CN105111413A - Preparation method and application of magnetic organic conjugated polymer microsphere - Google Patents
Preparation method and application of magnetic organic conjugated polymer microsphere Download PDFInfo
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- CN105111413A CN105111413A CN201510562945.7A CN201510562945A CN105111413A CN 105111413 A CN105111413 A CN 105111413A CN 201510562945 A CN201510562945 A CN 201510562945A CN 105111413 A CN105111413 A CN 105111413A
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Abstract
The invention provides a preparation method of a magnetic organic conjugated polymer microsphere. The preparation method comprises the steps of polymerizing acetylenyl benzene and halogeno benzene on a Fe3O4 surface to obtain a polymer; forming a hollow tubular polymer by using the polymer; and covering the hollow tubular polymer on the Fe3O4 surface to obtain a hydrophobic micro-nano structure to form a magnetic, oleophilic and hydrophobic microsphere. The polymer material prepared by using the method can selectively adsorb/separate oil or a nonpolar organic solvent in a water body. The polymer can be separated from a solution under the action of a magnetic field after being saturated through adsorbing organic matters in the mixed solution. Obviously, the recovering method is simple, high in operability and regenerating speed and capable of reducing the adsorption and separation costs so as to have a potential application value in the fields of crude oil leakage treatment, industrial organic wastewater treatment, liquid/liquid separation, water treatment, catalysis and the like.
Description
Technical field
The invention belongs to synthesis of polymer material and Application Areas, be specifically related to the preparation method of the magnetic conjugatd polymers microballoon of a kind of tool, and this material is in the application removing organic compound in water.
Background technology
Water resources is the important substance basis of economy and social sustainable development, but discharges the Marine Environmental Pollution that the water pollutions that causes and crude oil leakage cause due to industrial organic waste liquid, causes serious eco-catastrophe to Freshwater resources and ocean environment.As petrochemical production process produces the organic waste water of high density, because complicated component, organic compound content are high, cause the loss of body eutrophication and animals and plants species.Organism forms aggregation in water surface, and the oxygen that have impact in air enters into water body, reduces the self-purification capacity of water body.The crude oil amount of offshore production or transport sharply increases, and the impaired or oil tanker of drilling unit meets with the perils of the sea and causes the accident of crude oil leakage also again and again to occur.Leak crude oil except pollute sea table plane except, some intercept and capture by the seawater of different laminar flow, pollutent with ocean current diffusion cause more large-area pollution.Large-area oil film covers ocean surface, changes the reflectivity on sea, decreases the solar radiation entering sea surface, hinder evaporation of water, produces interference to the hydrometeorological condition in partial area.Mostly organism contained by industrial organic waste liquid is the components such as long chain alkane, aromatic hydrocarbon or oils, also a kind of resource.Organic compound Degradation and Transformation is carbonic acid gas, methane and water by current biochemical processing method, but can cause greenhouse gas emission, cost increase in treating processes.
Organic compound in application adsorption technology enrichment water body or crude oil leakage pollutent are protection of the environment a kind of economy, effective meanss, and the sorbing material researching and developing excellent performance is then key wherein.Some organic compound in water body due to the reason with nonpolar or low-pole water insoluble, hydrophobicly can be separated with the material of oleophilic properties with having.Conjugatd polymers has excellent hydrophobicity, and its advantage derives from two point: CMP and is made up of the very weak phenyl of polarity and acetylene bond, and therefore the general polarity of polymkeric substance is close with these organic compound; Containing rigidity and conjugated structure in material, intermolecular accumulation produces a large amount of hole, forms coarse micro nano structure.CMP is very little to the adsorptive power of water, but it has good adsorptive power to organic solvent, utilizes material to the difference of water and other organic compounds adsorb ability, can be used for enrichment, the organic compound be separated in water body.Mostly the conjugatd polymers of current report is to exist with amorphous, pulverous form, although there is the performance of good adsorb organic compound, recycling difficulty, range of application is little.And by such Polymer-supported in general sponge, the sorbing material with elasticity and hydrophobic property can be prepared, it can adsorb the organic compound on the water surface efficiently, realizes oil-water separation rapidly.But modified sponge is to the organic compounds adsorb weak effect be dissolved in water body, and deep purifying ability is poor.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of synthetic method with magnetic, oleophilic drainage, micro polymer ball material, and the application method of organic compound in Xuan Zexingxifu Separation of Water.Be specially and use acetylenylbenzene and halogeno-benzene at Fe
3o
4be polymerized on the surface, coated ball body forms hydrophobic micro nano structure, makes material have good hydrophobic property.Such as be polymerized at spherome surface by 1,3,5-tribromo-benzene and Isosorbide-5-Nitrae-diethynylbenzene, form the polymer wrapped Fe of hollow tubular
3o
4and be agglomerated into microballoon shape.The polymer microballoon of synthesis not only has larger granularity, but also inherits the hydrophobic oleophilic oil character of conjugatd polymers, has selective adsorption capacity (adsorbed oil or non-polar solvent, not planar water) to the oil in water body and non-polar solvent.To the adsorptive capacity of a series of oil, non-polar solvent and polar solvent between 200wt%-400wt%.This magnetic polymer microsphere material is joined in solution, uses the methods such as mechanical stirring to allow itself and solution fully contact, after polymkeric substance adsorb organic compounds in mixing solutions is saturated, then by the polymer microballoon of magnetic and solution separating under the action of a magnetic field.Obviously such absorption and recovery method simple, workable, reproduction speed is fast, reduces the cost of absorption, separation, therefore has good using value.
The preparation method of the magnetic conjugatd polymers microballoon of tool of the present invention, the technical scheme of employing comprises the steps:
A (), under protection of inert gas, adds non-polar solvent C and basic solvent D, then adds nanometer Fe in reaction flask
3o
4microballoon;
Solvent C is the one in benzene,toluene,xylene or trimethylbenzene; Solvent D is diethylamine or triethylamine; Wherein, non-polar solvent C plays dissemination, and basic solvent D is used to provide the environment of a meta-alkalescence, contributes to polyreaction and occurs.
B () under protection of inert gas, then adds with the substrate A of mol ratio 1 ~ 2:1 mixing and substrate B in reaction flask, and nanometer Fe
3o
4microballoon and substrate A mol ratio are 0.1 ~ 0.5:1; Wherein, nanometer Fe
3o
4the optimum mole ratio of microballoon and substrate A is 0.2:1.
Wherein: substrate A is Isosorbide-5-Nitrae-diethynylbenzene, substrate B is following one: 1,3,5-tribromo-benzene, 1,3,5-phenyl triiodide or
Wherein R is-OH ,-CH
3,-OCH
3,-CN ,-CHO ,-NH
2;
C (), under protection of inert gas, under room temperature condition, continues in reaction flask, add cuprous iodide and tetrakis triphenylphosphine palladium; Its add-on is substrate A+ substrate B: cuprous iodide: the mol ratio of tetrakis triphenylphosphine palladium is 1:(0.02 ~ 0.1): (0.02 ~ 0.1);
D step (c) gained mixture in 60 ~ 90 DEG C, after reaction 5 ~ 24h, after washing with alcohol, drying, then is separated parcel Fe with magnet by ()
3o
4polymer microballoon; Wherein, the optimal reaction temperature of step (c) gained mixture is 80 DEG C, and the reaction times is 12h;
E the polymer microballoon of step (d) gained is placed in beaker by (), then use ethanol, washed with methanol successively; Product obtains the magnetic conjugatd polymers microballoon of tool after vacuum-drying.
The method that the present invention is mentioned above, the washing in the step (e) described in it is, first uses ethanol to wash, re-uses Accelerate solvent extraction instrument washed with methanol.
The above-mentioned nano level Fe of the present invention
3o
4microballoon has the alternative product of multiple commercial sources, and the specific embodiment of the invention uses the reagent of Aladdin, is about the microballoon of 300nm level.
Another aspect of the present invention is to provide a kind of tool utilizing aforesaid method to synthesize magnetic conjugatd polymers microballoon.
Another aspect of the invention is to provide a kind of tool magnetic conjugatd polymers microballoon in the application removing organic solvent or compound in water: the polymer materials of described magnetic, its surface is alternately made up of nonpolar chemical bond benzyne, very weak to the adsorptive power of water, and very strong to nonpolar or weakly polar organic solvent or compound adsorptive power, such as: benzene, toluene, ethylbenzene, aniline, phenol, ethyl acetate, kerosene, methylene dichloride; Utilize the difference of absorption property, absorption with the field such as to be separated, prepared by environment protection, catalysis and to have good application.
Theoretical foundation of the present invention: by hypotoxic nano level Fe
3o
4ball is mixed in alkali organic solvent, forms suspension liquid.Due to Fe
3o
4active sites is many, and Adsorbed acetylene base benzene and bromobenzene are enriched in material surface.Add catalyzer and after raised temperature, Fe
3o
4acetylenylbenzene and the bromobenzene concentration on surface are high, and speed of response is fast, is first polymerized nucleation, then form the conjugatd polymers that phenyl and alkynyl replace, are coated on Fe
3o
4surface.Because substrate A1,4-diethynylbenzene is linear structure, it can play the effect of template and guiding at polymerization process, makes polymkeric substance become tubular-shaped structures, and with Fe
3o
4centered by outgrowth, be finally curled into parcel Fe
3o
4the conjugatd polymers microballoon of particle.This polymkeric substance is connected and composed by nonpolar or low-pole key, and the reason due to polarity easily adsorbs organism that is nonpolar or low-pole, and not planar water.Therefore oil (non-polar solvent)/water is separated and there is very high adsorption selectivity.The polymkeric substance of hollow tubular is at Fe simultaneously
3o
4outside defines micro nano structure, creates a large amount of space, the magnetic conjugatd polymers microballoon of final formation tool.Its to low density solvent if benzene adsorptive capacity is 2 times of own wt, to high-density solvent if the adsorptive capacity of oil of mirbane is 4 times of own wt.
This magnetic polymer microsphere material is joined in solution, uses the methods such as mechanical stirring to allow itself and solution fully contact, after polymkeric substance adsorb organic compounds in mixing solutions is saturated, then by the polymer microballoon of magnetic and solution separating under the action of a magnetic field.Obviously such absorption and recovery method simple, workable, reproduction speed is fast, reduces the cost of absorption, separation, therefore has good using value.
Different B substance is used to carry out polyreaction, the magnetic polymer microsphere with different functional groups and soda acid character can be obtained, these materials are having different absorption properties under different acid-base conditions, and the selectivity can carrying out small molecular organic compounds is under water caught and recovery etc.The novel absorption material of synthesis not only has the advantages such as loading capacity is large, selectivity is controlled, rate of adsorption is fast, and operational path is simple, and working method is easy, has a good application prospect.
Compared with prior art, the present invention has the following advantages:
1) material of the present invention's synthesis, due to its good surface hydrophobicity, oil-wet behavior, to the oil in water body and non-polar solvent have excellent selective adsorption separation performance;
2) material has larger loading capacity to organic solvent.Super-hydrophobic micropore conjugated polymers between 2 ~ 4 times, removes the small molecules organic pollutant in water body to the adsorptive capacity of a series of oil, non-polar solvent and polar solvent, and efficiency can reach more than 70% (organism original concentration is 1g/L);
3) material preparation process route is simple, and repeat performance is good;
4) this magnetic polymer microsphere using method is simple, can join in solution, allow itself and solution fully contact by methods such as mechanical stirring, and the method adsorb organic compounds speed is fast, and removal efficiency is high.And many Water warfare facilities have coagulation whipping appts, use this material can use existing equipment and carry out;
5) micrograde polymer granularity comparatively greatly easily filtering separation, and material has magnetic, can shift or be separated under the action of a magnetic field, adsorbs saturated rear convenient recovery.Therefore the present invention reveals process, industrial organic waste liquid process at crude oil, liquid/liquid is separated and the field such as water treatment, catalysis has potential using value.
Accompanying drawing explanation
The scanning electron microscopic picture of Fig. 1 embodiment 1;
The scanning electron microscopic picture of Fig. 2 embodiment 2;
The coated magnetic Fe that Fig. 3 embodiment 1 and 2 is obtained
3o
4conjugatd polymers microballoon 1 and the comparison of 2 pairs of different solvents adsorptive poweies.
Embodiment
Following non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.
Nano level Fe
3o
4ball is the reagent purchased from Aladdin, is about the microballoon of 300nm level; Isosorbide-5-Nitrae-diacetylene-benzene: Isosorbide-5-Nitrae-diethynylbenzene; 1,3,5-tribromo-benzene: 1,3,5-tribromobenzene; Tetrakis triphenylphosphine palladium: tetrakis (triphenylphosphine) palladium; Cuprous iodide: copper (I) iodide; 2,4,6-tribromophenol: 2,4,6-tribromophenol; 2,4,6-bromamide: 2,4,6-tribromaniline; Toluene: toluol; Dimethylbenzene: xylene; Diethylamine: diethylamine; Triethylamine: triethylamine.
The synthesis of embodiment 1 product
1. synthesize: by the nano level Fe of 150mg
3o
4ball is placed in the round-bottomed flask of 50ml drying, adds 5ml toluene and 5ml triethylamine in device, and under ar gas environment, vigorous stirring forms suspension liquid.Isosorbide-5-Nitrae-the diacetylene-benzene of 6mmol, 2,4, the 6-tribromophenols of 4mmol, the tetrakis triphenylphosphine palladium of 100mg, the cuprous iodide of 30mg is added again in solution.Then 80 DEG C are warming up to, reaction 10h.
2. wash: product is first used washing with alcohol, filter.Re-using full automatic extraction device, is that extraction liquid cleans with methyl alcohol.Under 100 DEG C of conditions, vacuumize dry 3h.Draw oarse-grained polymer materials with magnet, coated magnetic Fe can be obtained
3o
4conjugatd polymers microballoon 1.
The synthesis of embodiment 2 product
1. synthesize: by the nano level Fe of 300mg
3o
4ball is placed in the round-bottomed flask of 100ml drying, adds 15ml toluene and 15ml triethylamine in device, and vigorous stirring forms suspension liquid in a nitrogen environment.Isosorbide-5-Nitrae-the diacetylene-benzene of 9mmol, 2,4, the 6-bromamides of 7mmol, the tetrakis triphenylphosphine palladium of 300mg, the cuprous iodide of 60mg is added again in solution.Then 80 DEG C are warming up to, reaction 10h.
2. wash: by product washing with alcohol, filter.Re-using full automatic extraction device, is that extraction liquid cleans with methyl alcohol.Under 100 DEG C of conditions, vacuumize dry 3h.Draw with magnet, coated magnetic Fe can be obtained
3o
4conjugatd polymers microballoon 2.
The evaluation of embodiment 3 product
1. the detection of the adsorb organic compound ability of material:
Detection method: by sample (the coated magnetic Fe that embodiment 1 and 2 is obtained of 50mg
3o
4conjugatd polymers microballoon 1 and 2) be positioned in the Glass tubing of tool core plate of known quality, different organic solvents is injected in glass, Glass tubing to be placed on filter paper after static 5min, again the Glass tubing after adsorb organic compound and polymkeric substance are weighed, by calculating Polymer adsorption organism ability.
As shown in Figure 3, the different organic solvents shown in X-coordinate, ordinate zou is solvent and the coated magnetic Fe of absorption
3o
4the mass ratio of conjugatd polymers microballoon 1 and 2.By the comparison of polymkeric substance to different solvents adsorptive power, can find out that polymkeric substance is very weak to the adsorptive power of water, very strong adsorptive power is then had to organic solvent, the ability of wherein adsorbing toluene can reach 2 times of own wt, can reach 4 times of own wt for the oil of mirbane adsorptive power that density is larger.Due to polymer microballoon differing greatly to water and other organic solvent adsorptive power, make the organism that it can be used in desorption water.
2. adsorb organic detection on the water surface:
The mixing solutions of preparation water and toluene, because toluene and water do not dissolve each other, solution upper strata is toluene solution, and lower floor is water.For reaching better demonstrating effect, in toluene, add a small amount of red oiliness dyestuff.By coated magnetic Fe obtained for embodiment 1 and 2
3o
4conjugatd polymers microballoon 1 and 2 put in mixing solutions, then draw polymer beads with magnet, solution becomes clarification, shows that toluene is removed clean by polymkeric substance.
3. organic detection in adsorbed water body:
Compound concentration is phenol solution and the aniline solution of 1g/L respectively, respectively gets 10mL solution, adds the sample 1 of 5mg respectively.Then seal bottleneck, be positioned in vibrator and shake 4 hours.Take out mixing solutions and filter, recording the mixing solutions concentration after absorption by liquid chromatography and be respectively 0.27g/L and 0.15g/L.Show that it has and well remove organic ability in water body.
Claims (4)
1. a preparation method for the magnetic conjugatd polymers microballoon of tool, is characterized in that: comprise the steps:
A (), under protection of inert gas, adds non-polar solvent C and basic solvent D, then adds nanometer Fe in reaction flask
3o
4microballoon;
Solvent C is the one in benzene,toluene,xylene or trimethylbenzene; Solvent D is diethylamine or triethylamine;
B () under protection of inert gas, then adds with the substrate A of mol ratio 1 ~ 2:1 mixing and substrate B in reaction flask, and nanometer Fe
3o
4microballoon and substrate A mol ratio are 0.1 ~ 0.5:1;
Wherein: substrate A is Isosorbide-5-Nitrae-diethynylbenzene, substrate B is following one: 1,3,5-tribromo-benzene, 1,3,5-phenyl triiodide or
Wherein R is-OH ,-CH
3,-OCH
3,-CN ,-CHO ,-NH
2;
C (), under protection of inert gas, continues in reaction flask, add cuprous iodide and tetrakis triphenylphosphine palladium; Its add-on is substrate A+ substrate B: cuprous iodide: the mol ratio of tetrakis triphenylphosphine palladium is 1:0.02 ~ 0.1:0.02 ~ 0.1;
D step (c) gained mixture in 60 ~ 90 DEG C, after reaction 5 ~ 24h, after washing with alcohol, drying, then is separated parcel Fe with magnet by ()
3o
4polymer microballoon;
E the polymer microballoon of step (d) gained is placed in beaker by (), then use ethanol, washed with methanol successively; Product obtains the magnetic conjugatd polymers microballoon of tool after vacuum-drying.
2. method according to claim 1, is characterized in that: the washing in described step (e) is, first uses ethanol to wash, re-uses Accelerate solvent extraction instrument washed with methanol.
3. the magnetic conjugatd polymers microballoon of a kind of tool of the method for claim 1 synthesis.
4. the magnetic conjugatd polymers microballoon of tool as claimed in claim 3 is in the application removing organic solvent or compound in water.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109608879A (en) * | 2018-11-20 | 2019-04-12 | 郑州大学 | A kind of hollow ferroso-ferric oxide microballoon@polyaniline/polyimide composite film absorbing material and preparation method |
| CN110833825A (en) * | 2019-10-25 | 2020-02-25 | 河北大学 | Super-hydrophobic chromatographic stationary phase material and preparation method and application thereof |
| WO2024027742A1 (en) * | 2022-08-04 | 2024-02-08 | 大连理工大学 | Anhydrous anaerobic operation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504207A (en) * | 2011-12-01 | 2012-06-20 | 大连理工大学 | Elastic hydrophobic organic conjugated polymer, synthesizing method thereof and application thereof to removing of organic matters from water |
| CN103242557A (en) * | 2013-05-03 | 2013-08-14 | 大连理工大学 | Elastic hydrophobic material and synthetic method as well as application thereof |
| CN103965835A (en) * | 2014-05-13 | 2014-08-06 | 西南石油大学 | Ultra-light magnetic oil absorption material and preparation method thereof |
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2015
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504207A (en) * | 2011-12-01 | 2012-06-20 | 大连理工大学 | Elastic hydrophobic organic conjugated polymer, synthesizing method thereof and application thereof to removing of organic matters from water |
| CN103242557A (en) * | 2013-05-03 | 2013-08-14 | 大连理工大学 | Elastic hydrophobic material and synthetic method as well as application thereof |
| CN103965835A (en) * | 2014-05-13 | 2014-08-06 | 西南石油大学 | Ultra-light magnetic oil absorption material and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109608879A (en) * | 2018-11-20 | 2019-04-12 | 郑州大学 | A kind of hollow ferroso-ferric oxide microballoon@polyaniline/polyimide composite film absorbing material and preparation method |
| CN110833825A (en) * | 2019-10-25 | 2020-02-25 | 河北大学 | Super-hydrophobic chromatographic stationary phase material and preparation method and application thereof |
| WO2024027742A1 (en) * | 2022-08-04 | 2024-02-08 | 大连理工大学 | Anhydrous anaerobic operation method |
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