CN102603971A - Magnetic expansion adsorption resin and preparation method thereof - Google Patents
Magnetic expansion adsorption resin and preparation method thereof Download PDFInfo
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Abstract
The invention provides a magnetic expansion adsorption resin and a preparation method of the magnetic expansion adsorption resin. The magnetic expansion adsorption resin is compounded through polymerization reaction of the following components in parts by weight: larger than zero and less than or equal to 50 parts of magnetic powders, 50.0-100.0 parts of water-soluble ethylenically unsaturated monomers and 0.1-2.0 parts of cross linkers. The preparation method mainly adopts a water solution polymerization method or an inverse suspension polymerization method. The magnetic expansion adsorption resin prepared by the preparation method has an adsorption enrichment function to metal ions, such as heavy metal ions in water body, or soil, or a solid-liquid suspension (mixed) system, is easy to separate out by a magnet or magnetic separation machinery, has a simple preparation method, low cost and high expansion degree, can be widely used for separating the metal ions of a fluid bed or preparation equipment, provides an excellent adsorption material for automation and mass production in separation and purification, and is suitable for adsorption enrichment separation application in industries of environmental protection, pollution abatement, bioseparation, mineral separation, and the like.
Description
Technical field
The invention belongs to functional high molecule material and functional composite material technical field, relate in particular to a kind of magnetic expansion polymeric adsorbent and preparation method thereof.
Background technology
The equal function of dominant macromolecular material of polymeric adsorbent and swollen resin.Recent Development proof hydrogel expanding material has superpower adsorptive power of selectivity and super large loading capacity to metals ion such as heavy metal ion etc., so the hydrogel expanding material becomes the expansion sorbing material again.Usefulness inverse suspension polymerization methods such as Xie Jianjun have been synthesized ROHM/acrylic amide hydrogel (PAAAM) expansion sorbing material, are used for the fractionation by adsorption of Cu (II), Ni (II), Co (II); Also synthesized ZX-I hydrogel (PAAS) expansion sorbing material, studied the absorbent in single and mixture-metal ion nitrate soln, also studied it Pb (II); Cd (II); Ni (II), Cu (II), Zn (II); Mn (II), the absorption property of Cr (III).Above synthetic (PAAAM) and (PAAS) all nonmagnetic, inconvenience with from water body, separate.It is template that the patented claim of one Chinese patent application numbers 201010284643 and 200710072462 discloses with the hydrogel, is the method for feedstock production ferriferrous oxide nano-particle with Fe (III), Fe (II).Obvious this method is to prepare magnetic particle through behind the absorption iron ion chemical reaction taking place; And non magnetic hydrogel; And have the restriction that the intramolecularly adsorption group is saturated by iron, adsorptive capacity is little, be difficult to hydrogel magnetic power is significantly adjusted, preparation manipulation is complicated; Condition is difficult to control, uses it for the application of enrichment and separating metal ionic and is restricted.
Summary of the invention
The object of the present invention is to provide a kind of turgidity high, magnetic expansion polymeric adsorbent of high adsorption capacity and preparation method thereof.
In order to realize the object of the invention, the technical scheme that the present invention taked is:
A kind of magnetic expansion polymeric adsorbent, it by comprise weight part be respectively greater than zero and smaller or equal to 50 parts magnetic powder, 50.0～100.0 parts the water-soluble vinyl unsaturated monomer, and 0.1～2.0 part linking agent be composited through polyreaction.
In the such scheme, said magnetic powder chosen from Fe magnetic mineral or through becoming the material of magnetic mineral or iron ion is adsorbed in the hydrogel after the processing, the powdery magnetic of in-situ preparing, the median size of said magnetic powder is 0.1～150 μ m.
In the such scheme, the median size of said magnetic powder is 1.0-100 μ m.
In the such scheme, the weight part of said water-soluble vinyl unsaturated monomer is 70.0～100.0 parts.
In the such scheme, said water-soluble vinyl unsaturated monomer is 2-acrylamido-2-methyl propane sulfonic acid, and acrylic amide, or the one or any two or more mixing in the vinylformic acid mix with arbitrary proportion during mixing.
In the such scheme, said linking agent comprises that per molecule contains two polymerisable unsaturated groups at least, and said linking agent is N, N '-methylene-bisacrylamide.
A kind of preparation method of magnetic expansion polymeric adsorbent, it may further comprise the steps:
1) weight part is respectively greater than zero and smaller or equal to 50 parts magnetic powder, 50.0～100.0 parts water-soluble vinyl unsaturated monomer, 0.1～2.0 part linking agent, 0.05～10.0 part initiator and water mixing; Obtain mixture; Wherein, Water mixes the aqueous solution that obtains the water-soluble vinyl unsaturated monomer with the water-soluble vinyl unsaturated monomer; The mass percentage concentration of the aqueous solution of water-soluble vinyl unsaturated monomer is 15%～40%, and said mixture is disperseed;
2) make mixture after the above-mentioned dispersion in 10～80 ℃ of heating 1～3 hour, elevated temperature to 70～90 a ℃ reaction was carried out slaking in 1～5 hour again, obtained gluey polymerisate;
3) with getting granular or powdered magnetic expansion polymeric adsorbent after above-mentioned gluey polymerisate chopping, drying, the pulverizing.
A kind of preparation method of magnetic expansion polymeric adsorbent, it may further comprise the steps:
1) weight part is respectively greater than zero and smaller or equal to 50 parts magnetic powder, 50.0～100.0 parts water-soluble vinyl unsaturated monomer, 0.1～2.0 part linking agent, 0.05～10.0 part initiator and water mixing; Obtain mixture; Wherein, Water mixes the aqueous solution that obtains the water-soluble vinyl unsaturated monomer with the water-soluble vinyl unsaturated monomer, and the mass percentage concentration of the aqueous solution of water-soluble vinyl unsaturated monomer is 15%～30%;
2) at 10～80 ℃ said mixture is disperseed, obtain aqueous mixture;
3) suspension dispersive agent is scattered in the non-polar solvent, the mass percentage concentration of said suspension dispersive agent is 0.1%～10%, and deoxygenation then forms oil phase;
4) with step 2) aqueous mixture that obtains is added drop-wise in the above-mentioned oil phase, stirs, 10～80 ℃ of reactions 2～7 hours down;
5) said magnetic expansion polymeric adsorbent is filtered, washed, is drying to obtain to above-mentioned reaction product.
In the such scheme, said initiator is water-soluble radical polymerization initiator or water soluble oxidized reduction initiator, and said water-soluble radical polymerization initiator comprises persulphate.
A kind of preparation method of magnetic expansion polymeric adsorbent, it may further comprise the steps:
1) weight part is respectively greater than zero and smaller or equal to 50 parts magnetic powder, 50.0～100.0 parts water-soluble vinyl unsaturated monomer, 0.1～2.0 part linking agent and an amount of water mixing; Obtain mixture; Wherein, Water mixes the aqueous solution that obtains the water-soluble vinyl unsaturated monomer with the water-soluble vinyl unsaturated monomer, and the mass percentage concentration of the aqueous solution of water-soluble vinyl unsaturated monomer is 15%～35%, and said mixture is disperseed;
2) at room temperature, the mixture after the above-mentioned dispersion was reacted after 2～3 hours under ultraviolet light irradiation, elevated temperature to 70～90 a ℃ reaction was carried out slaking in 1～3 hour again, obtained gluey polymerisate;
3) with getting granular or powdered magnetic expansion polymeric adsorbent after above-mentioned gluey polymerisate chopping, drying, the pulverizing.
A kind of preparation method of magnetic expansion polymeric adsorbent, it may further comprise the steps:
1) weight part is respectively greater than zero and smaller or equal to 50 parts magnetic powder, 50.0～100.0 parts water-soluble vinyl unsaturated monomer, 0.1～2.0 part linking agent and water mixing; Obtain mixture; Wherein, Water mixes the aqueous solution that obtains the water-soluble vinyl unsaturated monomer with the water-soluble vinyl unsaturated monomer, and the mass percentage concentration of the aqueous solution of water-soluble vinyl unsaturated monomer is 15%～30%;
2) at 10～80 ℃ said mixture is disperseed, obtain aqueous mixture;
3) suspension dispersive agent is scattered in the non-polar solvent, the mass percentage concentration of said suspension dispersive agent is 0.1%～10%, and deoxygenation then forms oil phase;
4) with step 2) aqueous mixture that obtains is added drop-wise in the above-mentioned oil phase, stirs, and reaction stopped irradiation after 2～3 hours under ultraviolet light irradiation, and ℃ reacted 2～7 hours elevated temperature to 40～90 again;
5) said magnetic expansion polymeric adsorbent is filtered, washed, is drying to obtain to above-mentioned reaction product.
The invention has the beneficial effects as follows: utilize the macromolecule network process of expansion to strengthen in water body or in the soil or in solid-liquid suspension (mixing) system the adsorption and enrichment that expands such as metals ion such as heavy metal ion; Have simultaneously easily and from water body, soil, solid-liquid suspension system, separated by magnet or magnetic separation machinery; Method of manufacture is simple, cost is low; Turgidity is high; Can be widely used in thermopnore or preparation equipment and carry out robotization mass metal ion isolation, be suitable for sector applications such as environment protection, Pollution abatement, bioseparation, ore dressing.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to following embodiment.
Introduce related magnetic powder, water-soluble vinyl unsaturated monomer, linking agent, initiator, reaction medium and auxiliary agent among following all embodiment of the present invention below at first in detail.
1. magnetic powder
Magnetic powder mainly refers to contain powder, the iron powder of ferromagnetic mineral, or through becoming the material of magnetic mineral after the processing, like magnetic product that the rhombohedral iron ore reduction is obtained etc., or iron ion is adsorbed in the hydrogel powdery magnetic of in-situ preparing.Median size is 0.1～150 μ m, is preferably 1.0-100 μ m.Ferromagnetic mineral itself has stronger magnetic, and the specific magnetising moment is very big under the outside magnetic field effect, and magnetite is typical ferromagnetic mineral.It is strong and weak to regulate how many adjustable magnetic hydrogel magnetic of magnetic powder content, its addition be weight part greater than zero and smaller or equal to 50 parts, be preferably 1.0～30.0 parts.
2. water-soluble vinyl unsaturated monomer
The water-soluble vinyl unsaturated monomer is the main body that forms hydrogel, also is to bring adsorption group, produces the main internal cause of absorption property.Typical water-soluble ionic-type vinyl unsaturated monomer is: acrylic or methacrylic acid and verivate thereof.Typical nonionic monomers is: acrylic amide and verivate thereof.Wherein preferably the water-soluble vinyl unsaturated monomer is 2-acrylamido-2-methyl propane sulfonic acid (hereinafter to be referred as AMPS); Acrylic amide (hereinafter to be referred as AM); Wherein a kind in vinylformic acid (hereinafter to be referred as AA), these monomer mixtures more than 2 kinds or 2 kinds, if during mixture, its blending ratio is not limit; Its consumption is 50.0～100.0 parts of weight parts, is preferably 70.0-100.0 part.
3. linking agent
At least contain two polymerisable unsaturated groups in the cross-linker molecules, these linking agents make hydrogel form crosslinked or lightly crosslinked three-dimensional net structure at body in mutually, regulate its its gel-strength of consumption adjustable and water-retaining capacity.Typical linking agent has: N, N '-methylene-bisacrylamide, consumption are 0.1～2.0 part of weight part.
4. initiator
The water-soluble radical polymerization initiator that is fit to water solution polymerization process or inverse suspension polymerization method is a persulphate, as: Potassium Persulphate, Sodium Persulfate, ammonium persulphate, these water soluble starters can mix use.Also can fit in redox system with reducing substances such as ferrous ion, sodium sulfite anhy 96, S-WAT etc. uses.Each proportioning components is confirmed by the quantitative relation of chemical equation when being used.Initiator amount is 0.05～10.0 part of a weight part, preferred 0.1～2.0 part.Kick off temperature is 10 ℃～80 ℃, preferred 65 ℃～75 ℃ of single initiator, and the preferred temperature of redox initiator is 20 ℃～50 ℃.
5. reaction medium and auxiliary agent
When adopting water solution polymerization process, reaction medium is a water; When adopting the inverse suspension polymerization method, reaction medium is a non-polar solvent, like hexanaphthene, kerosene etc.Add tensio-active agent such as op simultaneously, this dish, or tween does suspension dispersive agent and carries out suspended dispersed, and addition is a mass percentage concentration 0.1%～10.0%.
Below the dispersing method mentioned among all embodiment can select for use impeller to carry out dispersed with stirring or disperse with colloidal mill, or adopt UW to carry out ultra-sonic dispersion.
Among the present invention, adopt following method to measure and calculate the turgidity of inhaling zero(ppm) water, tap water and saline water:
The granulated material that takes by weighing after 0.5～1.0g drying treatment places the 500-1000ml beaker; Granulated material after adding 450～900ml zero(ppm) water or tap water or taking by weighing 0.5～1.0g drying treatment places the 150ml beaker to add 100ml 0.9%NaCl solution; After leaving standstill 24 hours; With unnecessary water elimination, weigh up gel quality affects with 100 order mesh screens, be calculated as follows turgidity:
Turgidity=(gel quality affects-xerogel quality)/xerogel quality
Among the present invention,, adopt different analysis test methods to measure concentration of metal ions and change, characterize adsorptive power with adsorptive capacity (mg/g dried resin) according to the different metallic ion.
Magnetic expansion polymeric adsorbent by the present invention's preparation has 10～300 times of turgiditys, and Cu (II), Cd (II), Pb (II), Zn (II), Cr (III), Hg (II), As (III) etc. are had strong adsorptive power, and easy-to-use magnetic technology is separated.
Embodiment 1:
In the 1000ml beaker, add AMPS, each 50g of AM; Add water and be mixed with the aqueous solution that mass percentage concentration is the water-soluble vinyl unsaturated monomer of 40 %; Stir and add N down, N '-methylene-bisacrylamide (linking agent) 0.1g, Potassium Persulphate 0.05 gram, stirring and dissolving; Again median size 10.0 μ m, grade are added wherein 75 ℃ of dispersed with stirring 5 minutes greater than the magnetite powder 1.0g of TFe50%; Mixture after the above-mentioned dispersion was cooled to 10 ℃ of reactions after 3 hours, was increased to 80 ℃ of reactions 1 hour again, obtained gel (gluey polymerisate); The gel chopping that generates is to 2～10mm, in following 40 ℃ of dryings of vacuum condition 5 hours to water cut less than 10wt%, through mechanical disintegration to 0.1～5.0mm; Finally obtain particulate state magnetic expansion polymeric adsorbent finished product, its turgidity is 80～90, to Cd (II); Cu (II); The adsorptive capacity of Cr (III) is 20～400mg/g dried resin, explains that the expansion loading capacity is big, high adsorption capacity.
Embodiment 2:
In the 1000ml beaker, add 20g AMPS, 80g AM; Add water and be mixed with the aqueous solution that mass percentage concentration is 20% water-soluble vinyl unsaturated monomer; Stir and add N, N '-methylene-bisacrylamide 2.0g, Potassium Persulphate 1.0g, sodium sulfite anhy 96 1.0g, stirring and dissolving down; Again median size 100.0 μ m, grade are added wherein 70 ℃ of dispersed with stirring 15 minutes greater than TFe20% magnetite powder 3.0g; Mixture after the above-mentioned dispersion was cooled to 50 ℃ of reactions after 3 hours, was increased to 70 ℃ of reactions 3 hours again, obtained gel (gluey polymerisate); The gel chopping that generates is to 2～10mm, and 80 ℃ of vacuum-drying 3 hours to water cut is less than 10wt%, through mechanical disintegration to 0.1～5.0mm; Finally obtain particulate state magnetic expansion polymeric adsorbent finished product, its turgidity is 10～30, to Cd (II); Cu (II); The adsorptive capacity of Pb (II) is 20～400mg/g dried resin, explains that the expansion loading capacity is big, high adsorption capacity.
Embodiment 3:
In the 1000ml beaker, add 20g AMPS, 60g AM; 20g AA adds water and is mixed with the aqueous solution that mass percentage concentration is 15% water-soluble vinyl unsaturated monomer, stirs to add N down; N '-methylene-bisacrylamide 1.0g, Sodium Persulfate 10.0 grams; Stirring and dissolving adds median size 80.0 μ m, grade wherein greater than TFe30% magnetite powder 30.0g again, 70 ℃ of ultra-sonic dispersion 15 minutes; Mixture after the above-mentioned dispersion is cooled to 20 ℃, disperses through colloidal mill, react 3 hours again after, be increased to 90 ℃ of reactions 5 hours again, obtain gel (gluey polymerisate); The gel chopping that generates is to 2～10mm, and 70 ℃ of dryings 4 hours to water cut is less than 10wt%, through mechanical disintegration to 0.1～5.0mm; Finally obtain particulate state magnetic expansion polymeric adsorbent finished product, its turgidity is 200～300, to Cd (II); Cu (II); The adsorptive capacity of Pb (II) is 20～400mg/g dried resin, explains that the expansion loading capacity is big, high adsorption capacity.
Embodiment 4:
In the 1000ml beaker, add 30g AMPS, 40g AM; Add water and be mixed with the aqueous solution that mass percentage concentration is 30% water-soluble vinyl unsaturated monomer; Stir and add N down, N '-methylene-bisacrylamide 1.5g, ammonium persulphate 5.0 grams, stirring and dissolving; Again median size 40.0 μ m, grade are added wherein 70 ℃ of dispersed with stirring 15 minutes greater than TFe50% magnetite powder 5.0g; Mixture after the above-mentioned dispersion was cooled to 65 ℃ of reactions after 3 hours, was increased to 70 ℃ of reactions 3 hours again, obtained gel (gluey polymerisate); The gel chopping that generates is to 2～10mm, and 120 ℃ of dryings 3 hours to water cut is less than 10wt%, through mechanical disintegration to 0.1～5.0mm; Finally obtain particulate state magnetic expansion polymeric adsorbent finished product, its turgidity is 20～30, to Cd (II); Cu (II); The adsorptive capacity of Pb (II) is 20～400mg/g dried resin, explains that the expansion loading capacity is big, high adsorption capacity.
Embodiment 5:
In the 1000ml beaker, add 25g AMPS, 25g AM; Add water and be mixed with the aqueous solution that mass percentage concentration is 30% water-soluble vinyl unsaturated monomer; Stir and add N down, N '-methylene-bisacrylamide 1.5g, Potassium Persulphate 5.0 grams, stirring and dissolving; Again median size 1.0 μ m, grade are added wherein 70 ℃ of dispersed with stirring 15 minutes greater than TFe50% magnetite powder 50.0g; Mixture after the above-mentioned dispersion was warming up to 75 ℃ of reactions after 3 hours, was increased to 90 ℃ of reactions 3 hours again, obtained gel (gluey polymerisate); The gel chopping that generates is to 2～10mm, and 120 ℃ of dryings 3 hours to water cut is less than 10wt%, through mechanical disintegration to 0.1～5.0mm; Finally obtain particulate state magnetic expansion polymeric adsorbent finished product, its turgidity is 100～120, to Cd (II); Cu (II); The adsorptive capacity of Pb (II) is 20～400mg/g dried resin, explains that the expansion loading capacity is big, high adsorption capacity.
Embodiment 6:
With median size 48.0 μ m, smart powder (rhombohedral iron ore) 20g of TFe60% iron mixes the back and carries out magnetizing roasting at 400～600 ℃ with capacity powdered carbon (C powder), obtain magnetite powder.
In the 1000ml beaker, add 60g AMPS, 20g AM; 20gAA adds water and is mixed with the aqueous solution that mass percentage concentration is 25% water-soluble vinyl unsaturated monomer, stirs to add N down; N '-methylene-bisacrylamide 1.0g, Potassium Persulphate 0.1 gram; Stirring and dissolving, the magnetite powder 10.0g that will go up method preparation again adds wherein, 70 ℃ of dispersed with stirring 15 minutes; Mixture after the above-mentioned dispersion was cooled to 50 ℃ of reactions after 3 hours, was increased to 70 ℃ of reactions 3 hours again, obtained gel (gluey polymerisate); The gel chopping that generates is to 2～10mm, and 120 ℃ of dryings 3 hours to water cut is less than 10wt%, through mechanical disintegration to 0.1～5.0mm; Finally obtain particulate state magnetic expansion polymeric adsorbent finished product, its turgidity is 100～120, to Cd (II); Cu (II); The adsorptive capacity of Pb (II) is 20～400mg/g dried resin, explains that the expansion loading capacity is big, high adsorption capacity.
Embodiment 7:
Under the room temperature nitrogen protection, in the 1000ml beaker, add 30g AMPS, 10g AM; 10gAA adds water and is mixed with the aqueous solution that mass percentage concentration is 25% water-soluble vinyl unsaturated monomer, stirs to add N, N '-methylene-bisacrylamide 0.6g, stirring and dissolving down; Add each 2.5g of iron(ic)chloride and ferrous sulfate again, after the stirring and dissolving, solution was penetrated 2 hours with the 40w uv illumination; Stop irradiation, be increased to 70 ℃ of reactions 3 hours again, obtain gel (gluey polymerisate); The gel chopping that generates is to 2～10mm, adds mass percentage concentration and is 2% alkali lye 400ml and soaked 12 hours, leaches gel; 90 ℃ of dryings 8 hours to water cut through mechanical disintegration to 0.1～5.0mm, finally obtains particulate state magnetic expansion polymeric adsorbent finished product less than 10wt%; Its turgidity is 20～30; Adsorptive capacity to Zn (II), Cr (III), Hg (II), As (III) is 20～400mg/g dried resin, explains that the expansion loading capacity is big, high adsorption capacity.
Embodiment 8:
In the 1000ml beaker, add 30g AMPS, 10g AM; 10g AA adds water and is mixed with the aqueous solution that mass percentage concentration is 30% water-soluble vinyl unsaturated monomer, stirs to add N down; N '-methylene-bisacrylamide 0.6g, stirring and dissolving add median size 150.0 μ m, grade wherein greater than TFe50% magnetite powder 5.0g, after the stirring and dissolving again; In room temperature solution was penetrated 2 hours with the 40w uv illumination; Stop irradiation, be increased to 70 ℃ of reactions 3 hours again, obtain gel (gluey polymerisate); The gel chopping that generates is to 2～10mm, and 90 ℃ of dryings 8 hours to water cut is less than 10wt%, through mechanical disintegration to 0.1～5.0mm; Finally obtain particulate state magnetic expansion polymeric adsorbent finished product, its turgidity is 100～120, to Cd (II); Cu (II); The adsorptive capacity of Pb (II) is 20～400mg/g dried resin, explains that the expansion loading capacity is big, high adsorption capacity.
Embodiment 9:
3g Span-60 is scattered in the hexanaphthene, and the mass percentage concentration of this Span-60 is 0.1%.Be warming up to 75 ℃, logical nitrogen flooding is removed oxygen wherein, opens to stir Span-60 is dissolved fully, forms oil phase.
In the 100ml beaker, add 6.0g AMPS, 2.0g AM; 2.0gAA, add water and be mixed with the aqueous solution that mass percentage concentration is 30% water-soluble vinyl unsaturated monomer, stir and add 0.2g N down; N '-methylene-bisacrylamide, 0.2 gram Potassium Persulphate; Stirring and dissolving adds 1.0g median size 20.0 μ m, grade wherein greater than the TFe30% magnetite powder again, and 70 ℃ of dispersed with stirring got aqueous mixture in 15 minutes.
Again aqueous mixture is added drop-wise in the above-mentioned oil phase, stirs, at 70 ℃ of following polymerization 2h.Treat that temperature reduces to room temperature, cross and filter partical, use washing with alcohol; Less than 10wt%, obtain particulate state magnetic expansion polymeric adsorbent finished product in 80 ℃ of vacuum-drying to water cut, its turgidity is 80～100; To Cd (II), Cu (II), the adsorptive capacity of Pb (II) is 20～400mg/g dried resin; Explain that the expansion loading capacity is big, high adsorption capacity.
Embodiment 10:
3g op-10 is scattered in the kerosene, and the mass percentage concentration of this op-10 is 10%.The oxygen that the logical nitrogen flooding of normal temperature is removed wherein forms oil phase.
In the 100ml beaker, add 3.0g AMPS, 1.0g AM; 1.0gAA, add water and be mixed with the aqueous solution that mass percentage concentration is 15% water-soluble vinyl unsaturated monomer, stir and add 0.01g N down; N '-methylene-bisacrylamide, 0.005g Potassium Persulphate; Stirring and dissolving adds 0.1g median size 20.0 μ m, grade wherein greater than the TFe30% magnetite powder again, and 80 ℃ of dispersed with stirring got aqueous mixture in 15 minutes.
Again aqueous mixture is added drop-wise in the above-mentioned oil phase, stirs, at 80 ℃ of following polymerization 5h.Treat that temperature reduces to room temperature, cross and filter partical, use methanol wash; Less than 10wt%, obtain particulate state magnetic expansion polymeric adsorbent finished product in 120 ℃ of vacuum-drying to water cut, its turgidity is 100～120; To Cd (II), Cu (II), the adsorptive capacity of Pb (II) is 20～400mg/g dried resin; Explain that the expansion loading capacity is big, high adsorption capacity.
Embodiment 11:
With the 3g tween be scattered in the hexanaphthene, the mass percentage concentration of this tween is 5%.Stirring and dissolving, the oxygen that logical nitrogen flooding is removed wherein forms oil phase.
In the 100ml beaker, add 3.0g AMPS, 2.0g AM; 2.0gAA, add water and be mixed with the aqueous solution that mass percentage concentration is 20% water-soluble vinyl unsaturated monomer, stir and add 0.1g N down; N '-methylene-bisacrylamide, 0.5 gram Potassium Persulphate; Stirring and dissolving adds 3.0g median size 20.0 μ m, grade wherein greater than the TFe30% magnetite powder again, and 50 ℃ of dispersed with stirring got aqueous mixture in 15 minutes.
Again aqueous mixture is added drop-wise in the above-mentioned oil phase, stirs, at 40 ℃ of following polymerase 17 h.Treat that temperature reduces to room temperature, cross and filter partical, use washing with alcohol; Obtain particulate state magnetic expansion polymeric adsorbent finished product in 80 ℃ of vacuum-drying to water cut less than 10wt%, its turgidity is 250～260, to Cd (II); Cu (II); The adsorptive capacity of Pb (II) is 20～400mg/g dried resin, explains that the expansion loading capacity is big, high adsorption capacity.
Embodiment 12:
With the 3g tween be scattered in the hexanaphthene, the mass percentage concentration of this tween is 6%.Stirring and dissolving, the oxygen that logical nitrogen flooding is removed wherein forms oil phase.
In the 100ml beaker, add 3.0g AMPS, 3.0g AM; 3.0gAA, add water and be mixed with the aqueous solution that mass percentage concentration is 20% water-soluble vinyl unsaturated monomer, stir and add 0.2g N down; N '-methylene-bisacrylamide, 1 gram Potassium Persulphate; Stirring and dissolving adds 5.0g median size 20.0 μ m, grade wherein greater than the TFe30% magnetite powder again, and 40 ℃ of dispersed with stirring got aqueous mixture in 15 minutes.
Again aqueous mixture is added drop-wise in the above-mentioned oil phase, stirs, suspension-s was penetrated 2 hours with the 40w uv illumination, stop irradiation, be warming up to 50 ℃ of following polymerization 5h.Treat that temperature reduces to room temperature, cross and filter partical, use washing with alcohol; Less than 10wt%, obtain particulate state magnetic expansion polymeric adsorbent finished product in 40 ℃ of vacuum-drying to water cut, its turgidity is 290～300; To Cd (II), Cu (II), the adsorptive capacity of Pb (II) is 20～400mg/g dried resin; Explain that the expansion loading capacity is big, high adsorption capacity.
Each raw material that the present invention is cited, and the bound of each raw material of the present invention, interval value, and the bound of processing parameter (like temperature, concentration etc.), interval value can both realize the present invention, do not enumerate embodiment one by one at this.
Claims (11)
1. magnetic expansion polymeric adsorbent; It is characterized in that, it by comprise weight part be respectively greater than zero and smaller or equal to 50 parts magnetic powder, 50.0～100.0 parts the water-soluble vinyl unsaturated monomer, and 0.1～2.0 part linking agent be composited through polyreaction.
2. magnetic expansion polymeric adsorbent according to claim 1; It is characterized in that; Said magnetic powder chosen from Fe magnetic mineral or through becoming the material of magnetic mineral or iron ion is adsorbed in the hydrogel after the processing; The powdery magnetic of in-situ preparing, the median size of said magnetic powder are 0.1～150 μ m.
3. magnetic expansion polymeric adsorbent according to claim 2 is characterized in that, the median size of said magnetic powder is 1.0-100 μ m.
4. according to claim 1 or 2 or 3 described magnetic expansion polymeric adsorbents, it is characterized in that the weight part of said water-soluble vinyl unsaturated monomer is 70.0～100.0 parts.
5. magnetic expansion polymeric adsorbent according to claim 1; It is characterized in that said water-soluble vinyl unsaturated monomer is 2-acrylamido-2-methyl propane sulfonic acid, acrylic amide; Or the one or any two or more mixing in the vinylformic acid, mix with arbitrary proportion during mixing.
6. magnetic expansion polymeric adsorbent according to claim 1 is characterized in that, said linking agent comprises that per molecule contains two polymerisable unsaturated groups at least, and said linking agent is N, N '-methylene-bisacrylamide.
7. method for preparing magnetic expansion polymeric adsorbent as claimed in claim 1 is characterized in that it may further comprise the steps:
1) weight part is respectively greater than zero and smaller or equal to 50 parts magnetic powder, 50.0～100.0 parts water-soluble vinyl unsaturated monomer, 0.1～2.0 part linking agent, 0.05～10.0 part initiator and water mixing; Obtain mixture; Wherein, Water mixes the aqueous solution that obtains the water-soluble vinyl unsaturated monomer with the water-soluble vinyl unsaturated monomer; The mass percentage concentration of the aqueous solution of water-soluble vinyl unsaturated monomer is 15%～40%, and said mixture is disperseed;
2) make mixture after the above-mentioned dispersion in 10～80 ℃ of heating 1～3 hour, elevated temperature to 70～90 a ℃ reaction was carried out slaking in 1～5 hour again, obtained gluey polymerisate;
3) with getting granular or powdered magnetic expansion polymeric adsorbent after above-mentioned gluey polymerisate chopping, drying, the pulverizing.
8. method for preparing magnetic expansion polymeric adsorbent as claimed in claim 1 is characterized in that it may further comprise the steps:
1) weight part is respectively greater than zero and smaller or equal to 50 parts magnetic powder, 50.0～100.0 parts water-soluble vinyl unsaturated monomer, 0.1～2.0 part linking agent, 0.05～10.0 part initiator and water mixing; Obtain mixture; Wherein, Water mixes the aqueous solution that obtains the water-soluble vinyl unsaturated monomer with the water-soluble vinyl unsaturated monomer, and the mass percentage concentration of the aqueous solution of water-soluble vinyl unsaturated monomer is 15%～30%;
2) at 10～80 ℃ said mixture is disperseed, obtain aqueous mixture;
3) suspension dispersive agent is scattered in the non-polar solvent, the mass percentage concentration of said suspension dispersive agent is 0.1%～10%, and deoxygenation then forms oil phase;
4) with step 2) aqueous mixture that obtains is added drop-wise in the above-mentioned oil phase, stirs, 10～80 ℃ of reactions 2～7 hours down;
5) said magnetic expansion polymeric adsorbent is filtered, washed, is drying to obtain to above-mentioned reaction product.
9. according to claim 7 or 8 described preparing methods, it is characterized in that said initiator is water-soluble radical polymerization initiator or water soluble oxidized reduction initiator, said water-soluble radical polymerization initiator comprises persulphate.
10. method for preparing magnetic expansion polymeric adsorbent as claimed in claim 1 is characterized in that it may further comprise the steps:
1) weight part is respectively greater than zero and smaller or equal to 50 parts magnetic powder, 50.0～100.0 parts water-soluble vinyl unsaturated monomer, 0.1～2.0 part linking agent and an amount of water mixing; Obtain mixture; Wherein, Water mixes the aqueous solution that obtains the water-soluble vinyl unsaturated monomer with the water-soluble vinyl unsaturated monomer, and the mass percentage concentration of the aqueous solution of water-soluble vinyl unsaturated monomer is 15%～35%, and said mixture is disperseed;
2) at room temperature, the mixture after the above-mentioned dispersion was reacted after 2～3 hours under ultraviolet light irradiation, elevated temperature to 70～90 a ℃ reaction was carried out slaking in 1～3 hour again, obtained gluey polymerisate;
3) with getting granular or powdered magnetic expansion polymeric adsorbent after above-mentioned gluey polymerisate chopping, drying, the pulverizing.
11. a method for preparing magnetic expansion polymeric adsorbent as claimed in claim 1 is characterized in that it may further comprise the steps:
1) weight part is respectively greater than zero and smaller or equal to 50 parts magnetic powder, 50.0～100.0 parts water-soluble vinyl unsaturated monomer, 0.1～2.0 part linking agent and water mixing; Obtain mixture; Wherein, Water mixes the aqueous solution that obtains the water-soluble vinyl unsaturated monomer with the water-soluble vinyl unsaturated monomer, and the mass percentage concentration of the aqueous solution of water-soluble vinyl unsaturated monomer is 15%～30%;
2) at 10～80 ℃ said mixture is disperseed, obtain aqueous mixture;
3) suspension dispersive agent is scattered in the non-polar solvent, the mass percentage concentration of said suspension dispersive agent is 0.1%～10%, and deoxygenation then forms oil phase;
4) with step 2) aqueous mixture that obtains is added drop-wise in the above-mentioned oil phase, stirs, and reaction stopped irradiation after 2～3 hours under ultraviolet light irradiation, and ℃ reacted 2～7 hours elevated temperature to 40～90 again;
5) said magnetic expansion polymeric adsorbent is filtered, washed, is drying to obtain to above-mentioned reaction product.
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