CN104610473A - Modification method of polystyrene resin for adsorbing flavones - Google Patents
Modification method of polystyrene resin for adsorbing flavones Download PDFInfo
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- CN104610473A CN104610473A CN201510070769.5A CN201510070769A CN104610473A CN 104610473 A CN104610473 A CN 104610473A CN 201510070769 A CN201510070769 A CN 201510070769A CN 104610473 A CN104610473 A CN 104610473A
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Abstract
The invention discloses a modification method of a polystyrene resin for adsorbing flavones, which comprises the following steps: adding the polystyrene resin and chloromethyl ether into a three-neck flask which is provided with a stirrer, a thermometer and a reflux condenser, carrying out chloromethylation reaction under the action of a catalyst zinc chloride, carrying out vacuum filtration on the chloromethylation resin obtained by reaction, separating from the reaction solution, cleaning with ethanol, and swelling; and adding a chloromethylated resin and an amino reagent methylamine into the three-neck flask which is provided with the stirrer, thermometer and reflux condenser, and heating in a water bath to 45 DEG C to react for 12 hours, thereby obtaining the amino modified resin. When the modified resin is used for extracting total flavones in the ethanol extract, the adsorption capacity of every gram of modified resin reaches 58.776mg. The modification method has the advantages of mild reaction conditions, high practicality and the like, and is widely applicable to the polystyrene resin.
Description
Technical field
The present invention relates to macroporous adsorbent resin preparation field, being specifically related to a kind of macroporous adsorbent resin preparation method thereof for adsorbing the flavonoid compound with polarity.
Background technology:
Flavonoid substances is widely distributed at occurring in nature, in the leaf of many existence and plant and fruit, Physiological Activities of Flavonoid is strong thus it apply very extensive in medicine, as vasodilation, antisepsis and anti-inflammation, inhibition tumor cell grow, protect the liver and the effect such as anti-oxidant.Due to flavonoid compound itself look after one's family, the change of ring system, flavonoid, flavonols can be categorized as.Cinnamophenone, aurones, anthocyanidin and above-mentioned all kinds of dihydro derivative, flavonoid compound structure diversity causes physico-chemical property there are differences.
In recent years, the research of the purifying technique aspect of flavonoid compound is got more and more, macroporous adsorbent resin is widely used in the extraction of flavonoid compound as a kind of high-efficiency adsorbent, such as, extract the technical study etc. of flavones, HPD300 macroporous resin purification kumquat flavonoid compounds in Shell of Water Chestnut with AB-8 resin.Situation common in every research is: a kind of macroporous adsorbent resin can only adsorb one or more flavones, selects referential little to other flavonoid compound sorbent materials.Polystyrene macroporous adsorbent resin is conventional polymeric adsorbent, there is mature preparation process, be easy to advantages such as drawing materials, as introduced active group in polystyrene polymeric adsorbent, thus modified resin is made to have stronger adsorption to polar yellow ketone compounds.
Summary of the invention
The object of the present invention is to provide a kind of polystyrene resin method of modifying for adsorbing flavonoid compound, this method of modifying reaction conditions is gentle, practical, is generally applicable to the advantages such as polystyrene resin amino modified.
For achieving the above object, technical scheme provided by the invention is:
For adsorbing a polystyrene resin method of modifying for flavonoid, comprising:
Step 1: ethanol 60-80 hour put into by resin, fully swelling resin deionized water is cleaned;
Step 2: add macroporous adsorbent resin and chloromethyl ether in the there-necked flask that agitator, thermometer and reflux exchanger are housed, zinc chloride powder is slowly added after stirring, the mass ratio of resin and chloromethyl ether, zinc chloride is 1: 7-10: 0.3-0.8, to be mixed evenly after be warming up to 35-50 DEG C with heating in water bath, reaction times is 8-14 hour, and reaction terminates the rear cold decompress filter that goes and goes out chloromethyl resin;
Step 3: resin will be rinsed with ethanol clean, and wash ethanol off with deionized water afterwards;
Step 4: ethanol 8-12 hour put into by resin, fully swelling resin deionized water cleans ethanol;
Step 5: add chloromethyl resin and methylamine in the there-necked flask that agitator, thermometer and reflux exchanger are housed, the mass ratio of chloromethyl resin and methylamine is 1: 4-8,35-60 DEG C is warming up to heating in water bath, reaction times is 8-14 hour, and reaction terminates the rear cold decompress filter that goes and obtains aminated resin;
Step 6: resin will be rinsed with dimethyl formamide clean, and wash dimethyl formamide off with deionized water afterwards.
Preferably, described a kind of polystyrene resin method of modifying for adsorbing flavonoid, is characterized in that, in described step 1 resin in ethanol soak time be 72H.
Preferably, described a kind of polystyrene resin method of modifying for adsorbing flavonoid, is characterized in that, adds resin and chloromethyl ether, the mass ratio of zinc chloride is 1: 8: 0.7 in described step 2, water bath heating temperature is 45 DEG C, and the reaction times is 12H.
Preferably, described a kind of polystyrene resin method of modifying for adsorbing flavonoid, it is characterized in that, in described step 4, chloromethyl resin puts into the swelling 12H of ethanol.
Preferably, described a kind of polystyrene resin method of modifying for adsorbing flavonoid, it is characterized in that, in described step 5, the reaction times is 12H, and water bath heating temperature is 45 DEG C.
Preferably, described a kind of polystyrene resin method of modifying for adsorbing flavonoid, it is characterized in that, the aminated resin in described step 6 needs to carry out soda acid activation treatment before use.
Preferably, described a kind of polystyrene resin method of modifying for adsorbing flavonoid, it is characterized in that, described aminated macroporous adsorbent resin can be used for adsorbing the flavonoid compound with polarity.
Beneficial effect of the present invention is that polystyrene resin macroporous adsorbent resin first introduces chloromethylation, so that carry out aminated, make reaction conditions requirement gentle, and this method is practical, is generally applicable to polystyrene resin amino modified; Aminated modified resin is better to the flavonoid compound adsorption effect with polarity.
Embodiment
Below in conjunction with in conjunction with the present invention preferably specific embodiment the present invention is described in further details.
Embodiment 1
First resin carries out chloromethylation, and the resin of chloromethylation is easy to carry out aminated reaction.
Step 1: resin puts into ethanol swelling 72 hours, fully swelling resin deionized water is cleaned.
Step 2: add macroporous adsorbent resin 20g and chloromethyl ether 160g in the there-necked flask that agitator, thermometer and reflux exchanger are housed, 14g zinc chloride powder is slowly added after stirring, to be mixed evenly after be warming up to 45 DEG C with heating in water bath, isothermal reaction 12 hours, reaction terminates rear cooling mixing solution, and decompress filter goes out chloromethyl resin.
Step 3: rinsed well by resin with ethanol, cleans ethanol with deionized water afterwards.
Embodiment 2
Resin chloromethylation process detailed in Example 1, aminated reaction is carried out on the resin basis of chloromethylation.
Step 1: macroporous adsorbent resin is put into ethanol and soak 12 hours, afterwards with de-ionised water fully swellable resins, until the ethanol in eluted resin.
Step 2: add chloromethyl resin 20g and methylamine 80g in the there-necked flask that agitator, thermometer and reflux exchanger are housed, 45 DEG C are warming up to heating in water bath, react after 12 hours and terminate experiment, carry out decompress filter after the cooling of question response mixture, obtain aminated resin particle.
Step 3: rinse resin well with dimethyl formamide, washes dimethyl formamide off with deionized water afterwards.
Step 4: resin 1.5% salt acid soak 2H is neutral with washed with de-ionized water to solution PH; Soak 2H with 1.5%NaOH again, be neutral with washed with de-ionized water to solution PH, resin removes excessive moisture through decompress filter afterwards.
Aminated resin absorption performance test: add aminated resin 1.0g in round-bottomed flask and total flavones mass concentration is 631.46mg/L ethanol extract 100ml, stirs stopped reaction after 4H through agitator.Measuring total flavones concentration with ultraviolet spectrophotometer is 279mg/L.
Embodiment 3
Resin chloromethylation process detailed in Example 1, the resin of chloromethylation carries out aminated reaction.
Step 1: macroporous adsorbent resin is put into ethanol and soak 12 hours, afterwards with de-ionised water fully swellable resins, until the ethanol in eluted resin.
Step 2: add chloromethyl resin 20g and methylamine 100g in the there-necked flask that agitator, thermometer and reflux exchanger are housed, 45 DEG C are warming up to heating in water bath, react after 12 hours and terminate experiment, carry out decompress filter after the cooling of question response mixture, obtain aminated resin particle.
Step 3: rinse resin well with dimethyl formamide, washes dimethyl formamide off with deionized water afterwards.
Step 4: resin 1.5% salt acid soak 2H is neutral with washed with de-ionized water to solution PH; Soak 2H with 1.5%NaOH again, be neutral with washed with de-ionized water to solution PH, resin removes excessive moisture through decompress filter afterwards.
Aminated resin absorption performance test: add aminated resin 1.0g in round-bottomed flask and total flavones mass concentration is 631.46mg/L ethanol extract 100ml, stirs stopped reaction after 4H through agitator.Measuring total flavones concentration with ultraviolet spectrophotometer is 103.2mg/L.
Embodiment 4
Resin chloromethylation process detailed in Example 1, the resin of chloromethylation carries out aminated reaction.
Step 1: macroporous adsorbent resin is put into ethanol and soak 12 hours, afterwards with de-ionised water fully swellable resins, until the ethanol in eluted resin.
Step 2: add chloromethyl resin 20g and methylamine 120g in the there-necked flask that agitator, thermometer and reflux exchanger are housed, 45 DEG C are warming up to heating in water bath, react after 12 hours and terminate experiment, carry out decompress filter after the cooling of question response mixture, obtain aminated resin particle.
Step 3: rinse resin well with dimethyl formamide, washes dimethyl formamide off with deionized water afterwards.
Step 4: resin 1.5% salt acid soak 2H is neutral with washed with de-ionized water to solution PH; Soak 2H with 1.5%NaOH again, be neutral with washed with de-ionized water to solution PH, resin removes excessive moisture through decompress filter afterwards.
Aminated resin absorption performance test: add aminated resin 1.0g in round-bottomed flask and total flavones mass concentration is 631.46mg/L ethanol extract 100ml, stirs stopped reaction after 4H through agitator.Measuring total flavones concentration with ultraviolet spectrophotometer is 43.7mg/L.
Embodiment 5
Resin chloromethylation process detailed in Example 1, the resin of chloromethylation carries out aminated reaction.
Step 1: macroporous adsorbent resin is put into ethanol and soak 12 hours, afterwards with de-ionised water fully swellable resins, until the ethanol in eluted resin.
Step 2: add chloromethyl resin 20g and methylamine 140g in the there-necked flask that agitator, thermometer and reflux exchanger are housed, 45 DEG C are warming up to heating in water bath, react after 12 hours and terminate experiment, carry out decompress filter after the cooling of question response mixture, obtain aminated resin particle.
Step 3: rinse resin well with dimethyl formamide, washes dimethyl formamide off with deionized water afterwards.
Step 4: resin 1.5% salt acid soak 2H is neutral with washed with de-ionized water to solution PH; Soak 2H with 1.5%NaOH again, be neutral with washed with de-ionized water to solution PH, resin removes excessive moisture through decompress filter afterwards.
Aminated resin absorption performance test: add aminated resin 1.0g in round-bottomed flask and total flavones mass concentration is 631.46mg/L ethanol extract 100ml, stirs stopped reaction after 4H through agitator.Measuring total flavones concentration with ultraviolet spectrophotometer is 20.17mg/L.
Embodiment 6
Simultaneous test: with the polystyrene resin absorption total flavones extracting solution without amino modified.
Adding without the resin 1.0g of amino modified and total flavones mass concentration in round-bottomed flask is 631.46mg/L ethanol extract 100ml, stirs stopped reaction after 4H through agitator.Measuring total flavones concentration with ultraviolet spectrophotometer is 451.7mg/L.
Table 1
| Embodiment is numbered | Resin and methylamine mass ratio | 1 gram of resin total flavones adsorptive capacity (mg/g) |
| 2 | 1∶4 | 35.246 |
| 3 | 1∶5 | 52.836 |
| 4 | 1∶6 | 58.776 |
| 5 | 1∶7 | 61.129 |
| 6 | / | 17.976 |
From table 1, the adsorption effect of resin to total flavones after amido is modified significantly promotes, along with the mass ratio of resin and methylamine is increased to 1: 7 from 1: 4, total flavones adsorptive capacity rate of growth by fast gradually in slowly, considering adsorptive capacity and methylamine consumption, is optimal conditions when the mass ratio of resin and methylamine is 1: 6.
Beneficial effect of the present invention is that method of modifying reaction conditions is gentle, practical, is generally applicable to the advantages such as polystyrene resin amino modified
Although embodiment of the present invention are open as above, but it is not restricted to listed in specification sheets and embodiment utilization, it can be applied to various applicable the field of the invention completely, for those skilled in the art, can easily realize other amendment, therefore do not deviating under the universal that claim and equivalency range limit, the present invention is not limited to specific details and illustrates here and the legend described.
Claims (7)
1., for adsorbing a polystyrene resin method of modifying for flavonoid, it is characterized in that, comprise:
Step 1: ethanol 60-80 hour put into by resin, fully swelling resin deionized water is cleaned;
Step 2: add macroporous adsorbent resin and chloromethyl ether in the there-necked flask that agitator, thermometer and reflux exchanger are housed, zinc chloride powder is slowly added after stirring, the mass ratio of resin and chloromethyl ether, zinc chloride is 1: 7-10: 0.3-0.8, to be mixed evenly after be warming up to 35-50 DEG C with heating in water bath, reaction times is 8-14 hour, and reaction terminates rear cooling decompress filter and goes out chloromethyl resin;
Step 3: resin will be rinsed with ethanol clean, and wash ethanol off with deionized water afterwards;
Step 4: ethanol 8-12 hour put into by resin, fully swelling resin deionized water cleans ethanol;
Step 5: add chloromethyl resin and methylamine in the there-necked flask that agitator, thermometer and reflux exchanger are housed, the mass ratio of chloromethyl resin and methylamine is 1: 4-8,35-60 DEG C is warming up to heating in water bath, reaction times is 8-14 hour, and reaction terminates the rear cold decompress filter that goes and obtains aminated resin;
Step 6: resin will be rinsed with dimethyl formamide clean, and wash dimethyl formamide off with deionized water afterwards.
2. a kind of polystyrene resin method of modifying for adsorbing flavonoid as claimed in claim 1, is characterized in that, in described step 1 resin in ethanol soak time be 72H.
3. a kind of polystyrene resin method of modifying for adsorbing flavonoid as claimed in claim 1, it is characterized in that, add resin and chloromethyl ether in described step 2, the mass ratio of zinc chloride is 1: 8: 0.7, water bath heating temperature is 45 DEG C, and the reaction times is 12H.
4. a kind of polystyrene resin method of modifying for adsorbing flavonoid as claimed in claim 1, it is characterized in that, in described step 4, chloromethyl resin puts into the swelling 12H of ethanol.
5. a kind of polystyrene resin method of modifying for adsorbing flavonoid as claimed in claim 1, it is characterized in that, in described step 5, the reaction times is 12H, and water bath heating temperature is 45 DEG C.
6. a kind of polystyrene resin method of modifying for adsorbing flavonoid as claimed in claim 1, it is characterized in that, the aminated resin in described step 6 needs to carry out soda acid activation treatment before use.
7. a kind of polystyrene resin method of modifying for adsorbing flavonoid as described in claim 1 or 6, it is characterized in that, described aminated macroporous adsorbent resin can be used for adsorbing the flavonoid compound with polarity.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106206375A (en) * | 2015-06-01 | 2016-12-07 | 日东电工株式会社 | Semiconductor back surface thin film and application thereof |
| CN108452777A (en) * | 2018-01-09 | 2018-08-28 | 同济大学 | A kind of macroreticular resin method of modifying for adsorbing low-concentration sulfur dioxide in air |
| CN112826894A (en) * | 2021-02-08 | 2021-05-25 | 上海华源制药安徽广生药业有限公司 | Utilization method of leftovers from processing of traditional Chinese medicine decoction pieces |
| CN113101905A (en) * | 2021-05-14 | 2021-07-13 | 重庆恩斯特龙通用航空技术研究院有限公司 | Method for removing methyl orange in wastewater by using styrene-propylene copolymer fiber for adsorption |
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| CN101050227A (en) * | 2007-02-09 | 2007-10-10 | 南开大学 | Technique for extracting compound of flavone in high purity from whole individual plant of tartary buckwheat through method of adsorptive resin |
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2015
- 2015-02-11 CN CN201510070769.5A patent/CN104610473A/en active Pending
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| US4025705A (en) * | 1973-06-23 | 1977-05-24 | Bayer Aktiengesellschaft | Insoluble adsorber resin suitable for treating drinking water and sewage |
| CN101050227A (en) * | 2007-02-09 | 2007-10-10 | 南开大学 | Technique for extracting compound of flavone in high purity from whole individual plant of tartary buckwheat through method of adsorptive resin |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106206375A (en) * | 2015-06-01 | 2016-12-07 | 日东电工株式会社 | Semiconductor back surface thin film and application thereof |
| CN106206375B (en) * | 2015-06-01 | 2021-07-02 | 日东电工株式会社 | Film for semiconductor back surface and use thereof |
| CN108452777A (en) * | 2018-01-09 | 2018-08-28 | 同济大学 | A kind of macroreticular resin method of modifying for adsorbing low-concentration sulfur dioxide in air |
| CN112826894A (en) * | 2021-02-08 | 2021-05-25 | 上海华源制药安徽广生药业有限公司 | Utilization method of leftovers from processing of traditional Chinese medicine decoction pieces |
| CN113101905A (en) * | 2021-05-14 | 2021-07-13 | 重庆恩斯特龙通用航空技术研究院有限公司 | Method for removing methyl orange in wastewater by using styrene-propylene copolymer fiber for adsorption |
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