CN109999765A - The preparation method of beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material - Google Patents
The preparation method of beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material Download PDFInfo
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Abstract
The invention discloses the preparation methods of beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material, reaction is rocked the following steps are included: polyvinylidene fluoride material is placed in mixture A, it obtains Kynoar defluorinate material and immerses in mixture B, it obtains Kynoar hydroxylcontaining materials and immerses in mixture C to react, obtain acrylic acid-grafted Kynoar acryhic material, beta cyclo dextrin polymer is taken to be dissolved in anhydrous dimethyl formamide, catalyst is added, obtain mixture D, remove residual catalyst, glycidyl acrylate stirring is added, obtain GMA- beta cyclo dextrin polymer, Kynoar acryhic material is immersed in distilled water, GMA- beta cyclo dextrin polymer and initiator is added, obtain beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material.The material can directly apply in edible liquid, such as applied on the containers such as cup, pot, can effectively adsorb the heavy metal in edible liquid, guarantee the healthy diet of people.
Description
Technical field
The present invention relates to the preparation methods of adsorbent material more particularly to beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride to adsorb
The preparation method of material.
Background technique
It is heavy metal-polluted to have a finger in every pie the environmental pollution as caused by heavy metal or its compound, mainly by mining, exhaust gas discharge, dirt
Caused by water irrigates and uses the human factors such as heavy metals exceeding standard product, because mankind's activity causes the content of beary metal in environment to increase
Add, exceeds normal range (NR).These heavy metal pollutions are directly detrimental to health by water resource and food chain, and lead to environment
Deterioration, especially some direct edible liquids such as drinking water, tea, fruit drink, heavy metal in Chinese medicine soup liquid
Pollution be even more it is closely bound up with the edible safety and health of the majority of consumers.Before people drink these liquid, energy
It is very important for the heavy-metal residual for efficiently and rapidly removing in these liquid.
It is compared by a series of scientific and technical literatures as it can be seen that the beta cyclo dextrin polymer prepared by He Junyong et al.
(Rapid adsorption of Pb, Cu and Cd from aqueous solutions by β-cyclodextrin
Polymers, Applied Surface Science, 426:29-39,2017) it shows than other heavy-metal adsorption materials
More excellent performance.
And learned from nearest Chinese patent, such as Publication No. " CN106076286A ", a kind of entitled " complexing agent grafting
In the preparation method of Kynoar adsorbed film " patent application publication, Cui XueJun et al. application has sufficient mechanical strength
It is used as carrier with high temperature-resistant polymer film-Kynoar (PVDF), small molecule complexing agent is grafted on pvdf membrane, is made
Standby heavy metal ion adsorbed film out.
Such as Publication No. " CN106621842A ", entitled " a kind of to chelate the preparation methods of microfiltration membranes, regeneration method and answer
With " in patent application publication, small molecule chelators melamine is grafted on pvdf membrane by Liu Fuqiang et al., prepares energy
The chelating microfiltration membranes of enriching heavy metal.
Although the successful preparation of these Kynoar adsorbed films and chelating microfiltration membranes greatly enhances heavy metal
The practical application of absorption and enrichment, but for the application in directly edible liquid, there is small point of complexing or chelating ability
Sub- chemical reagent is clearly inappropriate.And optimal method is to use standard using some national food additives that meet,
And have been widely used for the natural polymer such as chitosan or natural cyclic oligosaccharides-β-of medical auxiliary materials and food additives
Cyclodextrin etc. is used as food-grade polymer adsorbing material.
Summary of the invention
The present invention can not be applied to direct for Kynoar adsorbed film existing in the prior art and chelating microfiltration membranes
The defects of edible liquid, provides a kind of preparation side of new beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material
Method.
In order to solve the above-mentioned technical problem, the invention is realized by the following technical scheme:
The preparation method of beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material, comprising the following steps:
(a) under inert gas protection, polyvinylidene fluoride material is placed in concentration is the alkaline molten of 0.5mol/L~0.8mol/L
Reaction is rocked 15~30 minutes in the mixture A for the liquor potassic permanganate that liquid and mass concentration are 2%~4%, the polyvinylidene fluoride
The mass ratio of alkene material and mixture A are 1:20~1:60, the quality of the mixture A neutral and alkali solution and liquor potassic permanganate
Than obtaining the Kynoar defluorinate material for sloughing HF for 100:1~100:5；
(b) by obtained Kynoar defluorinate material immersion mass concentration be 4%~6% sulfuric acid and mass concentration be 2%~4%
Solution of sodium bisulfite mixture B in, the mass ratio of the Kynoar defluorinate material and mixture B are 1:20~1:
The mass ratio of sulfuric acid and solution of sodium bisulfite is 1:0.5~1:1.5 in 60, the mixture B, in Kynoar defluorinate
Active group hydroxyl is obtained on material surface, to obtain Kynoar hydroxylcontaining materials；
(c) obtained Kynoar hydroxylcontaining materials are immersed to acrylic acid at 40 DEG C~60 DEG C and mass concentration is 95%-99%
Ethylene glycol mixture C in react 5~15 minutes, the mass ratio of the Kynoar hydroxylcontaining materials and mixture C is 1:
20~1:60, the mass ratio of acrylic acid and ethylene glycol is 1:4~1:9 in the mixture C, then at 80 DEG C~100 DEG C plus
Heat obtained acrylic acid-grafted Kynoar acryhic material after 3~5 hours；
(d) it takes beta cyclo dextrin polymer to be dissolved in anhydrous dimethyl formamide, and excessive catalyst is added, obtain mixture D,
Mixture D is stirred at room temperature up to not discharging gas, and is filtered to remove remaining catalyst, is subsequently added into acrylic acid shrink
Glyceride, the beta cyclo dextrin polymer, glycidyl acrylate mass ratio be 3:1, under inert gas protection in 90
DEG C stirring 4~6 hours, and glycidyl acrylate and beta cyclo dextrin polymer are made by the coupling reaction of adjoint ring opening process
It is connected, GMA- beta cyclo dextrin polymer is then obtained for several times and after drying by ethyl acetate washing；
(e) obtained Kynoar acryhic material is immersed in distilled water, and GMA- beta cyclo dextrin polymer is added and draws
Send out agent, the Kynoar acryhic material, distilled water, GMA- beta cyclo dextrin polymer, initiator mass ratio be 1:20:
0.4:0.02 incubates at 37 DEG C and shakes 12~24 hours, GMA- beta cyclo dextrin polymer is aggregated in Kynoar propylene
On sour material, and beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material is obtained after washed, drying.
Step (a) is by the mixture A of low concentration alkaline solution and liquor potassic permanganate processing, in polyvinylidene fluoride material
Upper success defluorinate simultaneously forms C=C double bond structure.Step (b) is by double bond nucleophilic addition on polyvinylidene fluoride material
It introduces hydroxyl (OH), to obtain the Kynoar hydroxylcontaining materials with surface hydrophilic.Step (c) then passes through polyvinylidene fluoride
Carboxyl (the CO on hydroxyl (OH) and acrylic acid on alkene hydroxylcontaining materials2H the esterification between), acrylic molecules are grafted to
On Kynoar hydroxylcontaining materials, to obtain Kynoar acryhic material, mentioned to carry out double-bond polymerization reaction on material
Functional condition is supplied.
The effect of step (d) is the grafting by carrying out glycidyl acrylate (GMA) on beta cyclo dextrin polymer
To introduce as functionality double bond necessary to polymerization reaction.And step (e) is then by Kynoar acryhic material
Between the double bond in glycidyl acrylate (GMA) in double bond and GMA- beta cyclo dextrin polymer in acrylic acid (AA)
Polymerization reaction (AA-GMA), so that finally beta cyclo dextrin polymer is grafted on polyvinylidene fluoride material by above step,
To obtain the beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material that can adsorb heavy metal ion.
Although the C=C double bond knot formed in the Kynoar defluorinate material obtained after polyvinylidene fluoride material defluorinate
In the GMA- beta cyclo dextrin polymer that structure can be obtained directly with beta cyclo dextrin polymer grafted propylene acid glycidyl ester (GMA)
Double bond carry out polymerization reaction, but polymerization reaction is led to due to C=C double bond steric hindrance in Kynoar defluorinate material
It is bad.The present invention first passes through double bond nucleophilic addition and introduces hydroxyl, then connects acrylic acid (AA) through hydroxy esterification, finally again
It is polymerize by the double bond in acrylic acid on Kynoar acryhic material with the double bond in GMA- beta cyclo dextrin polymer
Reaction, beta cyclo dextrin polymer is grafted on polyvinylidene fluoride material.The present invention passes through this on polyvinylidene fluoride material
Hydroxyl and acrylic acid are successively introduced, and utilizes the lesser double bond of steric hindrance in the acrylic acid on Kynoar acryhic material
Polymerization reaction is carried out with the double bond in GMA- beta cyclo dextrin polymer, to can get on polyvinylidene fluoride material highdensity
Beta cyclo dextrin polymer grafting.
Preferably, the preparation method of beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material described above, institute
State step (d), (e) replacement are as follows:
(f) it takes beta-cyclodextrin to be dissolved in anhydrous dimethyl formamide, and excessive catalyst is added, obtain mixture E, will mix
Object E is stirred at room temperature up to not discharging gas, and is filtered to remove remaining catalyst, is subsequently added into glycidyl
Ester, the beta-cyclodextrin, glycidyl acrylate mass ratio be 3:1, under inert gas protection in 90 DEG C stir 4~6
Hour, and by making glycidyl acrylate be connected with beta-cyclodextrin with the coupling reaction of ring opening process, then pass through
Ethyl acetate washing obtains GMA- beta-cyclodextrin for several times and after drying；
(g) obtained Kynoar acryhic material is immersed in distilled water, and GMA- beta-cyclodextrin and initiator is added, institute
State Kynoar acryhic material, distilled water, GMA- beta-cyclodextrin, initiator mass ratio be 1:20:0.4:0.02,37
It incubates and shakes 12~24 hours at DEG C, GMA- beta-cyclodextrin is aggregated on Kynoar acryhic material, obtains gathering inclined fluorine
Ethylene-GMA- beta-cyclodextrin material；
(h) obtained Kynoar-GMA- beta-cyclodextrin material is immersed in the ethylene glycol that mass concentration is 95%-99%, and
Beta-cyclodextrin, tetrafluoro terephthalonitrile and potassium carbonate, the Kynoar-GMA- beta-cyclodextrin material, ethylene glycol, four is added
Fluorine para-Phthalonitrile, potassium carbonate mass ratio be 1:20:0.5:3, reaction 48 hours is shaken at 85 DEG C, and washed, dry
After obtain beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material.
It is poly- except through beta-cyclodextrin during preparing beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material
(step d) and GMA- beta cyclo dextrin polymer are carried out with acrylic acid on Kynoar acryhic material for the GMA grafting of conjunction object
(other than step e), there are one alternatives: beta-cyclodextrin monomer being carried out GMA grafting first for GMA-AA polymerization reaction
(then beta-cyclodextrin monomer is connected on Kynoar acryhic material (step by GMA-AA polymerization reaction by step f)
It is rapid g), finally by the polymerization reaction on Kynoar-GMA- beta-cyclodextrin material by beta-cyclodextrin monomer polymerization at highly dense
Beta cyclo dextrin polymer (the step h) of degree.
Although the grafting (step d, f) of beta cyclo dextrin polymer or beta-cyclodextrin monomer and with Kynoar acrylic acid
Polymerization reaction (step e, g) on material is more similar, but compared with the polymerization reaction of beta-cyclodextrin in the solution, beta-cyclodextrin
It is first grafted on material and carries out solid-phase polymerization again with easily controllable, the product convenient separation of reaction and convenient for volume industrial
The advantages of metaplasia produces.
Preferably, the preparation method of beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material described above, institute
State in step (d), the beta cyclo dextrin polymer the preparation method comprises the following steps:
(d1) mixture F, tetrahydrofuran and diformazan in the mixture F are formed after mixing tetrahydrofuran and dimethylformamide
The mass ratio of base formamide is 19:1~9:1, and beta-cyclodextrin, tetrafluoro terephthalonitrile, potassium carbonate are added with the ratio of 2:1:3
It is stirred 2 days into mixture F, and in 85 DEG C of oil baths with 500 revs/min of speed, obtains mixture G；
(d2) gained mixture G is cooling and by being centrifugally separating to obtain mixture H, with water, tetrahydrofuran and methylene chloride according to
Secondary washing mixture H obtains beta cyclo dextrin polymer to remove remaining reactant.
, can be by beta-cyclodextrin monomer polymerization at highdensity beta cyclo dextrin polymer by above step, and walk above
It is rapid easily operated, beta cyclo dextrin polymer can be readily obtained.
Preferably, the preparation method of beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material described above, institute
It states in step (d2), by obtained beta cyclo dextrin polymer dry 24 in the vacuum freeze dryer that temperature is -20~-30 DEG C
~48 hours.
By the way that beta cyclo dextrin polymer is carried out vacuum freeze drying, beta cyclo dextrin polymer colloidal nano grain can be improved
The long-time stability of son.
Preferably, the preparation method of beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material described above, institute
It states in step (c), obtained Kynoar acryhic material is washed with distilled water, until removing all chemical reagent to obtain
Clean Kynoar acryhic material is obtained, and Kynoar acryhic material is stored in pure water.
Water-soluble excessive propene acid residual and water-soluble solvent ethylene glycol can be washed off by being washed repeatedly with distilled water, to obtain
Very pure Kynoar acryhic material is obtained, remaining acrylic acid, ethylene glycol is avoided to influence the progress of subsequent reactions.
Preferably, the preparation method of beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material described above, institute
It states washing, is dry to be washed using ethyl alcohol and deionized water, and at 60 DEG C after drying 24~48 hours, obtaining β-ring paste
Smart polymer grafted polyvinylidene vinyl fluoride adsorbent material.
Carrying out washing and abundant drying repeatedly to beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material can obtain
Beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material steady in a long-term, guarantees the stability of its performance.
Preferably, the preparation method of beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material described above, institute
Stating inert gas is nitrogen or argon gas.
It can be avoided the influence caused by chemical reaction of the oxygen in air using inert gas such as nitrogen or argon gas, guarantee
The stability of reaction.
Preferably, the preparation method of beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material described above, institute
Stating the alkaline solution in step (a) is potassium hydroxide solution, sodium hydroxide solution, calcium hydroxide solution, solution of potassium carbonate, carbonic acid
Any one of sodium solution, sodium bicarbonate solution, ammonium hydroxide.
Alkaline solution selects above several defluorination reaction efficiency that can further increase polyvinylidene fluoride material.
Preferably, the preparation method of beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material described above, institute
Stating catalyst is any one of sodium hydride, sodium borohydride, boron trifluoride ether, triethylamine.
It selects the above substance that can activate the hydroxyl (OH) on beta-cyclodextrin or beta cyclo dextrin polymer as catalyst, comes
Help the GMA of beta-cyclodextrin or beta cyclo dextrin polymer grafting.
Preferably, the preparation method of beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material described above, institute
The initiator stated is any one of ammonium persulfate, potassium peroxydisulfate, hydrogen peroxide, benzoyl peroxide, azodiisobutyronitrile.
Select the above substance that can preferably cause double-bond polymerization reaction as initiator, so that GMA- beta-cyclodextrin be gathered
It closes on object or GMA- grafted by beta cyclodextrin to Kynoar acryhic material.
The beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material obtained through the invention, can directly apply to food
In liquid, such as applied on the containers such as cup, pot, so as to effectively adsorb the heavy metal in edible liquid, protect
The healthy diet of witnesses.Wherein beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material can according to need in application
The forms such as film, plate, particle, coating specifically are made, consequently facilitating manufacturing.
Specific embodiment
Present invention is further described in detail With reference to embodiment, but they are not to limit of the invention
System:
Embodiment 1
The preparation method of beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material, comprising the following steps:
(a) under inert gas protection, by polyvinylidene fluoride material be placed in concentration be 0.5mol/L alkaline solution and quality it is dense
Degree rocks reaction 15 minutes, the matter of the polyvinylidene fluoride material and mixture A in the mixture A for 2% liquor potassic permanganate
Ratio is measured as 1:20, the mass ratio of the mixture A neutral and alkali solution and liquor potassic permanganate is 100:1, obtains sloughing the poly- of HF
Vinylidene defluorinate material；
(b) sulfurous acid for being 2% with mass concentration by the sulfuric acid that obtained Kynoar defluorinate material immersion mass concentration is 4%
In the mixture B of hydrogen sodium solution, the mass ratio of the Kynoar defluorinate material and mixture B are 1:20, the mixture B
The mass ratio of middle sulfuric acid and solution of sodium bisulfite is 1:0.5, to obtain active group on Kynoar defluorinate material surface
Group's hydroxyl, to obtain Kynoar hydroxylcontaining materials；
(c) obtained Kynoar hydroxylcontaining materials are immersed to the ethylene glycol that acrylic acid is 95% with mass concentration at 40 DEG C
It is reacted 5 minutes in mixture C, the mass ratio of the Kynoar hydroxylcontaining materials and mixture C is 1:20, the mixture C
The mass ratio of middle acrylic acid and ethylene glycol is 1:4, obtains acrylic acid-grafted polyvinylidene fluoride after then heating 3 hours at 80 DEG C
Alkene acryhic material；
(d) it takes beta cyclo dextrin polymer to be dissolved in anhydrous dimethyl formamide, and excessive catalyst is added, obtain mixture D,
Mixture D is stirred at room temperature up to not discharging gas, and is filtered to remove remaining catalyst, is subsequently added into acrylic acid shrink
Glyceride, the beta cyclo dextrin polymer, glycidyl acrylate mass ratio be 3:1, under inert gas protection in 90
DEG C stirring 4 hours, and glycidyl acrylate and beta cyclo dextrin polymer phase are made by the coupling reaction of adjoint ring opening process
Then connection obtains GMA- beta cyclo dextrin polymer for several times and after drying by ethyl acetate washing；
(e) obtained Kynoar acryhic material is immersed in distilled water, and GMA- beta cyclo dextrin polymer is added and draws
Send out agent, the Kynoar acryhic material, distilled water, GMA- beta cyclo dextrin polymer, initiator mass ratio be 1:20:
0.4:0.02 incubates at 37 DEG C and shakes 12 hours, GMA- beta cyclo dextrin polymer is aggregated in Kynoar acrylic acid material
On material, and beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material is obtained after washed, drying.
Preferably, be washed with distilled water obtained Kynoar acryhic material in the step (c), until
All chemical reagent are removed to obtain clean Kynoar acryhic material, and Kynoar acryhic material is stored
In pure water.
Preferably, the washing, drying are to be washed using ethyl alcohol and deionized water, and drying 24 is small at 60 DEG C
Shi Hou obtains beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material.
Preferably, the inert gas is nitrogen or argon gas.
Preferably, the alkaline solution in the step (a) is potassium hydroxide solution, sodium hydroxide solution, calcium hydroxide
Any one of solution, solution of potassium carbonate, sodium carbonate liquor, sodium bicarbonate solution, ammonium hydroxide.
Preferably, the catalyst is any one of sodium hydride, sodium borohydride, boron trifluoride ether, triethylamine.
Preferably, the initiator is ammonium persulfate, potassium peroxydisulfate, hydrogen peroxide, benzoyl peroxide, azo two
Any one of isobutyronitrile.
Embodiment 2
The preparation method of beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material, comprising the following steps:
(a) under inert gas protection, by polyvinylidene fluoride material be placed in concentration be 0.8mol/L alkaline solution and quality it is dense
Degree rocks reaction 15~30 minutes in the mixture A for 4% liquor potassic permanganate, the polyvinylidene fluoride material and mixture A
Mass ratio be 1:60, the mass ratio of the mixture A neutral and alkali solution and liquor potassic permanganate is 100:5, obtains sloughing HF
Kynoar defluorinate material；
(b) sulfurous acid for being 4% with mass concentration by the sulfuric acid that obtained Kynoar defluorinate material immersion mass concentration is 6%
In the mixture B of hydrogen sodium solution, the mass ratio of the Kynoar defluorinate material and mixture B are 1:60, the mixture B
The mass ratio of middle sulfuric acid and solution of sodium bisulfite is 1:1.5, to obtain active group on Kynoar defluorinate material surface
Group's hydroxyl, to obtain Kynoar hydroxylcontaining materials；
(c) obtained Kynoar hydroxylcontaining materials are immersed to the ethylene glycol that acrylic acid is 99% with mass concentration at 60 DEG C
It is reacted 15 minutes in mixture C, the mass ratio of the Kynoar hydroxylcontaining materials and mixture C is 1:60, the mixture C
The mass ratio of middle acrylic acid and ethylene glycol is 1:9, and acrylic acid-grafted poly- inclined fluorine is obtained after then heating 5 hours at 100 DEG C
Ethylene acrylic material；
(d) it takes beta cyclo dextrin polymer to be dissolved in anhydrous dimethyl formamide, and excessive catalyst is added, obtain mixture D,
Mixture D is stirred at room temperature up to not discharging gas, and is filtered to remove remaining catalyst, is subsequently added into acrylic acid shrink
Glyceride, the beta cyclo dextrin polymer, glycidyl acrylate mass ratio be 3:1, under inert gas protection in 90
DEG C stirring 6 hours, and glycidyl acrylate and beta cyclo dextrin polymer phase are made by the coupling reaction of adjoint ring opening process
Then connection obtains GMA- beta cyclo dextrin polymer for several times and after drying by ethyl acetate washing；
(e) obtained Kynoar acryhic material is immersed in distilled water, and GMA- beta cyclo dextrin polymer is added and draws
Send out agent, the Kynoar acryhic material, distilled water, GMA- beta cyclo dextrin polymer, initiator mass ratio be 1:20:
0.4:0.02 incubates at 37 DEG C and shakes 24 hours, GMA- beta cyclo dextrin polymer is aggregated in Kynoar acrylic acid material
On material, and beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material is obtained after washed, drying.
Preferably, be washed with distilled water obtained Kynoar acryhic material in the step (c), until
All chemical reagent are removed to obtain clean Kynoar acryhic material, and Kynoar acryhic material is stored
In pure water.
Preferably, the washing, drying are to be washed using ethyl alcohol and deionized water, and drying 48 is small at 60 DEG C
Shi Hou obtains beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material.
Preferably, the inert gas is nitrogen or argon gas.
Preferably, the alkaline solution in the step (a) is potassium hydroxide solution, sodium hydroxide solution, calcium hydroxide
Any one of solution, solution of potassium carbonate, sodium carbonate liquor, sodium bicarbonate solution, ammonium hydroxide.
Preferably, the catalyst is any one of sodium hydride, sodium borohydride, boron trifluoride ether, triethylamine.
Preferably, the initiator is ammonium persulfate, potassium peroxydisulfate, hydrogen peroxide, benzoyl peroxide, azo two
Any one of isobutyronitrile.
Embodiment 3
The preparation method of beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material, comprising the following steps:
(a) under inert gas protection, by polyvinylidene fluoride material be placed in concentration be 0.65mol/L alkaline solution and quality it is dense
Degree rocks reaction 20 minutes, the matter of the polyvinylidene fluoride material and mixture A in the mixture A for 3% liquor potassic permanganate
Ratio is measured as 1:40, the mass ratio of the mixture A neutral and alkali solution and liquor potassic permanganate is 100:3, obtains sloughing the poly- of HF
Vinylidene defluorinate material；
(b) sulfurous acid for being 3% with mass concentration by the sulfuric acid that obtained Kynoar defluorinate material immersion mass concentration is 5%
In the mixture B of hydrogen sodium solution, the mass ratio of the Kynoar defluorinate material and mixture B are 1:40, the mixture B
The mass ratio of middle sulfuric acid and solution of sodium bisulfite is 1:1, to obtain active group on Kynoar defluorinate material surface
Hydroxyl, to obtain Kynoar hydroxylcontaining materials；
(c) obtained Kynoar hydroxylcontaining materials are immersed to the ethylene glycol that acrylic acid is 97% with mass concentration at 50 DEG C
It is reacted 10 minutes in mixture C, the mass ratio of the Kynoar hydroxylcontaining materials and mixture C is 1:40, the mixture C
The mass ratio of middle acrylic acid and ethylene glycol is 1:7, obtains acrylic acid-grafted polyvinylidene fluoride after then heating 4 hours at 90 DEG C
Alkene acryhic material；
(d) it takes beta cyclo dextrin polymer to be dissolved in anhydrous dimethyl formamide, and excessive catalyst is added, obtain mixture D,
Mixture D is stirred at room temperature up to not discharging gas, and is filtered to remove remaining catalyst, is subsequently added into acrylic acid shrink
Glyceride, the beta cyclo dextrin polymer, glycidyl acrylate mass ratio be 3:1, under inert gas protection in 90
DEG C stirring 5 hours, and glycidyl acrylate and beta cyclo dextrin polymer phase are made by the coupling reaction of adjoint ring opening process
Then connection obtains GMA- beta cyclo dextrin polymer for several times and after drying by ethyl acetate washing；
(e) obtained Kynoar acryhic material is immersed in distilled water, and GMA- beta cyclo dextrin polymer is added and draws
Send out agent, the Kynoar acryhic material, distilled water, GMA- beta cyclo dextrin polymer, initiator mass ratio be 1:20:
0.4:0.02 incubates at 37 DEG C and shakes 18 hours, GMA- beta cyclo dextrin polymer is aggregated in Kynoar acrylic acid material
On material, and beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material is obtained after washed, drying.
Preferably, be washed with distilled water obtained Kynoar acryhic material in the step (c), until
All chemical reagent are removed to obtain clean Kynoar acryhic material, and Kynoar acryhic material is stored
In pure water.
Preferably, the washing, drying are to be washed using ethyl alcohol and deionized water, and drying 36 is small at 60 DEG C
Shi Hou obtains beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material.
Preferably, the inert gas is nitrogen or argon gas.
Preferably, the alkaline solution in the step (a) is potassium hydroxide solution, sodium hydroxide solution, calcium hydroxide
Any one of solution, solution of potassium carbonate, sodium carbonate liquor, sodium bicarbonate solution, ammonium hydroxide.
Preferably, the catalyst is any one of sodium hydride, sodium borohydride, boron trifluoride ether, triethylamine.
Preferably, the initiator is ammonium persulfate, potassium peroxydisulfate, hydrogen peroxide, benzoyl peroxide, azo two
Any one of isobutyronitrile.
Embodiment 4
In embodiment 1-3, in the step (d), the beta cyclo dextrin polymer the preparation method comprises the following steps:
(d1) mixture F, tetrahydrofuran and diformazan in the mixture F are formed after mixing tetrahydrofuran and dimethylformamide
The mass ratio of base formamide is 19:1, beta-cyclodextrin, tetrafluoro terephthalonitrile, potassium carbonate is added to the ratio of 2:1:3 mixed
It closes in object F, and is stirred 2 days in 85 DEG C of oil baths with 500 revs/min of speed, obtain mixture G；
(d2) gained mixture G is cooling and by being centrifugally separating to obtain mixture H, with water, tetrahydrofuran and methylene chloride according to
Secondary washing mixture H obtains beta cyclo dextrin polymer to remove remaining reactant.
Preferably, in the step (d2), the vacuum refrigeration for being -20 DEG C in temperature by obtained beta cyclo dextrin polymer
It is 24 hours dry in drier.
Other steps are the same as embodiment 1-3.
Embodiment 5
In embodiment 1-3, in the step (d), the beta cyclo dextrin polymer the preparation method comprises the following steps:
(d1) mixture F, tetrahydrofuran and diformazan in the mixture F are formed after mixing tetrahydrofuran and dimethylformamide
The mass ratio of base formamide is 9:1, and beta-cyclodextrin, tetrafluoro terephthalonitrile, potassium carbonate are added to mixing with the ratio of 2:1:3
It in object F, and is stirred 2 days in 85 DEG C of oil baths with 500 revs/min of speed, obtains mixture G；
(d2) gained mixture G is cooling and by being centrifugally separating to obtain mixture H, with water, tetrahydrofuran and methylene chloride according to
Secondary washing mixture H obtains beta cyclo dextrin polymer to remove remaining reactant.
Preferably, in the step (d2), the vacuum refrigeration for being -30 DEG C in temperature by obtained beta cyclo dextrin polymer
It is 48 hours dry in drier.
Other steps are the same as embodiment 1-3.
Embodiment 6
In embodiment 1-3, in the step (d), the beta cyclo dextrin polymer the preparation method comprises the following steps:
(d1) mixture F, tetrahydrofuran and diformazan in the mixture F are formed after mixing tetrahydrofuran and dimethylformamide
The mass ratio of base formamide is 14:1, beta-cyclodextrin, tetrafluoro terephthalonitrile, potassium carbonate is added to the ratio of 2:1:3 mixed
It closes in object F, and is stirred 2 days in 85 DEG C of oil baths with 500 revs/min of speed, obtain mixture G；
(d2) gained mixture G is cooling and by being centrifugally separating to obtain mixture H, with water, tetrahydrofuran and methylene chloride according to
Secondary washing mixture H obtains beta cyclo dextrin polymer to remove remaining reactant.
Preferably, in the step (d2), the vacuum refrigeration for being -25 DEG C in temperature by obtained beta cyclo dextrin polymer
It is 36 hours dry in drier.
Other steps are the same as embodiment 1-3.
Embodiment 7
In embodiment 1-3, the step (d), (e) replacement are as follows:
(f) it takes beta-cyclodextrin to be dissolved in anhydrous dimethyl formamide, and excessive catalyst is added, obtain mixture E, will mix
Object E is stirred at room temperature up to not discharging gas, and is filtered to remove remaining catalyst, is subsequently added into glycidyl
Ester, the beta-cyclodextrin, glycidyl acrylate mass ratio be 3:1, it is 4 small in 90 DEG C of stirrings under inert gas protection
When, and by making glycidyl acrylate be connected with beta-cyclodextrin with the coupling reaction of ring opening process, then pass through second
Acetoacetic ester washing obtains GMA- beta-cyclodextrin for several times and after drying；
(g) obtained Kynoar acryhic material is immersed in distilled water, and GMA- beta-cyclodextrin and initiator is added, institute
State Kynoar acryhic material, distilled water, GMA- beta-cyclodextrin, initiator mass ratio be 1:20:0.4:0.02,37
It incubates and shakes 12 hours at DEG C, GMA- beta-cyclodextrin is aggregated on Kynoar acryhic material, Kynoar-is obtained
GMA- beta-cyclodextrin material；
(h) obtained Kynoar-GMA- beta-cyclodextrin material is immersed in the ethylene glycol that mass concentration is 95%, and be added
Beta-cyclodextrin, tetrafluoro terephthalonitrile and potassium carbonate, the Kynoar-GMA- beta-cyclodextrin material, ethylene glycol, tetrafluoro pair
Benzene dicarbonitrile, potassium carbonate mass ratio be 1:20:0.5:3, shake reaction 48 hours at 85 DEG C, and it is washed, dry after
To beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material.
Other steps are the same as embodiment 1-3.
Embodiment 8
In embodiment 1-3, the step (d), (e) replacement are as follows:
(f) it takes beta-cyclodextrin to be dissolved in anhydrous dimethyl formamide, and excessive catalyst is added, obtain mixture E, will mix
Object E is stirred at room temperature up to not discharging gas, and is filtered to remove remaining catalyst, is subsequently added into glycidyl
Ester, the beta-cyclodextrin, glycidyl acrylate mass ratio be 3:1, it is 6 small in 90 DEG C of stirrings under inert gas protection
When, and by making glycidyl acrylate be connected with beta-cyclodextrin with the coupling reaction of ring opening process, then pass through second
Acetoacetic ester washing obtains GMA- beta-cyclodextrin for several times and after drying；
(g) obtained Kynoar acryhic material is immersed in distilled water, and GMA- beta-cyclodextrin and initiator is added, institute
State Kynoar acryhic material, distilled water, GMA- beta-cyclodextrin, initiator mass ratio be 1:20:0.4:0.02,37
It incubates and shakes 24 hours at DEG C, GMA- beta-cyclodextrin is aggregated on Kynoar acryhic material, Kynoar-is obtained
GMA- beta-cyclodextrin material；
(h) obtained Kynoar-GMA- beta-cyclodextrin material is immersed in the ethylene glycol that mass concentration is 99%, and be added
Beta-cyclodextrin, tetrafluoro terephthalonitrile and potassium carbonate, the Kynoar-GMA- beta-cyclodextrin material, ethylene glycol, tetrafluoro pair
Benzene dicarbonitrile, potassium carbonate mass ratio be 1:20:0.5:3, shake reaction 48 hours at 85 DEG C, and it is washed, dry after
To beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material.
Other steps are the same as embodiment 1-3.
Embodiment 9
In embodiment 1-3, the step (d), (e) replacement are as follows:
(f) it takes beta-cyclodextrin to be dissolved in anhydrous dimethyl formamide, and excessive catalyst is added, obtain mixture E, will mix
Object E is stirred at room temperature up to not discharging gas, and is filtered to remove remaining catalyst, is subsequently added into glycidyl
Ester, the beta-cyclodextrin, glycidyl acrylate mass ratio be 3:1, it is 5 small in 90 DEG C of stirrings under inert gas protection
When, and by making glycidyl acrylate be connected with beta-cyclodextrin with the coupling reaction of ring opening process, then pass through second
Acetoacetic ester washing obtains GMA- beta-cyclodextrin for several times and after drying；
(g) obtained Kynoar acryhic material is immersed in distilled water, and GMA- beta-cyclodextrin and initiator is added, institute
State Kynoar acryhic material, distilled water, GMA- beta-cyclodextrin, initiator mass ratio be 1:20:0.4:0.02,37
It incubates and shakes 18 hours at DEG C, GMA- beta-cyclodextrin is aggregated on Kynoar acryhic material, Kynoar-is obtained
GMA- beta-cyclodextrin material；
(h) obtained Kynoar-GMA- beta-cyclodextrin material is immersed in the ethylene glycol that mass concentration is 97%, and be added
Beta-cyclodextrin, tetrafluoro terephthalonitrile and potassium carbonate, the Kynoar-GMA- beta-cyclodextrin material, ethylene glycol, tetrafluoro pair
Benzene dicarbonitrile, potassium carbonate mass ratio be 1:20:0.5:3, shake reaction 48 hours at 85 DEG C, and it is washed, dry after
To beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material.
Other steps are the same as embodiment 1-3.
Embodiment 10
The liquid containing heavy metal lead is taken, show that the content of lead in the liquid containing heavy metal lead is after tested
The liquid containing heavy metal lead is divided into 18 equal portions by 11.086ug/mL, wherein putting in 9 parts of liquid containing heavy metal lead
Enter beta cyclo dextrin polymer to adsorb 2 hours, then tests the lead content in this 9 parts of liquid containing heavy metal lead, obtain its lead
Content value is 0.816-0.723, show that effective adsorption rate of beta cyclo dextrin polymer is 92.6%-93.5%.
Beta cyclo dextrin polymer obtained in embodiment 1-9 is each placed in other 9 parts of liquid containing heavy metal lead
Grafted polyvinylidene vinyl fluoride adsorbent material simultaneously adsorbs 2 hours, then tests the lead content in this 9 parts of liquid containing heavy metal lead,
Obtaining its lead content value is 0.037-0.029, obtains effective suction of beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material
Attached rate is 99.67%-99.74%.
In short, the foregoing is merely presently preferred embodiments of the present invention, made by all ranges according to the present patent application patent
Deng variation and modification, it is all covered by the present invention.
Claims (10)
1. the preparation method of beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material, it is characterised in that: the following steps are included:
(a) under inert gas protection, polyvinylidene fluoride material is placed in concentration is the alkaline molten of 0.5mol/L~0.8mol/L
Reaction is rocked 15~30 minutes in the mixture A for the liquor potassic permanganate that liquid and mass concentration are 2%~4%, the polyvinylidene fluoride
The mass ratio of alkene material and mixture A are 1:20~1:60, the quality of the mixture A neutral and alkali solution and liquor potassic permanganate
Than obtaining the Kynoar defluorinate material for sloughing HF for 100:1~100:5；
(b) by obtained Kynoar defluorinate material immersion mass concentration be 4%~6% sulfuric acid and mass concentration be 2%~4%
Solution of sodium bisulfite mixture B in, the mass ratio of the Kynoar defluorinate material and mixture B are 1:20~1:
The mass ratio of sulfuric acid and solution of sodium bisulfite is 1:0.5~1:1.5 in 60, the mixture B, in Kynoar defluorinate
Active group hydroxyl is obtained on material surface, to obtain Kynoar hydroxylcontaining materials；
(c) obtained Kynoar hydroxylcontaining materials are immersed to acrylic acid at 40 DEG C~60 DEG C and mass concentration is 95%-99%
Ethylene glycol mixture C in react 5~15 minutes, the mass ratio of the Kynoar hydroxylcontaining materials and mixture C is 1:
20~1:60, the mass ratio of acrylic acid and ethylene glycol is 1:4~1:9 in the mixture C, then at 80 DEG C~100 DEG C plus
Heat obtained acrylic acid-grafted Kynoar acryhic material after 3~5 hours；
(d) it takes beta cyclo dextrin polymer to be dissolved in anhydrous dimethyl formamide, and excessive catalyst is added, obtain mixture D,
Mixture D is stirred at room temperature up to not discharging gas, and is filtered to remove remaining catalyst, is subsequently added into acrylic acid shrink
Glyceride, the beta cyclo dextrin polymer, glycidyl acrylate mass ratio be 3:1, under inert gas protection in 90
DEG C stirring 4~6 hours, and glycidyl acrylate and beta cyclo dextrin polymer are made by the coupling reaction of adjoint ring opening process
It is connected, GMA- beta cyclo dextrin polymer is then obtained for several times and after drying by ethyl acetate washing；
(e) obtained Kynoar acryhic material is immersed in distilled water, and GMA- beta cyclo dextrin polymer is added and draws
Send out agent, the Kynoar acryhic material, distilled water, GMA- beta cyclo dextrin polymer, initiator mass ratio be 1:20:
0.4:0.02 incubates at 37 DEG C and shakes 12~24 hours, GMA- beta cyclo dextrin polymer is aggregated in Kynoar propylene
On sour material, and beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material is obtained after washed, drying.
2. the preparation method of beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material according to claim 1, special
Sign is: the step (d), (e) replacement are as follows:
(f) it takes beta-cyclodextrin to be dissolved in anhydrous dimethyl formamide, and excessive catalyst is added, obtain mixture E, will mix
Object E is stirred at room temperature up to not discharging gas, and is filtered to remove remaining catalyst, is subsequently added into glycidyl
Ester, the beta-cyclodextrin, glycidyl acrylate mass ratio be 3:1, under inert gas protection in 90 DEG C stir 4~6
Hour, and by making glycidyl acrylate be connected with beta-cyclodextrin with the coupling reaction of ring opening process, then pass through
Ethyl acetate washing obtains GMA- beta-cyclodextrin for several times and after drying；
(g) obtained Kynoar acryhic material is immersed in distilled water, and GMA- beta-cyclodextrin and initiator is added, institute
State Kynoar acryhic material, distilled water, GMA- beta-cyclodextrin, initiator mass ratio be 1:20:0.4:0.02,37
It incubates and shakes 12~24 hours at DEG C, GMA- beta-cyclodextrin is aggregated on Kynoar acryhic material, obtains gathering inclined fluorine
Ethylene-GMA- beta-cyclodextrin material；
(h) obtained Kynoar-GMA- beta-cyclodextrin material is immersed in the ethylene glycol that mass concentration is 95%-99%, and
Beta-cyclodextrin, tetrafluoro terephthalonitrile and potassium carbonate, the Kynoar-GMA- beta-cyclodextrin material, ethylene glycol, four is added
Fluorine para-Phthalonitrile, potassium carbonate mass ratio be 1:20:0.5:3, reaction 48 hours is shaken at 85 DEG C, and washed, dry
After obtain beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material.
3. the preparation method of beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material according to claim 1, special
Sign is: in the step (d), the beta cyclo dextrin polymer the preparation method comprises the following steps:
(d1) mixture F, tetrahydrofuran and diformazan in the mixture F are formed after mixing tetrahydrofuran and dimethylformamide
The mass ratio of base formamide is 19:1~9:1, and beta-cyclodextrin, tetrafluoro terephthalonitrile, potassium carbonate are added with the ratio of 2:1:3
It is stirred 2 days into mixture F, and in 85 DEG C of oil baths with 500 revs/min of speed, obtains mixture G；
(d2) gained mixture G is cooling and by being centrifugally separating to obtain mixture H, with water, tetrahydrofuran and methylene chloride according to
Secondary washing mixture H obtains beta cyclo dextrin polymer to remove remaining reactant.
4. the preparation method of beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material according to claim 3, special
Sign is: in the step (d2), the vacuum freeze drying for being -20~-30 DEG C in temperature by obtained beta cyclo dextrin polymer
It is 24~48 hours dry in device.
5. the preparation method of beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material according to claim 1, special
Sign is: in the step (c), obtained Kynoar acryhic material being washed with distilled water, until removing allization
Reagent is learned to obtain clean Kynoar acryhic material, and Kynoar acryhic material is stored in pure water.
6. the preparation method of beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material according to claim 1 or 2,
Be characterized in that: the washing, drying is are washed using ethyl alcohol and deionized water, and drying 24~48 hours at 60 DEG C
Afterwards, beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material is obtained.
7. the preparation method of beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material according to claim 1 or 2,
Be characterized in that: the inert gas is nitrogen or argon gas.
8. the preparation method of beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material according to claim 1, special
Sign is: the alkaline solution in the step (a) is potassium hydroxide solution, sodium hydroxide solution, calcium hydroxide solution, potassium carbonate
Any one of solution, sodium carbonate liquor, sodium bicarbonate solution, ammonium hydroxide.
9. the preparation method of beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material according to claim 1 or 2,
Be characterized in that: the catalyst is any one of sodium hydride, sodium borohydride, boron trifluoride ether, triethylamine.
10. the preparation method of beta cyclo dextrin polymer grafted polyvinylidene vinyl fluoride adsorbent material according to claim 1 or 2,
It is characterized by: the initiator is ammonium persulfate, potassium peroxydisulfate, hydrogen peroxide, benzoyl peroxide, azodiisobutyronitrile
Any one of.
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