CN106964324B - 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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- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- 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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- C07D311/26—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
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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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
- C08J2201/042—Elimination of an organic solid phase
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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 invention discloses a kind of isoflavones to isolate and purify the preparation method with macroporous absorbent resin, it is related to biological medicine technical field of purification, preparation method includes the following steps: the preparation of (1) macroporous absorbent resin, (2) pretreatment of macroporous absorbent resin, the modification of (3) macroporous absorbent resin.The made macroporous absorbent resin of the present invention reaches 17mg/g or more to the adsorbance of isoflavones, the efficient desorption of isoflavones is able to achieve after the flushing of 60% methanol solution, desorption efficiency reaches 98.5% or more, the purity of made isoflavones reaches 60% or more, therefore the macroporous absorbent resin is suitable for 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 technique:
Naturally occurring isoflavones shares 12 kinds, is divided into 3 major class of daidzin, genistin and C22H22O10.Greatly
Beans isoflavones has the function of anti-oxidant, pre- anti-cancer, strengthen immunity and improvement breeding performonce fo animals etc., has been widely used in
In the fields such as biology, feed, medicine and health care of food.The study found that the aglycon of only sequestered just has biological activity, need
The aglycon for being converted to sequestered through enzymatic hydrolysis or sour water solution glucosides could be absorbed by animal or human body.Currently, improving the different Huang of soybean
The method of Aglycones content mainly has extraction, physics auxiliary law, High Pressure Wet and ultrafiltration etc. in ketone, but there are works for these methods
The disadvantages of skill is more complex, higher cost and Determination of Residual Organic Solvents are high is unsuitable for mass preparation.
Flavonoids by Macroporous Adsorption Resin is in recent years using a kind of extensive purification process, other opposite purification process have selection
Property it is good, nontoxic and pollution-free the advantages that, but the adsorbance of macroporous absorbent resin used at present is lower, and while desorbing need it is a large amount of
Organic solvent rinses, even if these organic solvents can be recycled, it is also desirable to consume big energy to realize.
Summary of the invention:
Technical problem to be solved by the present invention lies in provide that a kind of adsorbance is high, desorption is easy and that Aglycones content is high is big
Beans isoflavones isolates and purifies the preparation method with macroporous absorbent resin.
The following technical solution is employed for the technical problems to be solved by the invention to realize:
A kind of isoflavones isolates and purifies the preparation method with macroporous absorbent resin, and preparation method includes following step
It is rapid:
(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, after being sufficiently mixed under supersonic frequency 40kHz, output power 200W
It is ultrasonically treated 15min, the microwave treatment 10min under microwave frequency 2450MHz, output power 700W, and in 0-5 DEG C of environment
30min is stood, continues microwave treatment 10min after mixing, 15min is then stood in -5-0 DEG C of environment, after mixing
Microwave treatment 10min again, gained mixed liquor are cooled to 0-5 DEG C of heat preservation mixing 1h with the cooling rate of 5 DEG C/min, will then mix
Liquid is closed to be separated by solid-liquid separation, gained solid phase obtains Archon with the washing of 35-40 DEG C of warm water three times, finally by Archon at 60-65 DEG C vacuum
Drying is to get macroporous absorbent resin；
(2) poloxamer, N- methylol the pretreatment of macroporous absorbent resin: are added into above-mentioned made macroporous absorbent resin
Acrylamide and hydrolysis of polymaleic anhydride, and 65-70 DEG C of heat preservation mixing 30min is warming up to the heating rate of 5 DEG C/min, then to
30-35 DEG C of water of 3 times of weight is added in gained mixture, continuation is warming up to reflux state heat preservation with the heating rate of 5 DEG C/min and mixes
15min is closed, then cooled to room temperature, filtering, gained resin sphere is washed three times, is finally dried in vacuo at 60-65 DEG C；
(3) nano-titanium dioxide and clothing health the modification of macroporous absorbent resin: are added into isocyanuric acid three-glycidyl ester
Acid anhydrides is warming up to 115-120 DEG C of heat preservation mixing 15min with the heating rate of 5 DEG C/min, adds macropore after pretreatment and inhale
Attached resin continues to mix 30min in 115-120 DEG C of heat preservation, after naturally cool to washing after room temperature three times, most afterwards through gained resin
Sphere is dried in vacuo at 60-65 DEG C.
Water, styrene, hydrogenated rosin acrylic acid glycerine ester, hydroxyethyl methacrylate, nanometer cause in the step (1)
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 hydrolysis of polymaleic anhydride
Mass ratio is 60-65:1-2:0.5-1:0.5-1.
Macroporous absorbent resin, isocyanuric acid three-glycidyl ester, nano-titanium dioxide 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 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 polydimethyl diallyl ammonium chloride, 0.5-1 parts of sodium gluconate, ferrocene
0.05-0.1 parts, 30-50 parts of water, preparation method are as follows: microcrystalline cellulose and rilanit special are added into water, and is warming up to back
Stream mode heat preservation mixing 15min, after naturally cool to addition polyglutamic acid and poly dimethyl allyl chlorination after 40-45 DEG C
Ammonium, stirring 30min form lotion, sodium gluconate and ferrocene are then added, be sent into gained mixture spray after mixing
In mist drying machine, particle is ground obtained by drying is made nanometer powder, finally adds water that solid content 30- is made nanometer powder
The lotion of 35wt% is to get nanometer pore-foaming agent.
The nano-titanium dioxide is the nano-powder made of after the modified processing of titanium dioxide, preparation method are as follows:
Crospovidone and hexamethylolmelamine pregnancy ether are added into titanium dioxide, is first heated up with the heating rate of 5 DEG C/min
30min is mixed to 120-125 DEG C of heat preservation, anionic polyacrylamide and epoxidized soybean oil is added, continues at 120-125 DEG C
Heat preservation mixing 30min, gained mixture is cooled to 40-50 DEG C with the cooling rate of 10 DEG C/min, and 40-50 DEG C of water is added, with
The heating rate of 10 DEG C/min is warming up to reflux state heat preservation mixing 10min, and 1h is stood after cooled to room temperature, is filtered,
Obtained solid is dried at 75-80 DEG C, is finally sent into nano-level grinder, ground to obtain nano-titanium dioxide.
The titanium dioxide, crospovidone, hexamethylolmelamine pregnancy ether, anionic polyacrylamide, 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 present invention are:
(1) it uses three step microwave treatment methods association with the operation that cools down in the preparatory phase of macroporous absorbent resin, is prepared shortening
The resistant of high or low temperature of macroporous absorbent resin is improved while time；
(2) it by the pretreatment of water-soluble poloxamer, N hydroxymethyl acrylamide and hydrolysis of polymaleic anhydride, reduces
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 dioxide and itaconic anhydride
Modification increases its specific surface area, enhances its adsorption activity；
(4) made macroporous absorbent resin reaches 17mg/g or more to the adsorbance of isoflavones, through 60% methanol solution
The efficient desorption of isoflavones is able to achieve after flushing, desorption efficiency reaches 98.5% or more, and the purity of made isoflavones reaches
To 60% or more, therefore the macroporous absorbent resin is suitable for efficiently separating for isoflavones.
Specific embodiment:
In order to be easy to understand the technical means, the creative features, the aims and the efficiencies achieved by the present invention, tie below
Specific embodiment is closed, the present invention is further explained.
Embodiment 1
(1) 45 parts of styrene, 30 parts of hydrogenated rosins third preparation of macroporous absorbent resin: 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 rear Yu Chao
It is ultrasonically treated 15min under acoustic frequency 40kHz, output power 200W, it is micro- under microwave frequency 2450MHz, output power 700W
Wave handles 10min, and 30min is stood in 0-5 DEG C of environment, continues microwave treatment 10min after mixing, then in -5-0 DEG C
15min is stood in environment, microwave treatment 10min, gained mixed liquor are cooled down again with the cooling rate of 5 DEG C/min after mixing
1h is mixed to 0-5 DEG C of heat preservation, is then separated by solid-liquid separation mixed liquor, gained solid phase obtains Archon with 35-40 DEG C of warm water washing three times,
Finally Archon is dried in vacuo at 60-65 DEG C to get macroporous absorbent resin；
(2) pretreatment of macroporous absorbent resin: into above-mentioned made 60 parts of macroporous absorbent resins be added 2 parts of poloxamers,
0.5 part of N hydroxymethyl acrylamide and 1 part of hydrolysis of polymaleic anhydride, and 65-70 DEG C of guarantor is warming up to the heating rate of 5 DEG C/min
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 the heating rate of 5 DEG C/min
Keep the temperature mixing 15min to reflux state, then cooled to room temperature, filtering, gained resin sphere washes three times, finally in
It is dried in vacuo at 60-65 DEG C；
(3) 3 parts of nano-titanium dioxides the modification of macroporous absorbent resin: are added into 10 parts of isocyanuric acid three-glycidyl esters
With 0.15 part of itaconic anhydride, 115-120 DEG C of heat preservation mixing 15min is warming up to the heating rate of 5 DEG C/min, adds and is located in advance
60 parts of macroporous absorbent resins after reason, continue in 115-120 DEG C of heat preservation mixing 30min, after naturally cool to washing three after room temperature
It is secondary, most it is dried in vacuo at 60-65 DEG C through gained resin sphere afterwards.
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 heat preservation 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 form lotion, 0.5 part of sodium gluconate and 0.05 part of ferrocene are then added, be uniformly 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 that the lotion of solid content 30-35wt% is made to get nanometer pore-foaming agent.
The preparation of nano-titanium dioxide: 3 parts of crospovidone 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 heat preservation with the heating rate of 5 DEG C/min and mixes 30min, add 3 parts of yin from
Sub- polyacrylamide and 0.2 part of epoxidized soybean oil continue the heat preservation mixing 30min at 120-125 DEG C, and gained mixture is with 10
DEG C/cooling rate of min is cooled to 40-50 DEG C, and 40-50 DEG C of 150 parts of water is added, it is warming up to the heating rate of 10 DEG C/min
Reflux state heat preservation mixing 10min, 1h is stood after cooled to room temperature, is filtered, and obtained solid is dried at 75-80 DEG C,
Finally it is sent into nano-level grinder, it is ground to obtain nano-titanium dioxide.
Embodiment 2
(1) 50 parts of styrene, 35 parts of hydrogenated rosins third preparation of macroporous absorbent resin: 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 rear Yu Chao
It is ultrasonically treated 15min under acoustic frequency 40kHz, output power 200W, it is micro- under microwave frequency 2450MHz, output power 700W
Wave handles 10min, and 30min is stood in 0-5 DEG C of environment, continues microwave treatment 10min after mixing, then in -5-0 DEG C
15min is stood in environment, microwave treatment 10min, gained mixed liquor are cooled down again with the cooling rate of 5 DEG C/min after mixing
1h is mixed to 0-5 DEG C of heat preservation, is then separated by solid-liquid separation mixed liquor, gained solid phase obtains Archon with 35-40 DEG C of warm water washing three times,
Finally Archon is dried in vacuo at 60-65 DEG C to get macroporous absorbent resin；
(2) 2 parts of poloxamers, 1 pretreatment of macroporous absorbent resin: are added into above-mentioned made 65 parts of macroporous absorbent resins
Part N hydroxymethyl acrylamide and 0.5 part of hydrolysis of polymaleic anhydride, and 65-70 DEG C of guarantor is warming up to the heating rate of 5 DEG C/min
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 the heating rate of 5 DEG C/min
Keep the temperature mixing 15min to reflux state, then cooled to room temperature, filtering, gained resin sphere washes three times, finally in
It is dried in vacuo at 60-65 DEG C
(3) 5 parts of nano-titanium dioxides the modification of macroporous absorbent resin: are added into 10 parts of isocyanuric acid three-glycidyl esters
With 0.15 part of itaconic anhydride, 115-120 DEG C of heat preservation mixing 15min is warming up to the heating rate of 5 DEG C/min, adds and is located in advance
65 parts of macroporous absorbent resins after reason, continue in 115-120 DEG C of heat preservation mixing 30min, after naturally cool to washing three after room temperature
It is secondary, most it is dried in vacuo at 60-65 DEG C through gained resin sphere afterwards.
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 heat preservation 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 form lotion, 0.5 part of sodium gluconate and 0.05 part of ferrocene are then added, be uniformly 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 that the lotion of solid content 30-35wt% is made to get nanometer pore-foaming agent.
The preparation of nano-titanium dioxide: 5 parts of crospovidone 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 heat preservation with the heating rate of 5 DEG C/min and mixes 30min, add 2 parts of yin from
Sub- polyacrylamide and 0.2 part of epoxidized soybean oil continue the heat preservation mixing 30min at 120-125 DEG C, and gained mixture is with 10
DEG C/cooling rate of min is cooled to 40-50 DEG C, and 40-50 DEG C of 150 parts of water is added, it is warming up to the heating rate of 10 DEG C/min
Reflux state heat preservation mixing 10min, 1h is stood after cooled to room temperature, is filtered, and obtained solid is dried at 75-80 DEG C,
Finally it is sent into nano-level grinder, it is ground to obtain nano-titanium dioxide.
Embodiment 3
(1) 50 parts of styrene, 35 parts of hydrogenated rosins third preparation of macroporous absorbent resin: 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 rear Yu Chao
It is ultrasonically treated 15min under acoustic frequency 40kHz, output power 200W, it is micro- under microwave frequency 2450MHz, output power 700W
Wave handles 10min, and 30min is stood in 0-5 DEG C of environment, continues microwave treatment 10min after mixing, then in -5-0 DEG C
15min is stood in environment, microwave treatment 10min, gained mixed liquor are cooled down again with the cooling rate of 5 DEG C/min after mixing
1h is mixed to 0-5 DEG C of heat preservation, is then separated by solid-liquid separation mixed liquor, gained solid phase obtains Archon with 35-40 DEG C of warm water washing three times,
Finally Archon is dried in vacuo at 60-65 DEG C to get macroporous absorbent resin；
(4) 2 parts of poloxamers, 1 pretreatment of macroporous absorbent resin: are added into above-mentioned made 65 parts of macroporous absorbent resins
Part N hydroxymethyl acrylamide and 0.5 part of hydrolysis of polymaleic anhydride, and 65-70 DEG C of guarantor is warming up to the heating rate of 5 DEG C/min
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 the heating rate of 5 DEG C/min
Keep the temperature mixing 15min to reflux state, then cooled to room temperature, filtering, gained resin sphere washes three times, finally in
It is dried in vacuo at 60-65 DEG C
(5) 5 parts of nano-titanium dioxides the modification of macroporous absorbent resin: are added into 10 parts of isocyanuric acid three-glycidyl esters
With 0.15 part of itaconic anhydride, 115-120 DEG C of heat preservation mixing 15min is warming up to the heating rate of 5 DEG C/min, adds and is located in advance
65 parts of macroporous absorbent resins after reason, continue in 115-120 DEG C of heat preservation mixing 30min, after naturally cool to washing three after room temperature
It is secondary, most it is dried in vacuo at 60-65 DEG C through gained resin sphere afterwards.
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 heat preservation 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 form lotion, 0.5 part of sodium gluconate and 0.05 part of ferrocene are then added, be uniformly 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 that the lotion of solid content 30-35wt% is made to get nanometer pore-foaming agent.
Reference examples 1
(1) 50 parts of styrene, 35 parts of hydrogenated rosins third preparation of macroporous absorbent resin: 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, in supersonic frequency after being sufficiently mixed
It is ultrasonically treated 15min under rate 40kHz, output power 200W, at microwave under microwave frequency 2450MHz, output power 700W
10min is managed, and stands 30min in 0-5 DEG C of environment, continues microwave treatment 10min after mixing, then in -5-0 DEG C of environment
Middle standing 15min, microwave treatment 10min, gained mixed liquor are cooled to 0- with the cooling rate of 5 DEG C/min again after mixing
5 DEG C of heat preservations mix 1h, are then separated by solid-liquid separation mixed liquor, and gained solid phase obtains Archon with 35-40 DEG C of warm water washing three times, finally
Archon is dried in vacuo at 60-65 DEG C to get macroporous absorbent resin；
(2) 2 parts of poloxamers, 1 pretreatment of macroporous absorbent resin: are added into above-mentioned made 65 parts of macroporous absorbent resins
Part N hydroxymethyl acrylamide and 0.5 part of hydrolysis of polymaleic anhydride, and 65-70 DEG C of guarantor is warming up to the heating rate of 5 DEG C/min
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 the heating rate of 5 DEG C/min
Keep the temperature mixing 15min to reflux state, then cooled to room temperature, filtering, gained resin sphere washes three times, finally in
It is dried in vacuo at 60-65 DEG C
(3) 5 parts of nano-titanium dioxides the modification of macroporous absorbent resin: are added into 10 parts of isocyanuric acid three-glycidyl esters
With 0.15 part of itaconic anhydride, 115-120 DEG C of heat preservation mixing 15min is warming up to the heating rate of 5 DEG C/min, adds and is located in advance
65 parts of macroporous absorbent resins after reason, continue in 115-120 DEG C of heat preservation mixing 30min, after naturally cool to washing three after room temperature
It is secondary, most it is dried in vacuo at 60-65 DEG C through gained resin sphere afterwards.
The preparation of nano-titanium dioxide: 5 parts of crospovidone 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 heat preservation with the heating rate of 5 DEG C/min and mixes 30min, add 2 parts of yin from
Sub- polyacrylamide and 0.2 part of epoxidized soybean oil continue the heat preservation mixing 30min at 120-125 DEG C, and gained mixture is with 10
DEG C/cooling rate of min is cooled to 40-50 DEG C, and 40-50 DEG C of 150 parts of water is added, it is warming up to the heating rate of 10 DEG C/min
Reflux state heat preservation mixing 10min, 1h is stood after cooled to room temperature, is filtered, and obtained solid is dried at 75-80 DEG C,
Finally it is sent into nano-level grinder, it is ground to obtain nano-titanium dioxide.
Reference examples 2
(1) 50 parts of styrene, 35 parts of hydrogenated rosins third preparation of macroporous absorbent resin: 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, in supersonic frequency after being sufficiently mixed
It is ultrasonically treated 15min under rate 40kHz, output power 200W, at microwave under microwave frequency 2450MHz, output power 700W
10min is managed, and stands 30min in 0-5 DEG C of environment, continues microwave treatment 10min after mixing, then in -5-0 DEG C of environment
Middle standing 15min, microwave treatment 10min, gained mixed liquor are cooled to 0- with the cooling rate of 5 DEG C/min again after mixing
5 DEG C of heat preservations mix 1h, are then separated by solid-liquid separation mixed liquor, and gained solid phase obtains Archon with 35-40 DEG C of warm water washing three times, finally
Archon is dried in vacuo at 60-65 DEG C to get macroporous absorbent resin；
(2) 2 parts of poloxamers, 1 pretreatment of macroporous absorbent resin: are added into above-mentioned made 65 parts of macroporous absorbent resins
Part N hydroxymethyl acrylamide and 0.5 part of hydrolysis of polymaleic anhydride, and 65-70 DEG C of guarantor is warming up to the heating rate of 5 DEG C/min
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 the heating rate of 5 DEG C/min
Keep the temperature mixing 15min to reflux state, then cooled to room temperature, filtering, gained resin sphere washes three times, finally in
It is dried in vacuo at 60-65 DEG C
(3) 5 parts of nano-titanium dioxides the modification of macroporous absorbent resin: are added into 10 parts of isocyanuric acid three-glycidyl esters
With 0.15 part of itaconic anhydride, 115-120 DEG C of heat preservation mixing 15min is warming up to the heating rate of 5 DEG C/min, adds and is located in advance
65 parts of macroporous absorbent resins after reason, continue in 115-120 DEG C of heat preservation mixing 30min, after naturally cool to washing three after room temperature
It is secondary, most it is dried in vacuo at 60-65 DEG C through gained resin sphere afterwards.
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
Amount and isolating and purifying with batch isoflavones extracting 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: being centrifuged after isoflavones ethanol extract is refrigerated 48h, and take supernatant, on
Then clear liquid concentration, then the degreasing after refrigerating for 24 hours adjust pH value to neutrality to get purifying to be separated with 5mol/L hydrochloric acid solution
Liquid；
Isoflavones isolates and purifies: glass adsorption column is packed into after macroporous absorbent resin plus equivalent amount of water are sufficiently soaked
In, then pass through adsorption column by equivalent and with batch refined solution to be separated, rinses macropore using 60% methanol solution after the completion of absorption
Resin is adsorbed, until the mass percent of isoflavones is lower than 0.5% in outflow solution, and after drying by gained eluent
The powder rich in isoflavones is made, measures macroporous absorbent resin in the adsorbance of isoflavones, desorption efficiency and powder
The purity of isoflavones, measurement result are as shown in table 1.
The treatment effect of the made macroporous absorbent resin of table 1
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, 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 (5)
1. a kind of isoflavones isolates and purifies the preparation method with macroporous absorbent resin, it is characterised in that: preparation method packet
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, it is ultrasonic under supersonic frequency 40kHz, output power 200W after being sufficiently mixed
15min, the microwave treatment 10min under microwave frequency 2450MHz, output power 700W are handled, and is stood in 0-5 DEG C of environment
30min continues microwave treatment 10min after mixing, 15min is then stood in -5-0 DEG C of environment, after mixing again
Microwave treatment 10min, gained mixed liquor is cooled to 0-5 DEG C of heat preservation mixing 1h with the cooling rate of 5 DEG C/min, then by mixed liquor
It being separated by solid-liquid separation, gained solid phase obtains Archon with 35-40 DEG C of warm water washing three times, finally Archon is dried in vacuo at 60-65 DEG C,
Up to macroporous absorbent resin；
(2) poloxamer, N- methylol propylene the pretreatment of macroporous absorbent resin: are added into above-mentioned made macroporous absorbent resin
Amide and hydrolysis of polymaleic anhydride, and 65-70 DEG C of heat preservation mixing 30min is warming up to the heating rate of 5 DEG C/min, 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 heat preservation mixing with the heating rate of 5 DEG C/min
15min, then cooled to room temperature, filtering, gained resin sphere are washed three times, are finally dried in vacuo at 60-65 DEG C；
(3) modification of macroporous absorbent resin: nano-titanium dioxide and itaconic anhydride being added into isocyanuric acid three-glycidyl ester,
It is warming up to 115-120 DEG C of heat preservation mixing 15min with the heating rate of 5 DEG C/min, adds macroporous absorption tree after pretreatment
Rouge continues to mix 30min in 115-120 DEG C of heat preservation, after naturally cool to washing after room temperature three times, most afterwards through gained resin sphere
It is dried in vacuo at 60-65 DEG C；
The nanometer pore-foaming agent is made of the raw material of following parts by weight: 5-10 parts of microcrystalline cellulose, 3-5 parts of polyglutamic acid,
1-2 parts of rilanit special, 0.5-1 parts of polydimethyl diallyl ammonium chloride, 0.5-1 parts of sodium gluconate, ferrocene 0.05-
0.1 part, 30-50 parts of water, preparation method are as follows: microcrystalline cellulose and rilanit special are added into water, and is warming up to reflux shape
State heat preservation mixing 15min, after naturally cool to polyglutamic acid and polydimethyl diallyl ammonium chloride are added after 40-45 DEG C,
It stirs 30min and forms lotion, sodium gluconate and ferrocene is then added, be after mixing sent into gained mixture spraying dry
In dry machine, particle is ground obtained by drying is made nanometer powder, finally adds water to be made solid content 30-35wt%'s nanometer powder
Lotion is to get nanometer pore-foaming agent；
The nano-titanium dioxide is the nano-powder made of after the modified processing of titanium dioxide, preparation method are as follows: to two
Crospovidone and hexamethylolmelamine pregnancy ether are added in titanium oxide, is first warming up to the heating rate of 5 DEG C/min
120-125 DEG C of heat preservation mixes 30min, adds anionic polyacrylamide and epoxidized soybean oil, and continuation is protected at 120-125 DEG C
Temperature mixing 30min, gained mixture is cooled to 40-50 DEG C with the cooling rate of 10 DEG C/min, and 40-50 DEG C of water is added, with 10
DEG C/heating rate of min is warming up to reflux state heat preservation mixing 10min, 1h is stood after cooled to room temperature, is filtered, institute
It obtains solid to dry at 75-80 DEG C, finally be sent into nano-level grinder, it is ground to obtain nano-titanium dioxide.
2. isoflavones according to claim 1 isolates and purifies the preparation method with macroporous absorbent resin, feature exists
In: water, styrene, hydrogenated rosin acrylic acid glycerine ester, hydroxyethyl methacrylate, nanometer pore-foaming agent in the step (1)
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, feature exists
In: the quality of macroporous absorbent resin, poloxamer, N hydroxymethyl acrylamide and hydrolysis of polymaleic anhydride in the step (2)
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, feature exists
In: the matter of macroporous absorbent resin, isocyanuric acid three-glycidyl ester, nano-titanium dioxide and itaconic anhydride in the step (3)
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, feature exists
In: the titanium dioxide, crospovidone, hexamethylolmelamine pregnancy ether, anionic polyacrylamide, 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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| CN1349987A (en) * | 2000-10-20 | 2002-05-22 | 中国食品发酵工业研究所 | Soybean isoflavone and its prepn process with macroporous adsorption resin |
| CN101525324A (en) * | 2009-04-03 | 2009-09-09 | 上海师范大学 | Method for separating genistein monomer from daidzein monomer |
| CN103585254A (en) * | 2013-11-22 | 2014-02-19 | 东北农业大学 | Method for synchronously extracting soy isoflavone and soy saponine from hydrolysate of aqueous enzymatic method |
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| CN1349987A (en) * | 2000-10-20 | 2002-05-22 | 中国食品发酵工业研究所 | Soybean isoflavone and its prepn process with macroporous adsorption resin |
| CN101525324A (en) * | 2009-04-03 | 2009-09-09 | 上海师范大学 | Method for separating genistein monomer from daidzein monomer |
| CN103585254A (en) * | 2013-11-22 | 2014-02-19 | 东北农业大学 | Method for synchronously extracting soy isoflavone and soy saponine from hydrolysate of aqueous enzymatic method |
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