CN109438597A - Magnetic polydivinylbenzene microsphere resin and preparation method and application thereof - Google Patents
Magnetic polydivinylbenzene microsphere resin and preparation method and application thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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Abstract
The invention discloses a magnetic polydivinylbenzene microsphere resin and a preparation method and application thereof, the magnetic polydivinylbenzene microsphere resin comprises a polydivinylbenzene microsphere resin framework and magnetic particles, the magnetic particles are uniformly distributed in the polydivinylbenzene microsphere resin framework, and the specific surface area of the magnetic polydivinylbenzene microsphere resin is 800m2/g～1200m2(ii) in terms of/g. The preparation method comprises the following steps: preparing a dispersion comprising a mixture of gelatin, trisodium phosphate and disodium phosphate; adding the modified magnetic particles, divinylbenzene, a pore-forming agent and an initiator into the dispersion liquid to carry out polymerization reaction; and cleaning and drying the obtained product to obtain the magnetic polydivinylbenzene microsphere resin. The magnetic polydivinylbenzene microsphere resin has the advantages of large specific surface area, narrow particle size distribution, good balling performance and high reusability, and can be used for efficiently removing nitrobenzene compounds; the preparation method has the advantages of simple operation, short process flow, short time consumption, simple raw materials and low cost.
Description
Technical field
The present invention relates to nitrobenzene class pollutant adsorbent material field, more particularly to magnetic poly- divinylbenzene microspheres resin and
Preparation method and application.
Background technique
Nitrobenzene compounds are widely used in the different types of product of production, such as dyestuff, explosive and agrochemical.It is often
It is released in the production process of explosive, organic chemicals and plastics etc..Nitrobenzene compounds are a kind of carcinogenic contaminants,
High risk may also be constituted to ecology and human health even at a low concentration.Due to its toxicity, nitrobenzene compounds are beautiful
Bureau for Environmental Protection, state is classified as priority pollutant.Therefore, people increasingly focus on the removal nitrobenzene chemical combination from water environment
Object.It can be divided into three categories from the conventional method for removing nitrobenzene compounds in aqueous solution: from physical method, chemical method and biology
Reason.Absorption resin refers to the artificial synthesized high molecular material of the one kind that can be used for water process, has comprehensive more than natural resin
A kind of material of performance.Absorption resin typically belongs to micron level, and according to the difference of synthesis condition, partial size is in 300 μm~1000 μ
M or so, mechanical strength is preferable, is smooth spherical shape or elliposoidal, and the specific surface area of resin has emphatically the absorption property of resin
It influences, the absorption property of the general large specific surface area of homogenous resins is more preferable.In addition, the molecular size of adsorbate and absorption resin hole
Matching degree between road structure size is also an important factor for influencing absorption property.Absorption resin also has excellent thermostabilization
Property, regeneration can be realized by simple and nondestructive method.Therefore, absorption resin is adsorbent from aqueous solution
Remove one of the most widely used candidate of pollutant.
Prepared on the market at present is the microballoon resin containing polarized or non-polar monomer, and wherein raw material is more multiple
It is miscellaneous, specific surface area is lower.The particle diameter distribution of existing microballoon resin different from due to the difference of dispersing agent, on the market mainly with
Polyvinyl alcohol is magnetic microsphere there is particle diameter distributions wide, the poor disadvantage of particle balling preparation of dispersing agent preparation.It is inhaled to improve
The performance of attached resin, the existing resin microsphere for adsorption treatment generally use two or more starting monomers and are polymerize,
And generally existing rear the step of modifying, complicated operation.The present invention is by using single monomer, the preparation of simple aggregation process
The excellent poly- divinylbenzene microspheres resin of magnetism of a kind of physicochemical property out.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art, provide a kind of large specific surface area, partial size point
Cloth is narrow, balling-up is good, reusable property is high, can efficiently remove the superior magnetism poly- two of nitrobenzene compounds, absorption property
Ethenylbenzene microballoon resin；A kind of magnetism poly- two easy to operate, process flow is short, time-consuming is short, raw material is simple, at low cost is also provided
Ethenylbenzene microballoon resin preparation method.
In order to solve the above technical problems, the invention adopts the following technical scheme:
A kind of poly- divinylbenzene microspheres resin of magnetism, the poly- divinylbenzene microspheres resin of magnetism includes that poly- divinylbenzene is micro-
Pelletized resin skeleton and magnetic-particle, the magnetic-particle are uniformly distributed in poly- divinylbenzene microspheres resin matrix, the magnetism
The specific surface area of poly- divinylbenzene microspheres resin is 800m2/ g~1200m2/g。
The disclosure of the invention total as one, the present invention also provides a kind of preparation sides of the poly- divinylbenzene microspheres resin of magnetism
Method includes the following steps:
S1, dispersing agent being dissolved in water, the dispersing agent is the mixture for including gelatin, tertiary sodium phosphate and disodium hydrogen phosphate,
Obtain dispersion liquid；
S2, it is added into dispersion liquid using the modified magnetic-particle of oleic acid, succinic acid or fluorine ether acid, divinylbenzene, pore
Agent and initiator are uniformly mixed, then carry out polymerization reaction；
S3, to after the reaction was completed, the resulting product of polymerization reaction be cleaned, is dried, obtain magnetic poly- divinylbenzene
Microballoon resin.
In the preparation method of the above-mentioned poly- divinylbenzene microspheres resin of magnetism, it is preferable that described using oil in the S2
The preparation method of the modified magnetic-particle of acid, succinic acid or fluorine ether acid includes: to be lived using ethyl alcohol or methanol to magnetic-particle
Change, ammonium hydroxide and activated magnetic-particle are added to the water, obtain the mixed liquor of alkalinity, and is added into mixed liquor dissolved with oil
The organic solvent of acid, succinic acid or fluorine ether acid, the organic solvent are acetone, ethyl alcohol or methanol, are stirred modification, described to change
Property carries out under an inert atmosphere, and after the completion of to be modified, pH value is adjusted to 6~8, isolates magnetic-particle, to gained magnetic-particle
It cleaned, dried to get modified magnetic-particle is arrived.
In the preparation method of the above-mentioned poly- divinylbenzene microspheres resin of magnetism, it is preferable that in the S1, the dispersing agent
Additional amount is the 1.6%~14.5% of water quality；In the dispersing agent, the quality of the gelatin, tertiary sodium phosphate, disodium hydrogen phosphate
Than for (1~3): 1: (2~5)；The concentration of tertiary sodium phosphate described in gained dispersion liquid is 2g/L~8g/L.
In the preparation method of the above-mentioned poly- divinylbenzene microspheres resin of magnetism, it is preferable that in the S2, the polymerization reaction
Temperature be 60 DEG C~120 DEG C；The time of the polymerization reaction is 6h~for 24 hours.
In the preparation method of the above-mentioned poly- divinylbenzene microspheres resin of magnetism, it is preferable that further include to dispersion in the S1
The step of sodium chloride is added in liquid；The quality of the sodium chloride is the 5%~20% of the water quality.
In the preparation method of the above-mentioned poly- divinylbenzene microspheres resin of magnetism, it is preferable that in the S2, the magnetic-particle
For the oxide Fe of iron3O4、γ-Fe2O3, nickel oxide or at least one of the oxide of cobalt；The grain of the magnetic-particle
Diameter is 5nm~20nm；The dosage of the magnetic-particle is the 1%~10% of divinylbenzene quality.
In the preparation method of the above-mentioned poly- divinylbenzene microspheres resin of magnetism, it is preferable that the oleic acid, succinic acid or fluorine ether
The dosage of acid is 1~10 times of the magnetic-particle quality；
The concentration of the ammonium hydroxide is 25wt.%~28wt.%；The volume ratio of the ammonium hydroxide and water is 1: (50~100).
In the preparation method of the above-mentioned poly- divinylbenzene microspheres resin of magnetism, it is preferable that in the S2, the pore-foaming agent is
At least one of cyclohexanol, amylalcohol, toluene, dimethylbenzene, lauryl alcohol, heptane and isooctane；The additional amount of the pore-foaming agent is two
The 10%~500% of Ethenylbenzene quality；
In the preparation method of the above-mentioned poly- divinylbenzene microspheres resin of magnetism, it is preferable that the initiator is benzoyl peroxide
Formyl and/or azodiisobutyronitrile；The additional amount of the initiator is the 0.5%~8% of divinylbenzene quality.
The inventive concept total as one, the present invention also provides a kind of above-mentioned poly- divinylbenzene microspheres resin of magnetism or on
The poly- divinylbenzene microspheres resin of magnetism made from the preparation method stated is used for the absorption of nitrobenzene compounds.
Compared with the prior art, the advantages of the present invention are as follows:
1, the poly- divinylbenzene microspheres resin balling-up of magnetism of the invention is good, large specific surface area, and particle diameter distribution is narrow, repeatable
Usability is high, it is superior efficiently to remove nitrobenzene compounds, absorption property.
2, it has been investigated that, the present invention uses specific mixed dispersant, is single with single crosslinking agent, that is, divinylbenzene
Modified magnetic-particle is added in body raw material, carries out polymerization reaction, prepares that balling-up is good, specific surface area is high, particle diameter distribution is narrow
The poly- divinylbenzene microspheres resin of magnetism.Preparation method process flow of the invention is short, time-consuming short, at low cost, simplifies preparation
Program improves specific surface area and phenyl ring utilization rate.
3, the present invention is modified magnetic-particle finished product using special process, can carry out high-volume and be modified, save the process
Time, to reduce cost, modified effect excellent.
4, the poly- divinylbenzene microspheres resin p-nitrophenyl class compound of magnetism of the invention has good absorption property, energy
It reaches and effectively removes nitrobenzene class pollutant in water removal, there is important application valence in adsorbing separations fields such as organic chemical waste water improvement
Value.The poly- divinylbenzene microspheres resin of magnetism of the invention is to 2- nitrotoleune, 2,4-DNT, 2,4,6- trinitrotoluene
Adsorption capacity respectively can be up to 394mg/g, 329mg/g, 244mg/g.
Detailed description of the invention
Fig. 1 is in embodiment 1 using the Fe of oleic acid before modified3O4With the modified obtained O-Fe of oleic acid3O4And oleic acid is red
Outer comparison diagram.
Fig. 2 is in embodiment 1 using the Fe of oleic acid before modified3O4With the modified obtained O-Fe of oleic acid3O4XRD comparison
Figure.
Fig. 3 is in embodiment 1 using the Fe of oleic acid before modified3O4With the modified obtained O-Fe of oleic acid3O4Hysteresis loop
Comparison diagram.
Fig. 4 is the infrared comparison diagram of the poly- divinylbenzene microspheres resin of magnetism of divinylbenzene and the preparation of the embodiment of the present invention 1.
Fig. 5 is the scanning electron microscope (SEM) photograph of the poly- divinylbenzene microspheres resin of magnetism prepared by the embodiment of the present invention 1.
Fig. 6 is the embodiment of the present invention 1~2, the partial size point of the poly- divinylbenzene microspheres resin of magnetism prepared by comparative example 1~3
Butut.
Fig. 7 is the embodiment of the present invention 1~2, and the nitrogen of the poly- divinylbenzene microspheres resin of magnetism prepared by comparative example 1~3 is inhaled
Attached-desorption curve.
Fig. 8 is that the embodiment of the present invention 3 measures the obtained poly- divinylbenzene microspheres resin of magnetism to 2,4,6- trinitrotoluene
Dynamic absorption curve.
Fig. 9 is that the embodiment of the present invention 3 measures the obtained poly- divinylbenzene microspheres resin of magnetism to 2,4-DNT
Dynamic absorption curve.
Figure 10 is the power that the embodiment of the present invention 3 measures the obtained poly- divinylbenzene microspheres resin of magnetism to 2- nitrotoleune
Learn adsorption curve.
Specific embodiment
The present invention is described in further details below with reference to Figure of description and specific embodiment.
A kind of preparation method of the poly- divinylbenzene microspheres resin of magnetism, comprising the following steps:
(1) magnetic-particle is modified: the purpose of this step is the magnetic metal oxide crossed using lipophilic organics modifications
Nano particle is magnetic core.Magnetic nanoparticle is taken to pass through 60 DEG C~100 DEG C ethyl alcohol or methanol eddy 10min~120min, it is dry,
It plays the activation to magnetic-particle and cleans magnetic-particle.The magnetic nanoparticle after drying, which is added to dropwise addition, again ammonia
In the three neck round bottom equipped with deionized water of water, ammonia concn is 25wt.%~28wt.%；Ammonium hydroxide and deionized water
Volume ratio is 1: (50~100).Adjusting mixing speed is 200rpm~1000rpm, and nitrogen or argon gas removal are passed through into solution
Temperature is risen to 60 DEG C~120 DEG C, and instill into mixed liquor then under nitrogen or ar gas environment by the dissolved oxygen in solution
Have been dissolved in one of oleic acid, succinic acid or the fluorine ether acid in one of organic solvent such as acetone, ethyl alcohol or methanol, reaction
After 10min~120min, it is further dropped into one of oleic acid, succinic acid, fluorine ether acid, to carry out two to magnetic nanoparticle surface
The modification of secondary supplement, the reaction was continued 10min~120min.After cooling, mixed solution pH is adjusted to 6~8 with hydrochloric acid or sulfuric acid, then
The particles of magnetic material after modification is separated using magnet, is cleaned using methanol, is dried in vacuo.Wherein, nano-magnetic
Particle is Fe3O4、γ-Fe2O3, the oxide of nickel, cobalt the magnetic good nano particle such as oxide.
(2) synthesis of magnetic poly- divinylbenzene microspheres resin: with adjacent divinylbenzene, divinylbenzene and in divinylbenzene
It is one or more be raw material monomer, using one kind of cyclohexanol, amylalcohol, toluene, dimethylbenzene, lauryl alcohol, heptane and isooctane
Or a variety of mixings make pore-foaming agent, are used as dispersing agent with the mixture of gelatin, tertiary sodium phosphate and disodium hydrogen phosphate, can add sodium chloride
Monomer solubility in water is reduced, makees initiator with benzoyl peroxide, azodiisobutyronitrile, is gathered using suspension polymerization
Close reaction, prepare divinylbenzene polymer, the temperature of polymerization reaction is 60 DEG C~120 DEG C, the time of polymerization reaction be 6h~
For 24 hours, the mixing speed of polymerization reaction is 200rpm~1000rpm, and distilled water, ethyl alcohol and acetone is selected to wash repeatedly, and removal causes
Hole agent and remaining dispersing agent, organic matter and inorganic salts, dry magnetic poly- divinylbenzene microspheres resin.
Magnetic-particle is Fe3O4、γ-Fe2O3, the oxide of nickel, cobalt oxide；The partial size of magnetic-particle be 5nm~
20nm；Particles of magnetic material dosage is the 1%~10% of monomer mass.
Pore-foaming agent is one or more mixing of cyclohexanol, amylalcohol, toluene, dimethylbenzene, lauryl alcohol, heptane and isooctane
Object, preferably toluene, dimethylbenzene or heptane, the additional amount of pore-foaming agent are the 10%~500% of divinylbenzene quality, preferably 150%
~200%.
The additional amount of initiator is the 0.5%~8% of monomer mass.
The additional amount of dispersing agent is the 1.6%~14.5% of deionized water quality, is the 20%~40% of monomer mass；Institute
State in dispersing agent, gelatin, tertiary sodium phosphate, disodium hydrogen phosphate mass ratio be (1~3): 1: (2~5), the tertiary sodium phosphate it is dense
Degree is 2g/L~8g/L.Wherein disodium hydrogen phosphate is Na2HPO4·12H2O。
The dosage of oleic acid, succinic acid or fluorine ether acid is 1~10 times of magnetic-particle quality；
The additional amount of sodium chloride is the 5%~20% of deionized water quality.
The temperature of polymerization reaction is preferably 80 DEG C~95 DEG C, and the time of polymerization reaction is preferably 6h~12h.
The obtained poly- divinylbenzene microspheres resin of magnetism contains a large amount of benzene ring structures, and specific surface area is high, and partial size is preferably 100
μm~200 μm, specific surface area 800m2/ g~1200m2/ g, such as can be 800~900m2/g。
Since the poly- divinylbenzene microspheres resin of magnetism of the invention is based on benzene ring structure, resin and nitrobenzene can be passed through
π-π effect between class compound is adsorbed, and the hydrophobicity and nitrobenzene compounds of resin skeleton itself can also be passed through
Hydrophobic part between occur hydrophobic adsorbent effect.The bridging that the present invention can be generated effectively using divinylbenzene in the reaction
Key increases duct quantity, increases the specific surface area of resin.
Embodiment 1
A kind of preparation method of the poly- divinylbenzene microspheres resin of magnetism of the invention, includes the following steps:
(1) synthesis of oil-soluble magnetic material:
By nano-magnetic Fe3O4By 80 DEG C of reflux 30min of 100mL ethyl alcohol, cooling drying.5g after drying is magnetic
Fe3O4The 500mL three-necked flask equipped with the 250mL deionized water that 2.5mL ammonium hydroxide (25wt.%~28wt.%) has been added dropwise is added
In, adjusting mixing speed is 450rpm, is passed through nitrogen, stirs 30min, removes oxygen in water, temperature is risen to 85 DEG C, and drip
Enter 25mL dissolved with the acetone of 5g oleic acid, after reacting 10min, 5g oleic acid is instilled, using the side to magnetic nano-particle multi-time modification
Formula keeps modification effect more preferable, the reaction was continued 30min.After cooling, gained mixed solution pH after reaction is adjusted to 7 with hydrochloric acid, is released
The self assembly effect between particle is modified, makes its sedimentation, then using magnet to magnetic Fe3O4Particle is separated, and methanol is used
Cleaning, vacuum drying.
(2) synthesis of magnetic poly- divinylbenzene microspheres resin:
S1, by 4g gelatin, 2g tertiary sodium phosphate and 10gNa2HPO4·12H2O is dissolved in 500mL ionized water as dispersed phase,
And 70g sodium chloride is added into dispersed phase, it is subsequently placed in the three neck round bottom of 1000mL；
S2, added into three neck round bottom by 50g to divinylbenzene, 5g by oleic acid modified Fe3O4Particle, 125g first
The oily phase of benzene and 1g benzoyl peroxide composition, is stirred under the mixing speed of 400rpm, is gradually heated to 95 DEG C, carries out
Polymerization reaction discharges after 12h.
S3, after reaction system is cooling, magnetic copolymer obtained is separated from reaction system using magnet, spend from
Sub- water cleans 3~5 times, then after clean 2 times with ethyl alcohol, acetone cleaning 1 time is dried in vacuo 8h, resulting resin is at 60 DEG C
For magnetic poly- divinylbenzene microspheres resin.
Embodiment 2
A kind of preparation method of the poly- divinylbenzene microspheres resin of magnetism of the invention, includes the following steps:
(1) synthesis of oil-soluble magnetic material:
By nano-magnetic γ-Fe2O3By 80 DEG C of reflux 30min of 100mL ethyl alcohol, cooling drying.5g after taking drying is magnetic
γ-Fe2O3Tri- mouthfuls of the 500mL burnings equipped with the 250mL deionized water that 2.5mL ammonium hydroxide (25wt.%~28wt.%) has been added dropwise are added
Bottle, adjusting mixing speed are 450rpm, are passed through nitrogen, stir 30min, remove oxygen in water, temperature is risen to 85 DEG C, and drip
Enter 25mL dissolved with the acetone of 5g oleic acid, after reacting 10min, instills 5g oleic acid, the reaction was continued 30min.After cooling, it will be mixed with hydrochloric acid
It closes pH value of solution and is adjusted to 7, then using magnet to magnetic γ-Fe2O3Particle is separated, and is cleaned using methanol, vacuum drying.
(2) synthesis of magnetic poly- divinylbenzene microspheres resin:
S1, by 4g gelatin, 2g tertiary sodium phosphate and 8gNa2HPO4·12H2O is dissolved in 500mL deionized water as dispersed phase,
And 70g sodium chloride is added into dispersed phase, it is subsequently placed in the three neck round bottom of 1000mL.
S2, added into three neck round bottom by 50g neighbour's divinylbenzene, 5g by oleic acid modified γ-Fe2O3Particle, 125g
The oily phase of dimethylbenzene and 1g benzoyl peroxide composition, is stirred under the mixing speed of 400rpm, is gradually heated to 95 DEG C,
Polymerization reaction is carried out, is discharged after 12h.
S3, after reaction system is cooling, magnetic copolymer obtained is separated from reaction system using magnet, spend from
Sub- water cleans 3~5 times, then after clean 2 times with ethyl alcohol, acetone cleaning 1 time is dried in vacuo 8h, resulting resin is at 60 DEG C
For magnetic poly- divinylbenzene microspheres resin.
Comparative example 1
A kind of preparation method of the poly- divinylbenzene microspheres resin of magnetism, includes the following steps:
(1) synthesis of oil-soluble magnetic material:
By nano-magnetic Fe3O4By 80 DEG C of reflux 30min of 100mL ethyl alcohol, cooling drying.5g after taking drying is magnetic
Fe3O4The 500mL three-necked flask equipped with the 250mL deionized water that 2.5mL ammonium hydroxide (25wt.%~28wt.%) has been added dropwise is added,
Adjusting mixing speed is 450rpm, is passed through nitrogen, stirs 30min, removes oxygen in water, temperature is risen to 85 DEG C, and instill
25mL after reacting 10min, instills 5g oleic acid, the reaction was continued 30min dissolved with the acetone of 5g oleic acid.After cooling, it will be mixed with hydrochloric acid
PH value of solution is adjusted to 7, then using magnet to magnetic Fe3O4Particle is separated, and is cleaned using methanol, vacuum drying.
(2) synthesis of magnetic poly- divinylbenzene microspheres resin:
S1,2g polyvinyl alcohol is dissolved in 500mL deionized water as dispersed phase, dispersion is added to 1000mL's
In three neck round bottom.
S2, into three neck round bottom and add by 50g neighbour's divinylbenzene, 5g by oleic acid modified Fe3O4Particle, 125g
The oily phase of lauryl alcohol and 1g benzoyl peroxide composition, is stirred under the mixing speed of 400rpm, is gradually heated to 95 DEG C,
Polymerization reaction is carried out, is discharged after 12h.
S3, after reaction system is cooling, magnetic copolymer obtained is separated from reaction system using magnet, spend from
Sub- water cleans 3~5 times, then after clean 2 times with ethyl alcohol, acetone cleaning 1 time.8h is dried in vacuo at 60 DEG C, resulting resin is
For magnetic poly- divinylbenzene microspheres resin.
In this comparative example, in actual fabrication process, when the sodium chloride of equivalent is added, it is unable to get the good magnetic of balling-up
The poly- divinylbenzene microspheres resin of property.
In this comparative example, in actual fabrication process, when the amount of polyvinyl alcohol is excessive, it is unable to get the good magnetic of balling-up
Property poly- divinyl microballoon resin, this comparative example is the preferable example of polyvinyl alcohol additional amount.
Comparative example 2
A kind of preparation method of the poly- divinylbenzene microspheres resin of magnetism, includes the following steps:
(1) synthesis of oil-soluble magnetic material:
By nano-magnetic Fe3O4By 80 DEG C of reflux 30min of 100mL ethyl alcohol, cooling drying.5g after taking drying is magnetic
Fe3O4The 500mL three-necked flask equipped with the 250mL deionized water that 2.5mL ammonium hydroxide (25wt.%~28wt.%) has been added dropwise is added,
Adjusting mixing speed is 450rpm, is passed through nitrogen, stirs 30min, removes oxygen in water, temperature is risen to 85 DEG C, and instill
25mL after reacting 10min, instills 5g oleic acid, the reaction was continued 30min dissolved with the acetone of 5g oleic acid.After cooling, it will be reacted with hydrochloric acid
Gained mixed solution pH is adjusted to 7 afterwards, then using magnet to magnetic Fe3O4Particle is separated, and is cleaned using methanol, and vacuum is dry
It is dry.
(2) synthesis of magnetic poly- divinylbenzene microspheres resin:
S1, by 0.6g nonylphenol polyoxyethylene ether and 1.2g polyvinyl alcohol, be dissolved in 500mL deionized water as dispersion
Phase.Dispersed phase is placed in the three neck round bottom of 1000mL.
S2, added into three neck round bottom by 50g to divinylbenzene, 5g by oleic acid modified Fe3O4Particle, 125g first
The oily phase of benzene and 1g benzoyl peroxide composition, is stirred under the mixing speed of 400rpm, is gradually heated to 95 DEG C, carries out
Polymerization reaction discharges after 12h.
S3, after reaction system is cooling, magnetic copolymer obtained is separated from reaction system using magnet, spend from
Sub- water cleans 3~5 times, then after clean 2 times with ethyl alcohol, acetone cleaning 1 time.8h is dried in vacuo at 60 DEG C, resulting resin is
For magnetic poly- divinylbenzene microspheres resin.
In this comparative example, in actual fabrication process, when sodium chloride is added, it is unable to get the preferable magnetism poly- two of balling-up
Ethenylbenzene microballoon resin.
It,, can not when the amount of nonylphenol polyoxyethylene ether and polyvinyl alcohol is excessive in actual fabrication process in this comparative example
The preferable magnetic poly- divinylbenzene microspheres resin of balling-up is obtained, this comparative example is that nonylphenol polyoxyethylene ether and polyvinyl alcohol add
Enter the preferable example of amount.
Comparative example 3
A kind of preparation method of the poly- divinylbenzene microspheres resin of magnetism, includes the following steps:
(1) synthesis of oil-soluble magnetic material:
By nano-magnetic Fe3O4By 80 DEG C of reflux 30min of 100mL ethyl alcohol, cooling drying.By 5g magnetism after will be dry
Fe3O4The 500mL three-necked flask equipped with the deionized water containing 250mL that 2.5mL ammonium hydroxide (25wt.%~28wt.%) has been added dropwise is added
In, adjusting mixing speed is 450rpm, is passed through nitrogen, stirs 30min, removes oxygen in water, temperature is risen to 85 DEG C, and drip
Enter 25mL dissolved with the acetone of 5g oleic acid, after reacting 10min, instills 5g oleic acid, the reaction was continued 30min.It, will be anti-with hydrochloric acid after cooling
Gained mixed solution pH is adjusted to 7 after answering, then using magnet to magnetic Fe3O4Particle is separated, and is cleaned using methanol, vacuum
It is dry.
(2) synthesis of magnetic poly- divinylbenzene microspheres resin:
S1,8g gelatin is dissolved in 500mL deionized water as dispersed phase, dispersed phase is placed in the three neck round bottoms of 1000mL
In flask.
S2, added into three neck round bottom by divinylbenzene between 50g, 5g by oleic acid modified Fe3O4Particle, 125g first
The oily phase of benzene and 1g benzoyl peroxide composition, is stirred under the mixing speed of 400rpm, is gradually heated to 95 DEG C, carries out
Polymerization reaction discharges after 12h.
S3, after reaction system is cooling, magnetic copolymer obtained is separated from reaction system using magnet, spend from
Sub- water cleans 3~5 times, then after clean 2 times with ethyl alcohol, acetone cleaning 1 time is dried in vacuo 8h, resulting resin is at 60 DEG C
For magnetic poly- divinylbenzene microspheres resin.
In this comparative example, in actual fabrication process, when sodium chloride is added, it is unable to get the preferable magnetism poly- two of balling-up
Ethenylbenzene microballoon resin.
In this comparative example, in actual fabrication process, when the amount of gelatin is excessive, it is preferable magnetic poly- to be unable to get balling-up
Divinylbenzene microspheres resin, this comparative example are the preferable example of gelatin additional amount.
The Fe of oleic acid before modified is used in embodiment 13O4, modified Fe3O4With infrared comparison diagram such as Fig. 1 institute of oleic acid
Show, Fe in Fig. 13O4In wave number 546cm-1There is strong vibration absorption peak at place, which belongs to Fe3O4Characteristic peak.What oleic acid was modified
O-Fe3O4Particle is in wave number 2971cm-1And 2877cm-1, there is-the CH of faint oleic acid molecular in place3With-CH2Stretching vibration
Peak；In wave number 3381cm-1Place is Fe3O4The stretching vibration peak of-the OH of nanoparticle surface, 538cm-1The strong absworption peak at place is opposite
In Fe3O4In 546cm-1Characteristic peak produce certain offset, this is because the interaction between COO-Fe affects Fe-
The bond energy of O key shows oleic acid success modified magnetic particle, so that magnetic-particle surface has wrapped lipophilic chain alkyl, this
So that magnetic-particle can be good at blending with organic phase, so that magnetic-particle can be uniformly dispersed in resin microsphere
During polymerization, and it is dispersed in the inside of resin microsphere well.
Fig. 2 is the Fe of embodiment 1 before modified using oleic acid3O4With the modified obtained O-Fe of oleic acid3O4XRD comparison diagram.
There are 6 characteristic peaks such as (220), (311), (400), (422), (511), (440) in figure, can be seen that from the comparison map of Fig. 2,
Through the modified O-Fe of oleic acid3O4Diffraction maximum and Fe3O4Position consistency, illustrate that the magnetic-particle Jing Guo surface modification does not cause
Variation in structure.Fig. 3 is the Fe of embodiment 1 before modified using oleic acid3O4With the modified obtained O-Fe of oleic acid3O4Magnetic hysteresis
Loop line comparison diagram, Fe in Fig. 33O4The modified O-Fe with oleic acid3O4Specific saturation magnetization be respectively 64.11emu/g and
49.66emu/g shows that resulting materials without remanent magnetism, have super suitable from figure 3, it can be seen that not occurring B-H loop after before modified
Magnetism, the modified O-Fe of oleic acid3O4The specific saturation magnetization of particle has dropped 22.54%, this may be due to Coated with Oleic Acid
The presence of layer, so that the quality of magnetic nano-particle reduces in unit mass, to specific saturation magnetization reduction occur
Phenomenon shows to be modified successfully, and the modified magnetic material of success can be preferably applied in the polymerization of resin microsphere, so that resin
It can use magnet in subsequent use and be collected processing to it.
Fig. 4 is the infrared comparison diagram of the poly- divinylbenzene microspheres resin of magnetism of divinylbenzene and the preparation of the embodiment of the present invention 1.
Divinylbenzene is in 1630cm-1There is-CH=CH at place2Characteristic absorption peak, and the infrared spectrum of magnetic poly- divinylbenzene microspheres resin
In then die down, the shape of binding resin judges magnetic poly- divinylbenzene microspheres resins synthesis success.
Fig. 5 is the scanning electron microscope (SEM) photograph of the poly- divinylbenzene microspheres resin of magnetism prepared by the embodiment of the present invention 1.The present invention is implemented
The monomer that example uses only includes divinylbenzene, and the surface of the resin shown under Electronic Speculum is relatively smooth, the partial size point of resin
Cloth is relatively narrow.
(a), (b), (c), (d), (e) are followed successively by the embodiment of the present invention 1, embodiment 2, comparative example 1,2 and of comparative example in Fig. 6
The grain size distribution of the poly- divinylbenzene microspheres resin of magnetism prepared by comparative example 3 is set in Examples 1 and 2 as can be seen from Figure 6
The partial size of rouge is substantially distributed in 100 μm~250 μm, and particle diameter distribution is relatively narrow, and the particle diameter distribution of resin is wider in comparative example 1,2 and 3,
Some is even up to 1000 μm or more, and there is clear superiorities in terms of the dispersion of distribution of partial size for the resin for illustrating in embodiment.
This is coefficient with monomer as a result, the dispersant component in embodiment enables to by the specific dispersant of the invention used
Monomer is stirred after paddle breaks up, and is wrapped up the monomer droplet broken up, so that it is not formed bulky grain during polymerization, not cruelly
It is poly-, moderate in grain size.Using divinylbenzene as monomer, since there are two the double bonds hung for its tool, so that resin microsphere is in formation
It is able to carry out in the process 3 D cross-linked, resin internal structure is compact, is also advantageous that in forming the relatively narrow situation of partial size.Partial size is relatively narrow
It is an excellent important behaviour of resin microsphere technology, the physicochemical property of the relatively narrow resin microsphere of particle diameter distribution is closer, right
It is higher in the reproducibility of follow-up study.
Using the BELSORP type specific surface area and hole analyzer of Japanese BEL company production to Examples 1 to 2 and comparative example 1
The poly- divinylbenzene microspheres resins of magnetism of~3 preparations are measured, and obtain its nitrogen adsorption-desorption isotherm, using BET method into
Row analysis, can be obtained total adsorbance Vm, specific surface area as,BET, total pore volume (p/p0=0.990) and the physical parameters such as average pore size.
The physical parameter of the poly- divinylbenzene microspheres resin of magnetism prepared by 1 Examples 1 to 2 of table and comparative example 1~3
Table 1 is to measure to the poly- divinylbenzene microspheres resin of magnetism prepared by the embodiment of the present invention 1~2 and comparative example 1~3
The physical parameter arrived, wherein Vm is total adsorbance, as,BETFor specific surface area.
(a), (b), (c), (d), (e) are followed successively by the embodiment of the present invention 1, embodiment 2, comparative example 1,2 and of comparative example in Fig. 7
Nitrogen adsorption-desorption curve of the poly- divinylbenzene microspheres resin of magnetism prepared by comparative example 3.As can be seen from Figure 7, it is inhaled in nitrogen
In attached-desorption process, the nitrogen adsorption effect of Examples 1 and 2 is apparently higher than in comparative example, illustrates the resin tool in embodiment
There is more abundant cellular structure, the N of resin in additional embodiment2Adsorbance variation tendency may determine that in resin there is
Large, medium and small hole, this feature are conducive to absorption of the resin in embodiment to a variety of adsorbates.
Embodiment 3
Using the poly- divinylbenzene microspheres resin of magnetism made from embodiment 1, to 2- nitrotoleune, 2,4- dinitrotoluene (DNT),
2,4,6-trinitrotoluene these types nitrobenzene compounds are adsorbed, to measure curve of adsorption kinetics.Solution after absorption
The concentration of middle nitrobenzene compounds needs to be determined with standard curve.
The measuring method utilized in the present embodiment is Static Adsorption characterizing method, and particle diameter distribution is narrow to be made in different batches
The reproducible probability of experimental result in adsorption process is bigger, the absorption research method-Dynamic Adsorption not used in the present invention
In research, particle diameter distribution is relatively narrow more advantageous for filling, so that packed column more consolidation, material obtains more fully sharp
With.
The measurement of standard curve:
Difference first dissolves a small amount of ethyl alcohol of TNT, DNT and o-MNT, then adds deionized water to be diluted to 1000mL respectively, matches
The o-MNT solution of the TNT solution of 150mg/L, the DNT solution of 250mg/L and 250mg/L is made.Above-mentioned solution is distinguished
Dilution is configured to following series of concentrations solution (i.e. 0mg/L, 10mg/L, 20mg/L, 30mg/L and 40mg/L), carries out ultraviolet light absorption
Degree test, and draw out the standard curve of Absorbance versus concentration.
The measurement of adsorption dynamics adsorption kinetics:
Resin 0.06g prepared by Example 1 is respectively placed in 250ml conical flask, is separately added into the 150mg/L of 180mL
TNT solution, the DNT solution of 250mg/L or the o-MNT solution of 250mg/L.It vibrates at 298K, 200rpm, is taken between timesharing
Sample carries out ultraviolet absorptivity test, finds solution corresponding concentration by standard curve, and the absorption that resin is calculated as follows is held
Amount:
Qt=(c0-ce)·V/W
In formula, QtThe adsorption capacity (mg/g) of resin when for time t (min), solution when ce is time t (min) it is dense
It spends (mg/L), c0For the initial concentration (mg/L) of solution, V is the volume (L) of solution, and W is the quality (g) of resin.
Fig. 8 is that embodiment 3 measures absorption of the obtained poly- divinylbenzene microspheres resin of magnetism to 2,4,6- trinitrotoluene
Performance characterization figure, as can be seen from Figure 8, in 240min, it is flat that magnetic poly- divinylbenzene microspheres resin just basically reaches absorption
Weighing apparatus, in the early stage, increase with time, the rate of adsorption increases sharply, and reaches adsorption equilibrium after slowing down gradually.Due to having inside resin
Cellular structure more abundant, therefore resin 2,4,6-trinitrotoluene biggish for molecular volume takes a long time
Adsorption equilibrium can be reached.It can be seen that magnetic poly- divinylbenzene microspheres resin to 2,4,6-trinitrotoluene according to effect in figure
Equilibrium adsorption capacities be about 244mg/g, illustrate that resin microsphere absorption property is excellent.
Fig. 9 is the adsorptivity that embodiment 3 measures the obtained poly- divinylbenzene microspheres resin of magnetism to 2,4-DNT
Energy phenogram, as can be seen from Figure 9, in 140min, resin just basically reaches adsorption equilibrium, and in the early stage, the rate of adsorption increases sharply,
Increase with time, adsorption equilibrium is reached after slowing down gradually.Magnetic poly- divinylbenzene microspheres resin puts down 2,4-DNT
The adsorption capacity that weighs is about 329mg/g, shows that resin has excellent absorption property to 2,4- dinitrotoluene (DNT).
Figure 10 is the absorption property table that embodiment 3 measures the obtained poly- divinylbenzene microspheres resin of magnetism to 2- nitrotoleune
Sign figure, as can be seen from Figure 10, in 60min, resin just basically reaches adsorption equilibrium, and in the early stage, the rate of adsorption increases sharply, at any time
Between increase, reach adsorption equilibrium after slowing down gradually.It is also known from Figure 10,2- nitrotoleune lesser for molecular volume, resin
Microballoon can reach adsorption equilibrium in 60min, and wherein 1g resin microsphere is up to 394mg to the absorption of 2- nitrotoleune, it is seen that resin
There is excellent absorption property to 2- nitrotoleune.
Although the present invention is disclosed as above with preferred embodiment, however, it is not intended to limit the invention.It is any to be familiar with ability
The technical staff in domain, without deviating from the scope of the technical scheme of the present invention, all using the technology contents pair of the disclosure above
Technical solution of the present invention makes many possible changes and modifications or equivalent example modified to equivalent change.Therefore, all
Without departing from the content of technical solution of the present invention, according to the present invention technical spirit any simple modification made to the above embodiment,
Equivalent variations and modification, all shall fall within the protection scope of the technical scheme of the invention.
Claims (10)
1. a kind of poly- divinylbenzene microspheres resin of magnetism, which is characterized in that the poly- divinylbenzene microspheres resin of magnetism includes poly-
Divinylbenzene microspheres resin matrix and magnetic-particle, the magnetic-particle are uniformly distributed in poly- divinylbenzene microspheres resin matrix
In, the specific surface area of the poly- divinylbenzene microspheres resin of magnetism is 800m2/ g~1200m2/g。
2. a kind of preparation method of the poly- divinylbenzene microspheres resin of magnetism, which comprises the steps of:
S1, dispersing agent is dissolved in water, the dispersing agent is the mixture for including gelatin, tertiary sodium phosphate and disodium hydrogen phosphate, is obtained
Dispersion liquid；
S2, be added into dispersion liquid using the modified magnetic-particle of oleic acid, succinic acid or fluorine ether acid, divinylbenzene, pore-foaming agent and
Initiator is uniformly mixed, then carries out polymerization reaction；
S3, to after the reaction was completed, the resulting product of polymerization reaction be cleaned, is dried, obtain magnetic poly- divinylbenzene microspheres
Resin.
3. the preparation method of the poly- divinylbenzene microspheres resin of magnetism according to claim 2, which is characterized in that the S2
In, the preparation method of the magnetic-particle modified using oleic acid, succinic acid or fluorine ether acid includes: using ethyl alcohol or methanol to magnetic
Property particle activated, ammonium hydroxide and activated magnetic-particle are added to the water, the mixed liquor of alkalinity is obtained, and into mixed liquor
The organic solvent dissolved with oleic acid, succinic acid or fluorine ether acid is added, the organic solvent is acetone, ethyl alcohol or methanol, is stirred
Modified, the modification carries out under an inert atmosphere, after the completion of to be modified, pH value is adjusted to 6~8, isolates magnetic-particle, to institute
Magnetic-particle is obtained to be cleaned, dried to get modified magnetic-particle is arrived.
4. the preparation method of the poly- divinylbenzene microspheres resin of magnetism according to claim 2 or 3, which is characterized in that described
In S1, the additional amount of the dispersing agent is the 1.6%~14.5% of water quality；In the dispersing agent, the gelatin, tricresyl phosphate
Sodium, disodium hydrogen phosphate mass ratio be (1~3): 1: (2~5)；The concentration of tertiary sodium phosphate described in gained dispersion liquid be 2g/L~
8g/L。
5. the preparation method of the poly- divinylbenzene microspheres resin of magnetism according to claim 2 or 3, which is characterized in that described
In S2, the temperature of the polymerization reaction is 60 DEG C~120 DEG C；The time of the polymerization reaction is 6h~for 24 hours.
6. the preparation method of the poly- divinylbenzene microspheres resin of magnetism according to claim 2 or 3, which is characterized in that described
In S1, further include the steps that sodium chloride is added into dispersion liquid；The quality of the sodium chloride be the water quality 5%~
20%.
7. the preparation method of the poly- divinylbenzene microspheres resin of magnetism according to claim 2 or 3, which is characterized in that described
In S2, the magnetic-particle is Fe3O4、γ-Fe2O3, nickel oxide or at least one of the oxide of cobalt；The magnetism
The partial size of particle is 5nm~20nm；The dosage of the magnetic-particle is the 1%~10% of divinylbenzene quality.
8. the preparation method of the poly- divinylbenzene microspheres resin of magnetism according to claim 3, which is characterized in that the oil
The dosage of acid, succinic acid or fluorine ether acid is 1~10 times of the magnetic-particle quality；
The concentration of the ammonium hydroxide is 25wt.%~28wt.%；The volume ratio of the ammonium hydroxide and water is 1: (50~100).
9. the preparation method of the poly- divinylbenzene microspheres resin of magnetism according to claim 2 or 3, which is characterized in that described
In S2, the pore-foaming agent is at least one of cyclohexanol, amylalcohol, toluene, dimethylbenzene, lauryl alcohol, heptane and isooctane；The cause
The additional amount of hole agent is the 10%~500% of divinylbenzene quality；
The initiator is benzoyl peroxide and/or azodiisobutyronitrile；The additional amount of the initiator is divinylbenzene matter
The 0.5%~8% of amount.
10. the poly- divinylbenzene microspheres resin of magnetism according to claim 1 or according to claim 2~9 any one institute
The poly- divinylbenzene microspheres resin of magnetism made from the method stated is used for the absorption of nitrobenzene compounds.
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| CN111804289A (en) * | 2019-04-12 | 2020-10-23 | 中国科学院化学研究所 | Magnetic polydivinylbenzene nanofiber composite oil absorption material and preparation and application thereof |
| CN112452308A (en) * | 2020-12-09 | 2021-03-09 | 昆明理工大学 | Synthetic method and application of pyridine amide-containing adsorption polymer |
| CN117756971A (en) * | 2023-12-29 | 2024-03-26 | 同宇新材料(广东)股份有限公司 | Low-dielectric hydrocarbon resin and synthesis method and application thereof |
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| WO2011061229A1 (en) * | 2009-11-19 | 2011-05-26 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Polymerisable coordination complexes and polymer materials obtained from said monomers |
| CN102516679A (en) * | 2011-12-19 | 2012-06-27 | 南京大学 | Magnetic microsphere resin with high specific surface area and preparation method and application thereof |
| CN105199135A (en) * | 2015-03-02 | 2015-12-30 | 中国科学院理化技术研究所 | Preparation method of magnetic composite microspheres |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2011061229A1 (en) * | 2009-11-19 | 2011-05-26 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Polymerisable coordination complexes and polymer materials obtained from said monomers |
| CN102516679A (en) * | 2011-12-19 | 2012-06-27 | 南京大学 | Magnetic microsphere resin with high specific surface area and preparation method and application thereof |
| CN105199135A (en) * | 2015-03-02 | 2015-12-30 | 中国科学院理化技术研究所 | Preparation method of magnetic composite microspheres |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111804289A (en) * | 2019-04-12 | 2020-10-23 | 中国科学院化学研究所 | Magnetic polydivinylbenzene nanofiber composite oil absorption material and preparation and application thereof |
| CN112452308A (en) * | 2020-12-09 | 2021-03-09 | 昆明理工大学 | Synthetic method and application of pyridine amide-containing adsorption polymer |
| CN112452308B (en) * | 2020-12-09 | 2022-10-25 | 昆明理工大学 | Synthetic method and application of pyridine amide-containing adsorption polymer |
| CN117756971A (en) * | 2023-12-29 | 2024-03-26 | 同宇新材料(广东)股份有限公司 | Low-dielectric hydrocarbon resin and synthesis method and application thereof |
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