Embodiment 6
Perfluor (alkyl vinyl ether) selects CF
3o (CF
2o)
2cF
2cF
2oCF=CF
2, the other the same as in Example 1.Products obtained therefrom is numbered SX-6.
Embodiment 7
Perfluor (alkyl vinyl ether) selects CF
3o (CF
2o)
4cF
2cF
2oCF=CF
2, the other the same as in Example 1.Products obtained therefrom is numbered SX-7.
Embodiment 8
Perfluor (alkyl vinyl ether) selects CF
3o (CF
2o)
3cF
2cF
2oCF=CF
2, the other the same as in Example 1.Products obtained therefrom is numbered SX-8.
Embodiment 9
Perfluor (alkyl vinyl ether) selects CF
3o (CF
2o)
5cF
2cF
2oCF=CF
2, the other the same as in Example 1.Products obtained therefrom is numbered SX-9.
Comparative example 1
Do not add perfluor (alkyl vinyl ether), the other the same as in Example 1.Products obtained therefrom is numbered SX-10.
By Fourier transform infrared spectrometer, pressing potassium bromide troche does Infrared spectroscopy to synthesized each resin.Infrared spectra from reaction product: SX1-SX12 is at 1730cm
-1near there is the carbonyl peak of ester group, SX1-SX5, SX8-SX11 are at 3310cm
-1near there is N-H stretching vibration peak, 3310cm
-1near there is C=C-H symmetric vibration peak, illustrate and introduce acrylamide group in the skeleton of polystyrene resin; At 1120cm in the collection of illustrative plates of SX1-SX11 sample
-1near have C-O-C absorption peak, at 1230cm
-1near have CF
3stretching vibration peak, illustrated that perfluor (alkyl vinyl ether) exists, so can determine that this patent product generates by the polymkeric substance of methyl acrylate cross-linking system and perfluor (alkyl vinyl ether) monomer copolymerization.
Embodiment 13
By Chinese medicine producting rule with the obtained resin of the present invention of embodiment and commercially available Extraction of Flavonoids from Ginkgo Leaves by Adsorptive Resin, result is as follows:
| Production code member | Adsorptive capacity mg/g | Resolution factor % | Reusable number of times |
| SX-1 | 143 | 98 | 6 |
| SX-2 | 136 | 96 | 6 |
| SX-3 | 132 | 98 | 6 |
| SX-4 | 138 | 98 | 7 |
| SX-5 | 165 | 95 | 6 |
| SX-6 | 143 | 92 | 4 |
| SX-7 | 135 | 98 | 5 |
| SX-8 | 133 | 99 | 6 |
| SX-9 | 156 | 98 | 5 |
| SX-10 | 110 | 89 | 2 |
Claims (3)
1. be applied to a polyacrylic adsorbent resin preparation method thereof for flavonoid compound purifying, it is characterized in that comprising the following steps:
The preparation of step 1. aqueous phase
By weight, add 100 parts of pure water 0.5-2 part organic chemistry dispersion agents in pressure reaction still, stir.Described chemical dispersant is selected from polyvinyl alcohol, gelatin or Walocel MT 20.000PV etc.
The preparation of step 2. oil phase
By weight, by 100 parts of methyl acrylates, 50-100 part linking agent, 0.5-2 part perfluor (alkyl vinyl ether) mixing, then add 0.5-3 part peroxide initiator, 10-40 part pore-creating agent, stir.
Step 3. suspension polymerization
Being added in step 1 to be equipped with by the oil-phase solution prepared in step 2 beaker prepares in the pressure reaction still of aqueous phase, at 70-100 DEG C of staged temperature reaction 10-20h, reaction terminates rear blowing, and washing microballoon is limpid to water, after oven dry, pore-creating agent extracting is clean, obtain product.
2. be applied to a polyacrylic adsorbent resin preparation method thereof for flavonoid compound purifying, it is characterized in that, perfluor (alkyl vinyl ether) structural formula described in step 2 is as follows:
CF
3O(CF
2O)nCF
2CF
2OCF＝CF
2n＝1-5。
Comprise: CF
3oCF
2oCF
2cF
2oCF=CF
2, CF
3o (CF
2o)
2cF
2cF
2oCF=CF
2, CF
3o (CF
2o)
4cF
2cF
2oCF=CF
2, CF
3o (CF
2o)
3cF
2cF
2oCF=CF
2, CF
3o (CF
2o)
5cF
2cF
2oCF=CF
2.
3. according to a kind of polyacrylic adsorbent resin preparation method thereof being applied to flavonoid compound purifying that the described preparation method of one of claim 1-2 obtains.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105906752A (en) * | 2016-05-05 | 2016-08-31 | 巨化集团技术中心 | Preparation method of adsorbing material for extracting perfluorooctanoic acid |
| CN113769699A (en) * | 2021-09-22 | 2021-12-10 | 安徽蓝科新材料有限公司 | Preparation equipment and method of heat-resistant acrylate resin monomer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1036526C (en) * | 1991-01-29 | 1997-11-26 | 华南理工大学 | Preparation of magnetic macroporous ion-exchange resin for adsorption |
| CN1289183C (en) * | 2004-01-30 | 2006-12-13 | 浙江科锐生物科技有限公司 | Method for preparing macromolecule resin type bilirubin sorbent |
| CN102603971A (en) * | 2012-02-27 | 2012-07-25 | 中国地质大学（武汉） | Magnetic expansion adsorption resin and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105906752A (en) * | 2016-05-05 | 2016-08-31 | 巨化集团技术中心 | Preparation method of adsorbing material for extracting perfluorooctanoic acid |
| CN105906752B (en) * | 2016-05-05 | 2018-05-11 | 巨化集团技术中心 | A kind of preparation method for extracting perfluoro caprylic acid sorbing material |
| CN113769699A (en) * | 2021-09-22 | 2021-12-10 | 安徽蓝科新材料有限公司 | Preparation equipment and method of heat-resistant acrylate resin monomer |
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