CN106964324A - A kind of isoflavones isolates and purifies the preparation method with macroporous absorbent resin - Google Patents
A kind of isoflavones isolates and purifies the preparation method with macroporous absorbent resin Download PDFInfo
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- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
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- C07D311/36—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 3 only not hydrogenated in the hetero ring, e.g. isoflavones
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- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
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- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
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Abstract
The preparation method with macroporous absorbent resin is isolated and purified the invention discloses a kind of isoflavones, is related to biological medicine technical field of purification, preparation method comprises the following steps：(1) preparation of macroporous absorbent resin, the pretreatment of (2) macroporous absorbent resin, the modification of (3) macroporous absorbent resin.The made macroporous absorbent resin of the present invention reaches more than 17mg/g to the adsorbance of isoflavones, the efficient desorption of isoflavones can be realized after being rinsed through 60% methanol solution, desorption efficiency reaches more than 98.5%, the purity of made isoflavones reaches more than 60%, therefore the macroporous absorbent resin is applied to efficiently separating for isoflavones.
Description
Technical field：
The present invention relates to biological medicine technical field of purification, and in particular to a kind of isoflavones is isolated and purified to be inhaled with macropore
The preparation method of attached resin.
Background technology：
Naturally occurring isoflavones has 12 kinds, is divided into daidzin, genistin and the major class of C22H22O10 3.Greatly
Beans isoflavones has anti-oxidant, pre- anti-cancer, strengthen immunity and improves the functions such as breeding performonce fo animals, has been widely used in
In the fields such as biology, feed, medicine and health care of food.Research finds that only the aglycon of sequestered just has biological activity, needs
The aglycon for changing into sequestered through enzymolysis or sour water solution glucosides could be absorbed by animal or human body.At present, the different Huang of soybean is improved
The method of Aglycones content mainly has extraction, physics auxiliary law, High Pressure Wet and ultrafiltration etc. in ketone, but these methods have work
Skill is more complicated, cost is higher and the shortcomings of high Determination of Residual Organic Solvents, is unsuitable for mass preparation.
Flavonoids by Macroporous Adsorption Resin is in recent years, using a kind of extensive purification process, to have selection with respect to other purification process
Property it is good, nontoxic and pollution-free the advantages of, but the adsorbance of the macroporous absorbent resin used at present is relatively low, and is needed during desorption a large amount of
Organic solvent is rinsed, even if these organic solvents can be recycled, it is also desirable to consume big energy to realize.
The content of the invention：
The technical problems to be solved by the invention are to provide that a kind of adsorbance is high, desorption easily and high big of Aglycones content
Beans isoflavones isolates and purifies the preparation method with macroporous absorbent resin.
The technical problems to be solved by the invention are realized using following technical scheme：
A kind of isoflavones isolates and purifies the preparation method with macroporous absorbent resin, and its preparation method includes following step
Suddenly：
(1) preparation of macroporous absorbent resin：Xiang Shuizhong be proportionally added into styrene, hydrogenated rosin acrylic acid glycerine ester,
Hydroxyethyl methacrylate, nanometer pore-foaming agent and initiator, are sufficiently mixed after under supersonic frequency 40kHz, power output 200W
Ultrasonically treated 15min, the microwave treatment 10min under microwave frequency 2450MHz, power output 700W, and in 0-5 DEG C of environment
30min is stood, continues microwave treatment 10min after being well mixed, 15min is then stood in -5-0 DEG C of environment, after being well mixed
Microwave treatment 10min again, gained mixed liquor is cooled to 0-5 DEG C of insulation mixing 1h with 5 DEG C/min cooling rate, then will be mixed
Liquid separation of solid and liquid is closed, gained solid phase is washed three times with 35-40 DEG C of warm water and obtains Archon, finally by Archon in vacuum at 60-65 DEG C
Dry, produce macroporous absorbent resin；
(2) pretreatment of macroporous absorbent resin：Poloxamer, N- methylols are added into above-mentioned made macroporous absorbent resin
Acrylamide and HPMA, and with 5 DEG C/min programming rate be warming up to 65-70 DEG C insulation mixing 30min, then to
30-35 DEG C of water of 3 times of weight is added in gained mixture, it is mixed that continuation is warming up to reflux state insulation with 5 DEG C/min programming rate
15min is closed, room temperature is then naturally cooled to, filtered, gained resin spheroid is washed three times, most after vacuum drying at 60-65 DEG C；
(3) modification of macroporous absorbent resin：Nano titanium oxide and clothing health are added into isocyanuric acid three-glycidyl ester
Acid anhydrides, is warming up to 115-120 DEG C of insulation mixing 15min with 5 DEG C/min programming rate, adds macropore after pretreatment and inhale
Attached resin, continues, in 115-120 DEG C of insulation mixing 30min, to wash three times after naturally cool to after room temperature, most afterwards through gained resin
Spheroid is in vacuum drying at 60-65 DEG C.
Step (1) reclaimed water, styrene, hydrogenated rosin acrylic acid glycerine ester, hydroxyethyl methacrylate, nanometer are caused
The mass ratio of hole agent and initiator is 300-400:45-50:30-35:15-20:40-45:0.5-1.
Macroporous absorbent resin in the step (2), poloxamer, N hydroxymethyl acrylamide and HPMA
Mass ratio is 60-65:1-2:0.5-1:0.5-1.
Macroporous absorbent resin, isocyanuric acid three-glycidyl ester, nano titanium oxide and itaconic anhydride in the step (3)
Mass ratio be 60-65:5-10:3-5:0.1-0.2.
The nanometer pore-foaming agent is made up of the raw material of following parts by weight：5-10 parts of microcrystalline cellulose, polyglutamic acid 3-5
Part, 1-2 parts of rilanit special, 0.5-1 parts of PDDA, 0.5-1 parts of sodium gluconate, ferrocene
0.05-0.1 parts, 30-50 parts of water, its preparation method is：Xiang Shuizhong adds microcrystalline cellulose and rilanit special, and is warming up to back
Stream mode insulation mixing 15min, after naturally cool to addition polyglutamic acid and poly dimethyl allyl chlorination after 40-45 DEG C
Ammonium, stirring 30min formation emulsions, then adds sodium gluconate and ferrocene, sends into gained mixture after being well mixed and spray
In mist drying machine, particle is ground obtained by drying is made nanometer powder, and finally nanometer powder, which adds water, is made solid content 30-
35wt% emulsion, produces a nanometer pore-foaming agent.
The nano titanium oxide is the nano-powder being made after the modified processing of titanium dioxide, and its preparation method is：
PVPP and hexamethylolmelamine pregnancy ether are added into titanium dioxide, is first heated up with 5 DEG C/min programming rate
To 120-125 DEG C of insulation mixing 30min, PAMA and epoxidized soybean oil are added, is continued at 120-125 DEG C
Insulation mixing 30min, gained mixture is cooled to 40-50 DEG C with 10 DEG C/min cooling rate, and adds 40-50 DEG C of water, with
10 DEG C/min programming rate is warming up to reflux state insulation mixing 10min, and 1h is stood after naturally cooling to room temperature, is filtered,
Gained solid is finally sent into nano-level grinder in being dried at 75-80 DEG C, ground to obtain nano titanium oxide.
The titanium dioxide, PVPP, hexamethylolmelamine pregnancy ether, PAMA, epoxy
The mass ratio of soybean oil and water is 30-40:3-5:0.5-1:2-3:0.1-0.3:100-150.
The beneficial effects of the invention are as follows：
(1) use three step microwave treatment methods association with the operation that cools in the preparatory phase of macroporous absorbent resin, prepared shortening
The resistant of high or low temperature of macroporous absorbent resin is improved while time；
(2) by the pretreatment of water miscible poloxamer, N hydroxymethyl acrylamide and HPMA, reduction
The surface tension of macroporous absorbent resin, increases the surface-active of macroporous absorbent resin, in favor of the modification of lower step；
(3) macroporous absorbent resin is carried out using isocyanuric acid three-glycidyl ester, nano titanium oxide and itaconic anhydride
Modification, increases its specific surface area, strengthens its adsorption activity；
(4) made macroporous absorbent resin reaches more than 17mg/g to the adsorbance of isoflavones, through 60% methanol solution
The efficient desorption of isoflavones can be realized after flushing, desorption efficiency reaches more than 98.5%, and the purity of made isoflavones reaches
To more than 60%, therefore the macroporous absorbent resin is applied to efficiently separating for isoflavones.
Embodiment：
In order that the technical means, the inventive features, the objects and the advantages of the present invention are easy to understand, tie below
Specific embodiment is closed, the present invention is expanded on further.
Embodiment 1
(1) preparation of macroporous absorbent resin：45 parts of styrene, 30 parts of hydrogenated rosins third are proportionally added into 350 parts of water
Olefin(e) acid glycerine ester, 15 parts of hydroxyethyl methacrylates, 40 parts of nanometer pore-foaming agents and 0.5 part of initiator, are sufficiently mixed after super
Ultrasonically treated 15min under acoustic frequency 40kHz, power output 200W, it is micro- under microwave frequency 2450MHz, power output 700W
Ripple handles 10min, and stands 30min in 0-5 DEG C of environment, continues microwave treatment 10min after being well mixed, then in -5-0 DEG C
15min is stood in environment, microwave treatment 10min again after being well mixed, gained mixed liquor is cooled with 5 DEG C/min cooling rate
To 0-5 DEG C of insulation mixing 1h, then by mixed liquor separation of solid and liquid, gained solid phase is washed three times with 35-40 DEG C of warm water and obtains Archon,
Archon is finally produced into macroporous absorbent resin in being dried in vacuo at 60-65 DEG C；
(2) pretreatment of macroporous absorbent resin：Added into above-mentioned made 60 parts of macroporous absorbent resins 2 parts of poloxamers,
0.5 part of N hydroxymethyl acrylamide and 1 part of HPMA, and 65-70 DEG C of guarantor is warming up to 5 DEG C/min programming rate
Temperature mixing 30min, then 30-35 DEG C of water of 3 times of weight is added into gained mixture, continue to heat up with 5 DEG C/min programming rate
To reflux state insulation mixing 15min, then naturally cool to room temperature, filter, gained resin spheroid wash three times, most after
It is dried in vacuo at 60-65 DEG C；
(3) modification of macroporous absorbent resin：3 parts of nano titanium oxides are added into 10 parts of isocyanuric acid three-glycidyl esters
With 0.15 part of itaconic anhydride, 115-120 DEG C of insulation mixing 15min is warming up to 5 DEG C/min programming rate, added through pre- place
60 parts of macroporous absorbent resins after reason, continue in 115-120 DEG C of insulation mixing 30min, after naturally cool to washing three after room temperature
It is secondary, most afterwards through gained resin spheroid in vacuum drying at 60-65 DEG C.
The preparation of nanometer pore-foaming agent：5 parts of microcrystalline celluloses and 1 part of rilanit special are added into 50 parts of water, and is warming up to
Reflux state insulation mixing 15min, after naturally cool to 5 parts of polyglutamic acids of addition and 0.5 part of poly dimethyl two after 40-45 DEG C
Allyl ammonium chloride, stirring 30min formation emulsions, then adds 0.5 part of sodium gluconate and 0.05 part of ferrocene, is well mixed
Gained mixture is sent into spray dryer afterwards, particle is ground obtained by drying is made nanometer powder, finally by nanometer powder
Add water and solid content 30-35wt% emulsion is made, produce a nanometer pore-foaming agent.
The preparation of nano titanium oxide：3 parts of PVPPs and 0.5 part of hexamethylol three are added into 40 parts of titanium dioxide
Poly cyanamid pregnancy ether, is first warming up to 120-125 DEG C of insulation mixing 30min with 5 DEG C/min programming rate, add 3 parts of the moon from
Sub- polyacrylamide and 0.2 part of epoxidized soybean oil, continue the insulation mixing 30min at 120-125 DEG C, gained mixture is with 10
DEG C/min cooling rate is cooled to 40-50 DEG C, and adds 40-50 DEG C of 150 parts of water, it is warming up to 10 DEG C/min programming rate
Reflux state insulation mixing 10min, 1h is stood after naturally cooling to room temperature, filter, gained solid at 75-80 DEG C dry,
It is ground to obtain nano titanium oxide finally in feeding nano-level grinder.
Embodiment 2
(1) preparation of macroporous absorbent resin：50 parts of styrene, 35 parts of hydrogenated rosins third are proportionally added into 350 parts of water
Olefin(e) acid glycerine ester, 15 parts of hydroxyethyl methacrylates, 40 parts of nanometer pore-foaming agents and 0.5 part of initiator, are sufficiently mixed after super
Ultrasonically treated 15min under acoustic frequency 40kHz, power output 200W, it is micro- under microwave frequency 2450MHz, power output 700W
Ripple handles 10min, and stands 30min in 0-5 DEG C of environment, continues microwave treatment 10min after being well mixed, then in -5-0 DEG C
15min is stood in environment, microwave treatment 10min again after being well mixed, gained mixed liquor is cooled with 5 DEG C/min cooling rate
To 0-5 DEG C of insulation mixing 1h, then by mixed liquor separation of solid and liquid, gained solid phase is washed three times with 35-40 DEG C of warm water and obtains Archon,
Archon is finally produced into macroporous absorbent resin in being dried in vacuo at 60-65 DEG C；
(2) pretreatment of macroporous absorbent resin：2 parts of poloxamers, 1 are added into above-mentioned made 65 parts of macroporous absorbent resins
Part N hydroxymethyl acrylamide and 0.5 part of HPMA, and 65-70 DEG C of guarantor is warming up to 5 DEG C/min programming rate
Temperature mixing 30min, then 30-35 DEG C of water of 3 times of weight is added into gained mixture, continue to heat up with 5 DEG C/min programming rate
To reflux state insulation mixing 15min, then naturally cool to room temperature, filter, gained resin spheroid wash three times, most after
It is dried in vacuo at 60-65 DEG C
(3) modification of macroporous absorbent resin：5 parts of nano titanium oxides are added into 10 parts of isocyanuric acid three-glycidyl esters
With 0.15 part of itaconic anhydride, 115-120 DEG C of insulation mixing 15min is warming up to 5 DEG C/min programming rate, added through pre- place
65 parts of macroporous absorbent resins after reason, continue in 115-120 DEG C of insulation mixing 30min, after naturally cool to washing three after room temperature
It is secondary, most afterwards through gained resin spheroid in vacuum drying at 60-65 DEG C.
The preparation of nanometer pore-foaming agent：10 parts of microcrystalline celluloses and 2 parts of rilanit specials are added into 50 parts of water, and are warming up to
Reflux state insulation mixing 15min, after naturally cool to 5 parts of polyglutamic acids of addition and 0.5 part of poly dimethyl two after 40-45 DEG C
Allyl ammonium chloride, stirring 30min formation emulsions, then adds 0.5 part of sodium gluconate and 0.05 part of ferrocene, is well mixed
Gained mixture is sent into spray dryer afterwards, particle is ground obtained by drying is made nanometer powder, finally by nanometer powder
Add water and solid content 30-35wt% emulsion is made, produce a nanometer pore-foaming agent.
The preparation of nano titanium oxide：5 parts of PVPPs and 0.5 part of hexamethylol three are added into 40 parts of titanium dioxide
Poly cyanamid pregnancy ether, is first warming up to 120-125 DEG C of insulation mixing 30min with 5 DEG C/min programming rate, add 2 parts of the moon from
Sub- polyacrylamide and 0.2 part of epoxidized soybean oil, continue the insulation mixing 30min at 120-125 DEG C, gained mixture is with 10
DEG C/min cooling rate is cooled to 40-50 DEG C, and adds 40-50 DEG C of 150 parts of water, it is warming up to 10 DEG C/min programming rate
Reflux state insulation mixing 10min, 1h is stood after naturally cooling to room temperature, filter, gained solid at 75-80 DEG C dry,
It is ground to obtain nano titanium oxide finally in feeding nano-level grinder.
Embodiment 3
(1) preparation of macroporous absorbent resin：50 parts of styrene, 35 parts of hydrogenated rosins third are proportionally added into 350 parts of water
Olefin(e) acid glycerine ester, 15 parts of hydroxyethyl methacrylates, 40 parts of nanometer pore-foaming agents and 0.5 part of initiator, are sufficiently mixed after super
Ultrasonically treated 15min under acoustic frequency 40kHz, power output 200W, it is micro- under microwave frequency 2450MHz, power output 700W
Ripple handles 10min, and stands 30min in 0-5 DEG C of environment, continues microwave treatment 10min after being well mixed, then in -5-0 DEG C
15min is stood in environment, microwave treatment 10min again after being well mixed, gained mixed liquor is cooled with 5 DEG C/min cooling rate
To 0-5 DEG C of insulation mixing 1h, then by mixed liquor separation of solid and liquid, gained solid phase is washed three times with 35-40 DEG C of warm water and obtains Archon,
Archon is finally produced into macroporous absorbent resin in being dried in vacuo at 60-65 DEG C；
(4) pretreatment of macroporous absorbent resin：2 parts of poloxamers, 1 are added into above-mentioned made 65 parts of macroporous absorbent resins
Part N hydroxymethyl acrylamide and 0.5 part of HPMA, and 65-70 DEG C of guarantor is warming up to 5 DEG C/min programming rate
Temperature mixing 30min, then 30-35 DEG C of water of 3 times of weight is added into gained mixture, continue to heat up with 5 DEG C/min programming rate
To reflux state insulation mixing 15min, then naturally cool to room temperature, filter, gained resin spheroid wash three times, most after
It is dried in vacuo at 60-65 DEG C
(5) modification of macroporous absorbent resin：5 parts of nano titanium oxides are added into 10 parts of isocyanuric acid three-glycidyl esters
With 0.15 part of itaconic anhydride, 115-120 DEG C of insulation mixing 15min is warming up to 5 DEG C/min programming rate, added through pre- place
65 parts of macroporous absorbent resins after reason, continue in 115-120 DEG C of insulation mixing 30min, after naturally cool to washing three after room temperature
It is secondary, most afterwards through gained resin spheroid in vacuum drying at 60-65 DEG C.
The preparation of nanometer pore-foaming agent：10 parts of microcrystalline celluloses and 2 parts of rilanit specials are added into 50 parts of water, and are warming up to
Reflux state insulation mixing 15min, after naturally cool to 5 parts of polyglutamic acids of addition and 0.5 part of poly dimethyl two after 40-45 DEG C
Allyl ammonium chloride, stirring 30min formation emulsions, then adds 0.5 part of sodium gluconate and 0.05 part of ferrocene, is well mixed
Gained mixture is sent into spray dryer afterwards, particle is ground obtained by drying is made nanometer powder, finally by nanometer powder
Add water and solid content 30-35wt% emulsion is made, produce a nanometer pore-foaming agent.
Reference examples 1
(1) preparation of macroporous absorbent resin：50 parts of styrene, 35 parts of hydrogenated rosins third are proportionally added into 350 parts of water
Olefin(e) acid glycerine ester, 15 parts of hydroxyethyl methacrylates, 40 parts of isooctane and 0.5 part of initiator, are sufficiently mixed after supersonic frequency
Ultrasonically treated 15min under rate 40kHz, power output 200W, at microwave under microwave frequency 2450MHz, power output 700W
10min is managed, and 30min is stood in 0-5 DEG C of environment, continues microwave treatment 10min after being well mixed, then in -5-0 DEG C of environment
Middle standing 15min, microwave treatment 10min again after being well mixed, gained mixed liquor is cooled to 0- with 5 DEG C/min cooling rate
5 DEG C of insulation mixing 1h, then by mixed liquor separation of solid and liquid, gained solid phase is washed three times with 35-40 DEG C of warm water and obtains Archon, finally
By Archon in being dried in vacuo at 60-65 DEG C, macroporous absorbent resin is produced；
(2) pretreatment of macroporous absorbent resin：2 parts of poloxamers, 1 are added into above-mentioned made 65 parts of macroporous absorbent resins
Part N hydroxymethyl acrylamide and 0.5 part of HPMA, and 65-70 DEG C of guarantor is warming up to 5 DEG C/min programming rate
Temperature mixing 30min, then 30-35 DEG C of water of 3 times of weight is added into gained mixture, continue to heat up with 5 DEG C/min programming rate
To reflux state insulation mixing 15min, then naturally cool to room temperature, filter, gained resin spheroid wash three times, most after
It is dried in vacuo at 60-65 DEG C
(3) modification of macroporous absorbent resin：5 parts of nano titanium oxides are added into 10 parts of isocyanuric acid three-glycidyl esters
With 0.15 part of itaconic anhydride, 115-120 DEG C of insulation mixing 15min is warming up to 5 DEG C/min programming rate, added through pre- place
65 parts of macroporous absorbent resins after reason, continue in 115-120 DEG C of insulation mixing 30min, after naturally cool to washing three after room temperature
It is secondary, most afterwards through gained resin spheroid in vacuum drying at 60-65 DEG C.
The preparation of nano titanium oxide：5 parts of PVPPs and 0.5 part of hexamethylol three are added into 40 parts of titanium dioxide
Poly cyanamid pregnancy ether, is first warming up to 120-125 DEG C of insulation mixing 30min with 5 DEG C/min programming rate, add 2 parts of the moon from
Sub- polyacrylamide and 0.2 part of epoxidized soybean oil, continue the insulation mixing 30min at 120-125 DEG C, gained mixture is with 10
DEG C/min cooling rate is cooled to 40-50 DEG C, and adds 40-50 DEG C of 150 parts of water, it is warming up to 10 DEG C/min programming rate
Reflux state insulation mixing 10min, 1h is stood after naturally cooling to room temperature, filter, gained solid at 75-80 DEG C dry,
It is ground to obtain nano titanium oxide finally in feeding nano-level grinder.
Reference examples 2
(1) preparation of macroporous absorbent resin：50 parts of styrene, 35 parts of hydrogenated rosins third are proportionally added into 350 parts of water
Olefin(e) acid glycerine ester, 15 parts of hydroxyethyl methacrylates, 40 parts of isooctane and 0.5 part of initiator, are sufficiently mixed after supersonic frequency
Ultrasonically treated 15min under rate 40kHz, power output 200W, at microwave under microwave frequency 2450MHz, power output 700W
10min is managed, and 30min is stood in 0-5 DEG C of environment, continues microwave treatment 10min after being well mixed, then in -5-0 DEG C of environment
Middle standing 15min, microwave treatment 10min again after being well mixed, gained mixed liquor is cooled to 0- with 5 DEG C/min cooling rate
5 DEG C of insulation mixing 1h, then by mixed liquor separation of solid and liquid, gained solid phase is washed three times with 35-40 DEG C of warm water and obtains Archon, finally
By Archon in being dried in vacuo at 60-65 DEG C, macroporous absorbent resin is produced；
(2) pretreatment of macroporous absorbent resin：2 parts of poloxamers, 1 are added into above-mentioned made 65 parts of macroporous absorbent resins
Part N hydroxymethyl acrylamide and 0.5 part of HPMA, and 65-70 DEG C of guarantor is warming up to 5 DEG C/min programming rate
Temperature mixing 30min, then 30-35 DEG C of water of 3 times of weight is added into gained mixture, continue to heat up with 5 DEG C/min programming rate
To reflux state insulation mixing 15min, then naturally cool to room temperature, filter, gained resin spheroid wash three times, most after
It is dried in vacuo at 60-65 DEG C
(3) modification of macroporous absorbent resin：5 parts of nano titanium oxides are added into 10 parts of isocyanuric acid three-glycidyl esters
With 0.15 part of itaconic anhydride, 115-120 DEG C of insulation mixing 15min is warming up to 5 DEG C/min programming rate, added through pre- place
65 parts of macroporous absorbent resins after reason, continue in 115-120 DEG C of insulation mixing 30min, after naturally cool to washing three after room temperature
It is secondary, most afterwards through gained resin spheroid in vacuum drying at 60-65 DEG C.
Embodiment 4
Equivalent embodiment 1, embodiment 2, embodiment 3, reference examples 1 and the made macroporous absorbent resin of reference examples 2 are used for etc.
Amount and isolating and purifying with batch isoflavones extract solution, and the commercially available macroporous absorbent resin HP-20 of equivalent is set as reference examples
3。
The preparation of refined solution to be separated：Isoflavones ethanol extract is refrigerated and centrifuged after 48h, and takes supernatant, on
Clear liquid is concentrated, then the degreasing after refrigerating 24h, is then adjusted pH value to neutrality with 5mol/L hydrochloric acid solutions, is produced purifying to be separated
Liquid；
Isoflavones is isolated and purified：Load glass adsorption column after macroporous absorbent resin plus equivalent water are fully soaked
In, macropore is then rinsed using 60% methanol solution after the completion of absorption by adsorption column by equivalent and with batch refined solution to be separated
Polymeric adsorbent, until the mass percent of isoflavones is less than 0.5% in outflow solution, and by gained eluent after drying
The powder rich in isoflavones is made, macroporous absorbent resin is determined in the adsorbance of isoflavones, desorption efficiency and powder
The purity of isoflavones, measurement result is as shown in table 1.
The treatment effect of the made macroporous absorbent resin of table 1
The general principle and principal character and advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the simply explanation described in above-described embodiment and specification is originally
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (7)
1. a kind of isoflavones isolates and purifies the preparation method with macroporous absorbent resin, it is characterised in that：Its preparation method bag
Include following steps：
(1) preparation of macroporous absorbent resin：Xiang Shuizhong is proportionally added into styrene, hydrogenated rosin acrylic acid glycerine ester, methyl
Hydroxy-ethyl acrylate, nanometer pore-foaming agent and initiator, are sufficiently mixed after ultrasonic under supersonic frequency 40kHz, power output 200W
15min, the microwave treatment 10min under microwave frequency 2450MHz, power output 700W are handled, and is stood in 0-5 DEG C of environment
30min, continues microwave treatment 10min after being well mixed, 15min is then stood in -5-0 DEG C of environment, after being well mixed again
Microwave treatment 10min, gained mixed liquor is cooled to 0-5 DEG C of insulation mixing 1h with 5 DEG C/min cooling rate, then by mixed liquor
Separation of solid and liquid, gained solid phase is washed three times with 35-40 DEG C of warm water and obtains Archon, finally by Archon in vacuum drying at 60-65 DEG C,
Produce macroporous absorbent resin；
(2) pretreatment of macroporous absorbent resin：Poloxamer, N- methylol propylene are added into above-mentioned made macroporous absorbent resin
Acid amides and HPMA, and 65-70 DEG C of insulation mixing 30min is warming up to 5 DEG C/min programming rate, then to gained
30-35 DEG C of water of 3 times of weight is added in mixture, continues to be warming up to reflux state insulation mixing with 5 DEG C/min programming rate
15min, then naturally cools to room temperature, filtering, and gained resin spheroid is washed three times, most after vacuum drying at 60-65 DEG C；
(3) modification of macroporous absorbent resin：Nano titanium oxide and itaconic anhydride are added into isocyanuric acid three-glycidyl ester,
115-120 DEG C of insulation mixing 15min is warming up to 5 DEG C/min programming rate, macroporous absorption tree after pretreatment is added
Fat, continues, in 115-120 DEG C of insulation mixing 30min, to wash three times after naturally cool to after room temperature, most afterwards through gained resin spheroid
In vacuum drying at 60-65 DEG C.
2. isoflavones according to claim 1 isolates and purifies the preparation method with macroporous absorbent resin, its feature exists
In：Step (1) reclaimed water, styrene, hydrogenated rosin acrylic acid glycerine ester, hydroxyethyl methacrylate, nanometer pore-foaming agent
Mass ratio with initiator is 300-400:45-50:30-35:15-20:40-45:0.5-1.
3. isoflavones according to claim 1 isolates and purifies the preparation method with macroporous absorbent resin, its feature exists
In：Macroporous absorbent resin in the step (2), poloxamer, the quality of N hydroxymethyl acrylamide and HPMA
Than for 60-65:1-2:0.5-1:0.5-1.
4. isoflavones according to claim 1 isolates and purifies the preparation method with macroporous absorbent resin, its feature exists
In：Macroporous absorbent resin in the step (3), isocyanuric acid three-glycidyl ester, the matter of nano titanium oxide and itaconic anhydride
Amount is than being 60-65:5-10:3-5:0.1-0.2.
5. isoflavones according to claim 1 isolates and purifies the preparation method with macroporous absorbent resin, its feature exists
In：The nanometer pore-foaming agent is made up of the raw material of following parts by weight：5-10 parts of microcrystalline cellulose, 3-5 parts of polyglutamic acid, hydrogen
Change 1-2 parts of castor oil, 0.5-1 parts of PDDA, 0.5-1 parts of sodium gluconate, ferrocene 0.05-0.1
Part, 30-50 parts of water, its preparation method is：Xiang Shuizhong adds microcrystalline cellulose and rilanit special, and is warming up to reflux state guarantor
Temperature mixing 15min, after naturally cool to polyglutamic acid and PDDA is added after 40-45 DEG C, is stirred
30min formation emulsions, then add sodium gluconate and ferrocene, gained mixture are sent into spray dryer after being well mixed
In, particle is ground obtained by drying is made nanometer powder, and finally nanometer powder, which adds water, is made solid content 30-35wt% breast
Liquid, produces a nanometer pore-foaming agent.
6. isoflavones according to claim 1 isolates and purifies the preparation method with macroporous absorbent resin, its feature exists
In：The nano titanium oxide is the nano-powder being made after the modified processing of titanium dioxide, and its preparation method is：To dioxy
Change and PVPP and hexamethylolmelamine pregnancy ether are added in titanium, 120- is first warming up to 5 DEG C/min programming rate
125 DEG C of insulation mixing 30min, add PAMA and epoxidized soybean oil, continue to be incubated at 120-125 DEG C and mix
Close 30min, gained mixture is cooled to 40-50 DEG C with 10 DEG C/min cooling rate, and add 40-50 DEG C of water, with 10 DEG C/
Min programming rate is warming up to reflux state insulation mixing 10min, and 1h is stood after naturally cooling to room temperature, is filtered, gained is solid
Body is finally sent into nano-level grinder in being dried at 75-80 DEG C, ground to obtain nano titanium oxide.
7. isoflavones according to claim 6 isolates and purifies the preparation method with macroporous absorbent resin, its feature exists
In：The titanium dioxide, PVPP, hexamethylolmelamine pregnancy ether, PAMA, epoxidized soybean oil
Mass ratio with water is 30-40:3-5:0.5-1:2-3:0.1-0.3:100-150.
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| CN108808012A (en) * | 2018-06-11 | 2018-11-13 | 四会市恒星智能科技有限公司 | A method of prevent lead-acid battery electrode plate active material from falling off |
| CN108847487A (en) * | 2018-06-11 | 2018-11-20 | 四会市恒星智能科技有限公司 | A kind of micropore anticreep agent for preventing chloride plate active material from falling off |
| CN113145088A (en) * | 2020-01-22 | 2021-07-23 | 中国科学院大连化学物理研究所 | Hydrophilic integral material and preparation and application thereof |
| CN113244899A (en) * | 2021-05-28 | 2021-08-13 | 重庆智伦电镀有限公司 | Adsorption resin recycling process for industrial wastewater treatment |
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| CN108808012A (en) * | 2018-06-11 | 2018-11-13 | 四会市恒星智能科技有限公司 | A method of prevent lead-acid battery electrode plate active material from falling off |
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| CN113145088A (en) * | 2020-01-22 | 2021-07-23 | 中国科学院大连化学物理研究所 | Hydrophilic integral material and preparation and application thereof |
| CN113244899A (en) * | 2021-05-28 | 2021-08-13 | 重庆智伦电镀有限公司 | Adsorption resin recycling process for industrial wastewater treatment |
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