CN107286314B - Porous cross-linked polyurea microspheres, preparation method and application thereof - Google Patents

Porous cross-linked polyurea microspheres, preparation method and application thereof Download PDF

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CN107286314B
CN107286314B CN201610225294.7A CN201610225294A CN107286314B CN 107286314 B CN107286314 B CN 107286314B CN 201610225294 A CN201610225294 A CN 201610225294A CN 107286314 B CN107286314 B CN 107286314B
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linked polyurea
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CN107286314A (en
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丛海林
于冰
罗永丽
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Qingdao University
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    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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Abstract

The invention relates to a preparation method of porous cross-linked polyurea microspheres, which comprises the following steps: adding a prepolymerization monomer into the silicon dioxide dispersion liquid, reacting for 0.8-1.2 hours at the temperature of 25-35 ℃ after uniform dispersion, dropwise adding a cross-linking agent into the reaction liquid, fully reacting for 0.8-1.2 hours to obtain a solution containing the porous cross-linked polyurea microspheres, centrifugally separating, and washing filter residues to obtain the porous cross-linked polyurea microspheres. The preparation method of the porous cross-linked polyurea microspheres has the advantages of simple process, low production cost and good repeatability, and the surfaces of the prepared porous cross-linked polyurea microspheres have a microporous structure and good monodispersity, so that the porous cross-linked polyurea microspheres can be widely applied to the fields of wastewater adsorption treatment and the like.

Description

Porous cross-linked polyurea microspheres, preparation method and application thereof
Technical Field
The invention relates to the technical field of porous cross-linked polyurea microspheres, in particular to a porous cross-linked polyurea microsphere with a surface microporous structure, a method for preparing the surface cross-linked polyurea microsphere with the surface microporous structure by adopting a one-step method, and application of the porous cross-linked polyurea microsphere in the aspect of dye adsorption.
Background
With the development of dyes and related industries, organic pigment wastewater is a great problem for industrial treatment. The existing methods for treating pigment production wastewater are mainly divided into biochemical methods and physicochemical methods. Wherein adsorption is one of the important treatment methods. The commonly used adsorption materials are mainly porous materials with high specific surface area, such as activated carbon, molecular sieves, synthetic polymer materials and the like. The polymer material is favored by the advantages of more types of pore structures, high specific surface area, high adsorption performance and the like.
At present, there are many researches on the treatment of dye wastewater by porous polymer materials, and some documents adopt the following preparation methods: (1) wang Chaoyang et al, journal 2015 of Composites Science and Technology, 107,137-144, reported a method of suspension polymerization using oil and water emulsion, using styrene and divinylbenzene as raw materials, synthesizing porous microspheres and further loading Ag for treating dye wastewater; (2) the synthesis of magnetic microporous beads using macroporous polydivinylbenzene as a template and used for treating wastewater was reported by Liu Qingquan et al in Journal of hazardous materials 2010,181,586 and 592; (3) yangxing et al, The Journal of The Process Engineering 2009,1009,31-34, reported that a reverse phase suspension method was used to prepare porous crosslinked chitosan microspheres with liquid paraffin as an organic dispersion medium, epichlorohydrin as a crosslinking agent, and polyethylene glycol as a pore-forming agent, and studied The adsorption performance of The microspheres to organic dyes.
The preparation methods listed above are complicated, include the steps such as synthesis and surface modification of the polymer, need to add pore-forming agent and stabilizer, etc. in the synthetic process, the process is tedious, time-consuming, and the preparation process produces waste gas and waste liquid and harmful organic solvent to pollute the environment, the pore-forming agent used, stabilizer residue can also influence the performance of the product.
Disclosure of Invention
Therefore, the technical problems to be solved by the invention are that the existing preparation process of the porous polymer material is complex and waste gas and waste liquid are generated to pollute the environment, and the preparation method of the porous cross-linked polyurea microspheres has the advantages of simple process, low production cost and good repeatability, and the surfaces of the prepared porous cross-linked polyurea microspheres have a microporous structure and good monodispersity and can be widely used in the fields of wastewater adsorption treatment and the like.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of porous cross-linked polyurea microspheres comprises the following steps:
adding a prepolymerization monomer into the silicon dioxide dispersion liquid, reacting for 0.8-1.2 hours at the temperature of 25-35 ℃ after uniform dispersion, dropwise adding a cross-linking agent into the reaction liquid, fully reacting for 0.8-1.2 hours to obtain a solution containing the porous cross-linked polyurea microspheres, centrifugally separating, and washing filter residues to obtain the porous cross-linked polyurea microspheres.
The prepolymerization monomer is isophorone diisocyanate (IPDI), and the cross-linking agent is triethylene tetramine (TETA).
The preparation method of the silicon dioxide dispersion liquid comprises the following steps: dispersing the monodisperse silicon dioxide particles in a solvent, stirring by a glass rod and ultrasonically dispersing for 12-17min to obtain uniformly dispersed silicon dioxide dispersion liquid.
The solvent is a mixed solvent consisting of acetone and water.
Preferably, the mass ratio of the monodisperse silica particles, acetone, water, IPDI, TETA is: (0.5-1.5): 66.5: 28.5: 5: (0.822 to 6.576).
Adding the pre-polymerized monomer into the silicon dioxide dispersion liquid, and shaking for 0.5-1.5 min.
And washing filter residues by using acetone and water.
The porous cross-linked polyurea microspheres prepared by the method.
An application of the porous cross-linked polyurea microspheres in dye sewage treatment, in particular to an application in adsorbing iodine and methyl orange dye in dye sewage.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) the preparation method of the porous cross-linked polyurea microspheres comprises the steps of adding a prepolymerization monomer into a silicon dioxide dispersion liquid, reacting for 0.8-1.2 hours at the temperature of 25-35 ℃ after uniform dispersion, dripping a cross-linking agent into the reaction liquid, fully reacting for 0.8-1.2 hours to obtain a solution containing the porous cross-linked polyurea microspheres, carrying out centrifugal separation, and washing filter residues to obtain the porous cross-linked polyurea microspheres. The polyurea microspheres with the surface microporous structure can be obtained by adopting a one-step synthesis method. Firstly, polyurea microspheres are formed by precipitation polymerization, then silicon dioxide and the polyurea microspheres are combined through electrostatic action, and finally added TETA is alkaline and can etch away the silicon dioxide, so that the polyurea microspheres become porous spheres.
(2) The surface of the porous cross-linked polyurea microsphere prepared by the invention has micropores, and the average pore diameter of the micropores on the surface of the microsphere is 0.15-0.95 mu m through measurement, so that the monodispersity is good, and the adsorption capacity of the microsphere to dye is greatly improved. The pore diameter of the microsphere surface can be changed by changing the particle size of the added silicon dioxide in the experiment, for example, the experiment uses silicon dioxide of 200nm, 375nm,450nm and 1200nm respectively; or the amount of the silica used in the experiment is changed, for example, different amounts of silica such as 0.5g, 1.0g, 1.2g and 1.5g are used in the experiment to change the pore diameter on the surface of the microsphere. Can be widely used in the fields of wastewater adsorption treatment and the like, and is particularly suitable for the fields of dye sewage treatment and the like.
(3) The preparation process of the porous cross-linked polyurea microspheres is simple and efficient, the repeatability is good, the used raw materials are easy to obtain, and the production cost is low; the prepared porous cross-linked polyurea microspheres have a microporous structure on the surfaces and good monodispersity.
Drawings
FIG. 1 is a scanning electron micrograph of porous cross-linked polyurea microspheres obtained in example 1;
FIG. 2 is a scanning electron micrograph of the porous cross-linked polyurea microspheres obtained in example 2;
FIG. 3 is a scanning electron micrograph of the porous cross-linked polyurea microspheres obtained in example 3;
FIG. 4 is a scanning electron micrograph of the porous cross-linked polyurea microspheres obtained in example 4;
FIG. 5 is a scanning electron micrograph of the porous cross-linked polyurea microspheres obtained in example 5;
FIG. 6 is a scanning electron micrograph of the porous cross-linked polyurea microspheres obtained in example 6.
FIG. 7 is a scanning electron micrograph of the porous crosslinked polyurea microspheres obtained in example 7.
FIG. 8 is a scanning electron micrograph of the porous crosslinked polyurea microspheres obtained in example 8.
FIG. 9 is a graph comparing the porous cross-linked polyurea microspheres added with the iodine solution of 245mg/L obtained in application example 1 with that without the addition of the porous cross-linked polyurea microspheres.
FIG. 10 is a graph showing the comparison of the porous crosslinked polyurea microspheres obtained in application example 2 with a 10mg/L methyl orange solution without the addition of the porous crosslinked polyurea microspheres.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in further detail below. This invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete and will fully convey the concept of the invention to those skilled in the art, and the present invention will only be defined by the appended claims.
The preparation method of the porous cross-linked polyurea microspheres provided by the invention comprises the following steps:
dispersing monodisperse silicon dioxide particles in a mixed solvent consisting of acetone and water, stirring by a glass rod and ultrasonically dispersing for 12-17min to obtain uniformly dispersed silicon dioxide dispersion liquid;
adding a prepolymerized monomer isophorone diisocyanate (IPDI) into the silicon dioxide dispersion liquid, shaking for 0.5-1.5min to uniformly disperse the silicon dioxide dispersion liquid, reacting at the temperature of 25-35 ℃ for 0.8-1.2 hours, dropwise adding a cross-linking agent triethylene tetramine (TETA) into the reaction liquid, fully reacting for 0.8-1.2 hours after dropwise adding is finished to obtain a solution containing porous cross-linked polyurea microspheres, centrifugally separating, and washing filter residues with acetone/water to obtain the porous cross-linked polyurea microspheres.
The mass ratio of the monodisperse silicon dioxide particles to the acetone to the water to the IPDI to the TETA is as follows: (0.5-1.5): 66.5: 28.5: 5: (0.822 to 6.576).
The invention also provides the porous cross-linked polyurea microspheres prepared by the method and application of the porous cross-linked polyurea microspheres in dye sewage treatment, in particular application in adsorbing iodine and methyl orange dye in dye sewage.
Example 1
The porous cross-linked polyurea microspheres of the present example had a surface microporous structure, and the average pore diameter of the surface micropores was 0.3 μm.
The preparation method of the porous cross-linked polyurea microspheres comprises the following steps:
s1, dispersing 0.5g of monodisperse silica particles with the average particle size of 375nm in a mixed solvent consisting of 66.5g of acetone and 28.5g of water, stirring by a glass rod and ultrasonically dispersing for 15min to obtain a uniformly dispersed silica dispersion liquid.
S2, adding 5g of monomer isophorone diisocyanate (IPDI) into the monodisperse silica dispersion liquid, shaking for 1 minute to enable the monomer to be uniformly dispersed, standing at the temperature of 30 ℃ and reacting for 1 hour.
S3, adding 1.644g of a cross-linking agent triethylene tetramine TETA into the solution after the reaction for 1 hour, and after the addition is finished, fully reacting for 1 hour to obtain the solution containing the porous cross-linked polyurea microspheres.
S4, centrifuging the solution of the porous cross-linked polyurea microspheres, and washing the porous cross-linked polyurea microspheres by using a mixed solvent formed by acetone and water to obtain the porous cross-linked polyurea microspheres, wherein the using amount of the porous cross-linked polyurea microspheres and the mixed solvent is 70mL/30 mL.
The mass ratio of the monodisperse silicon dioxide particles to the acetone to the water to the IPDI to the TETA is as follows: 0.5: 66.5: 28.5: 5: 1.644.
the scanning electron microscope of the porous cross-linked polyurea microspheres prepared in this example is shown in fig. 1, and it can be seen from fig. 1 that the microspheres have many pores on the surface, and are uniformly distributed and relatively uniform in pore size.
Example 2
The porous cross-linked polyurea microspheres of the present example had a surface microporous structure, and the average pore diameter of the surface micropores was 0.3 μm.
The preparation method of the porous cross-linked polyurea microspheres of the embodiment comprises the following steps:
s1, dispersing 1.2g of monodisperse silica particles with the average particle size of 375nm in a solvent consisting of 66.5g of acetone and 28.5g of water, stirring by a glass rod and ultrasonically dispersing for 15min to obtain a uniformly dispersed silica dispersion liquid.
S2, adding 5g of monomer isophorone diisocyanate (IPDI) into the monodisperse silica dispersion liquid, shaking for 1 minute to enable the monomer IPDI to be uniformly dispersed, and standing at the temperature of 30 ℃ to react for 1 hour.
S3, adding 1.644g of a cross-linking agent triethylene tetramine TETA into the solution after the reaction for 1 hour, and after the addition is finished, fully reacting for 1 hour to obtain the solution containing the porous cross-linked polyurea microspheres.
S4, centrifuging the solution of the porous cross-linked polyurea microspheres, and washing with a mixed solvent formed by acetone and water to obtain the porous cross-linked polyurea microspheres, wherein the using amount of the porous cross-linked polyurea microspheres is 70mL/30 mL.
The mass ratio of the monodisperse silicon dioxide particles to the acetone to the water to the IPDI to the TETA is as follows: 1.2: 66.5: 28.5: 5: 1.644.
the scanning electron microscope of the porous cross-linked polyurea microspheres prepared in this example is shown in fig. 2, and it can be seen from fig. 2 that the microspheres have many pores on the surface, and are uniformly distributed and relatively uniform in pore size.
Example 3
The porous cross-linked polyurea microspheres of the present example had a surface microporous structure, and the average pore diameter of the surface micropores was 0.3 μm.
The preparation method of the porous cross-linked polyurea microspheres of the embodiment comprises the following steps:
s1, dispersing 1.2g of monodisperse silica particles with the average particle size of 375nm in a solvent consisting of 66.5g of acetone and 28.5g of water, stirring by a glass rod and ultrasonically dispersing for 15min to obtain a uniformly dispersed silica dispersion liquid.
S2, adding 5g of monomer IPDI into the monodisperse silicon dioxide dispersion liquid, shaking for 1 minute to enable the monomer IPDI to be uniformly dispersed, and standing at the temperature of 30 ℃ to react for 1 hour.
S3, adding 6.576g of cross-linking agent TETA into the solution after the reaction for 1 hour, and fully reacting for 1 hour after the addition is finished to obtain the solution containing the porous cross-linked polyurea microspheres.
S4, centrifuging the solution of the porous cross-linked polyurea microspheres, and washing with a mixed solvent formed by acetone/water to obtain the porous cross-linked polyurea microspheres, wherein the using amount of the porous cross-linked polyurea microspheres and the mixed solvent is 70mL/30 mL.
The mass ratio of the monodisperse silicon dioxide particles to the acetone to the water to the IPDI to the TETA is as follows: 1.2: 66.5: 28.5: 5: 6.576.
the scanning electron microscope of the porous cross-linked polyurea microspheres prepared in this example is shown in fig. 3, and it can be seen from fig. 3 that the microspheres have many pores on the surface, and are uniformly distributed and relatively uniform in pore size.
Example 4
The porous cross-linked polyurea microspheres of the present example had a surface microporous structure, and the average pore diameter of the surface micropores was 0.15. mu.m.
The preparation method of the porous cross-linked polyurea microspheres of the embodiment comprises the following steps:
s1, dispersing 1.2g of monodisperse silica particles with the average particle size of 200nm in a solvent consisting of 66.5g of acetone and 28.5g of water, stirring by a glass rod and ultrasonically dispersing for 15min to obtain a uniformly dispersed silica dispersion liquid.
S2, adding 5g of monomer IPDI into the monodisperse silicon dioxide dispersion liquid, shaking for 1 minute to enable the monomer IPDI to be uniformly dispersed, and standing at the temperature of 30 ℃ to react for 1 hour.
S3, adding 1.644g of cross-linking agent TETA into the solution after the reaction for 1 hour, and fully reacting for 1 hour after the addition is finished to obtain the solution containing the porous cross-linked polyurea microspheres.
S4, centrifuging the solution of the porous cross-linked polyurea microspheres, and washing with a mixed solvent formed by acetone and water to obtain the porous cross-linked polyurea microspheres, wherein the using amount of the porous cross-linked polyurea microspheres is 70mL/30 mL.
The mass ratio of the monodisperse silicon dioxide particles to the acetone to the water to the IPDI to the TETA is as follows: 1.2: 66.5: 28.5: 5: 1.644.
the monomer is isophorone diisocyanate (IPDI); the solvent is acetone and water; the cross-linking agent is triethylene tetramine (TETA).
The weight ratio of the monodisperse silica particles to the solvent is 1.2: 95.
the scanning electron microscope of the porous cross-linked polyurea microspheres prepared in this example is shown in fig. 4, and it can be seen from fig. 4 that the microspheres have many pores on the surface, and are uniformly distributed and relatively uniform in pore size.
Example 5
The porous cross-linked polyurea microspheres of the present example had a surface microporous structure, and the average pore diameter of the surface micropores was 0.3 μm.
The preparation method of the porous cross-linked polyurea microspheres of the embodiment comprises the following steps:
s1, dispersing 1.2g of monodisperse silica particles with the average particle size of 375nm in a solvent consisting of 66.5g of acetone and 28.5g of water, stirring by a glass rod and ultrasonically dispersing for 15min to obtain a uniformly dispersed silica dispersion liquid.
S2, adding 5g of monomer IPDI into the monodisperse silicon dioxide dispersion liquid, shaking for 1 minute to enable the monomer IPDI to be uniformly dispersed, and standing at the temperature of 30 ℃ to react for 1 hour.
S3, adding 1.644g of cross-linking agent TETA into the solution after the reaction for 1 hour, and fully reacting for 1 hour after the addition is finished to obtain the solution containing the porous cross-linked polyurea microspheres.
S4, centrifuging the solution of the porous cross-linked polyurea microspheres, and washing with a mixed solvent formed by acetone and water to obtain the porous cross-linked polyurea microspheres, wherein the using amount of the porous cross-linked polyurea microspheres is 70mL/30 mL.
The mass ratio of the monodisperse silicon dioxide particles to the acetone to the water to the IPDI to the TETA is as follows: 1.2: 66.5: 28.5: 5: 1.644.
the monomer is isophorone diisocyanate (IPDI); the solvent is acetone and water; the cross-linking agent is triethylene tetramine (TETA).
The weight ratio of the monodisperse silica particles to the solvent is 1.2: 95.
the scanning electron microscope of the porous cross-linked polyurea microspheres prepared in this example is shown in fig. 5, and it can be seen from fig. 5 that the microspheres have many pores on the surface, and are uniformly distributed and relatively uniform in pore size.
Example 6
The porous cross-linked polyurea microspheres of the present example had a surface microporous structure, and the average pore diameter of the surface micropores was 0.95. mu.m.
The preparation method of the porous cross-linked polyurea microspheres of the embodiment comprises the following steps:
s1, dispersing 1.2g of monodisperse silica particles with the average particle size of 1200nm in a solvent consisting of 66.5g of acetone and 28.5g of water, stirring by a glass rod and ultrasonically dispersing for 15min to obtain a uniformly dispersed silica dispersion liquid.
S2, adding 5g of monomer IPDI into the monodisperse silicon dioxide dispersion liquid, shaking for 1 minute to enable the monomer IPDI to be uniformly dispersed, and standing at the temperature of 30 ℃ to react for 1 hour.
S3, adding 1.644g of cross-linking agent TETA into the solution after the reaction for 1 hour, and fully reacting for 1 hour after the addition is finished to obtain the solution containing the porous cross-linked polyurea microspheres.
S4, centrifuging the solution of the porous cross-linked polyurea microspheres, and washing with a mixed solvent formed by acetone and water to obtain the porous cross-linked polyurea microspheres, wherein the using amount of the porous cross-linked polyurea microspheres is 70mL/30 mL.
The mass ratio of the monodisperse silicon dioxide particles to the acetone to the water to the IPDI to the TETA is as follows: 1.2: 66.5: 28.5: 5: 1.644.
the monomer is isophorone diisocyanate (IPDI); the solvent is acetone and water; the cross-linking agent is triethylene tetramine (TETA).
The weight ratio of the monodisperse silica particles to the solvent is 1.2: 95.
the scanning electron microscope of the porous cross-linked polyurea microspheres prepared in this example is shown in fig. 6, and it can be seen from fig. 6 that the surfaces of the microspheres have a small number of pores and a large pore ratio.
Example 7
The porous cross-linked polyurea microspheres of the present example had a surface microporous structure, and the average pore diameter of the surface micropores was 0.3 μm.
The preparation method of the porous cross-linked polyurea microspheres of the embodiment comprises the following steps:
s1, dispersing 1.2g of monodisperse silica particles with the average particle size of 375nm in a solvent consisting of 66.5g of acetone and 28.5g of water, stirring by a glass rod and ultrasonically dispersing for 15min to obtain a uniformly dispersed silica dispersion liquid.
S2, adding 5g of monomer IPDI into the monodisperse silicon dioxide dispersion liquid, shaking for 1 minute to enable the monomer IPDI to be uniformly dispersed, and standing at the temperature of 30 ℃ to react for 1 hour.
S3, 0.822g of cross-linking agent TETA is dripped into the solution after the reaction for 1 hour, and the solution is fully reacted for 1 hour after the dripping is finished, so that the solution containing the porous cross-linked polyurea microspheres is obtained.
S4, centrifuging the solution of the porous cross-linked polyurea microspheres, and washing with a mixed solvent formed by acetone and water to obtain the porous cross-linked polyurea microspheres, wherein the using amount of the porous cross-linked polyurea microspheres is 70mL/30 mL.
The mass ratio of the monodisperse silicon dioxide particles to the acetone to the water to the IPDI to the TETA is as follows: 1.2: 66.5: 28.5: 5: 0.822.
the monomer is isophorone diisocyanate (IPDI); the solvent is acetone and water; the cross-linking agent is triethylene tetramine (TETA).
The weight ratio of the monodisperse silica particles to the solvent is 1.2: 95.
a scanning electron microscope of the porous cross-linked polyurea microspheres prepared in this example is shown in FIG. 7. As can be seen from FIG. 7, the microspheres have many pores on the surface, and are uniformly distributed and have relatively uniform pore sizes.
Example 8
The porous cross-linked polyurea microspheres of the present example had a surface microporous structure, and the average pore diameter of the surface micropores was 0.3 μm.
The preparation method of the porous cross-linked polyurea microspheres of the embodiment comprises the following steps:
s1, dispersing 1.2g of monodisperse silica particles with the average particle size of 375nm in a solvent consisting of 66.5g of acetone and 28.5g of water, stirring by a glass rod and ultrasonically dispersing for 15min to obtain a uniformly dispersed silica dispersion liquid.
S2, adding 5g of monomer IPDI into the monodisperse silicon dioxide dispersion liquid, shaking for 1 minute to enable the monomer IPDI to be uniformly dispersed, and standing at the temperature of 30 ℃ to react for 1 hour.
S3, adding 1.644g of cross-linking agent TETA into the solution after the reaction for 1 hour, and fully reacting for 1 hour after the addition is finished to obtain the solution containing the porous cross-linked polyurea microspheres.
S4, centrifuging the solution of the porous cross-linked polyurea microspheres, and washing with a mixed solvent formed by acetone and water to obtain the porous cross-linked polyurea microspheres, wherein the using amount of the porous cross-linked polyurea microspheres is 70mL/30 mL.
The mass ratio of the monodisperse silicon dioxide particles to the acetone to the water to the IPDI to the TETA is as follows: 1.2: 66.5: 28.5: 5: 1.644.
the monomer is isophorone diisocyanate (IPDI); the solvent is acetone and water; the cross-linking agent is triethylene tetramine (TETA).
The weight ratio of the monodisperse silica particles to the solvent is 1.2: 95.
a scanning electron microscope of the porous cross-linked polyurea microspheres prepared in this example is shown in FIG. 8. As can be seen from FIG. 8, the microspheres have many pores on the surface, and are uniformly distributed and have relatively uniform pore diameters.
Application example 1
The porous cross-linked polyurea microspheres prepared in example 8 were added to a pre-prepared 245mg/L iodine solution, shaken for 3min, allowed to stand for a while until the solution turns colorless from brown, and then compared with the 245mg/L iodine solution without the porous cross-linked polyurea microspheres, to obtain FIG. 9. As can be seen from FIG. 9, the iodine solution to the left without the porous cross-linked polyurea microspheres is brown, and the iodine solution to the right with the porous cross-linked polyurea microspheres is colorless. Measured by
Figure BDA0000963553070000111
Wherein η is adsorption rate, specifically η ═ C0-Ce)·100％/C0，(C0Is the initial concentration of iodine solution, CeIs the equilibrium concentration of the iodine solution)
Application example 2
The porous cross-linked polyurea microspheres prepared in example 8 are added into a pre-prepared 10mg/L methyl orange solution, and then the mixture is shaken for 3min, and is kept still for a period of time, the solution changes from orange to colorless, and then the comparison with the 10mg/L methyl orange solution without the porous cross-linked polyurea microspheres is carried out to obtain a graph 10, as can be seen from the graph 10, the methyl orange solution without the porous cross-linked polyurea microspheres added to the left side is orange, and the methyl orange solution with the porous cross-linked polyurea microspheres added to the right side is colorless. The detected data are as follows:
Figure BDA0000963553070000112
wherein η is adsorption rate, specifically η ═ C0-Ce)·100％/C0，(C0Is the initial concentration of methyl orange solution, CeIs the equilibrium concentration of methyl orange solution)
The above examples are merely illustrative for clarity and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (8)

1. A preparation method of porous cross-linked polyurea microspheres is characterized by comprising the following steps:
adding a prepolymerization monomer into the silicon dioxide dispersion liquid, reacting for 0.8-1.2 hours at the temperature of 25-35 ℃ after uniform dispersion, dropwise adding a cross-linking agent into the reaction liquid, fully reacting for 0.8-1.2 hours to obtain a solution containing porous cross-linked polyurea microspheres, centrifugally separating, and washing filter residues to obtain the porous cross-linked polyurea microspheres;
the prepolymerization monomer is isophorone diisocyanate (IPDI), and the cross-linking agent is triethylene tetramine (TETA);
the preparation method of the silicon dioxide dispersion liquid comprises the following steps: dispersing the monodisperse silicon dioxide particles in a solvent, stirring by a glass rod and ultrasonically dispersing for 12-17min to obtain uniformly dispersed silicon dioxide dispersion liquid.
2. The method for preparing porous cross-linked polyurea microspheres according to claim 1, wherein the solvent is a mixed solvent of acetone and water.
3. The method for preparing porous cross-linked polyurea microspheres according to claim 2, wherein the mass ratio of the monodisperse silica particles to the acetone to the water to the IPDI to the TETA is: (0.5-1.5): 66.5: 28.5: 5: (0.822 to 6.576).
4. The method of preparing porous cross-linked polyurea microspheres according to claim 3, wherein the pre-polymerized monomer is added to the silica dispersion and shaken for 0.5 to 1.5 min.
5. The method for preparing porous cross-linked polyurea microspheres according to claim 4, wherein the filter residue is washed with acetone and water.
6. Porous cross-linked polyurea microspheres prepared according to the process of any one of claims 1 to 5.
7. Use of the porous cross-linked polyurea microspheres according to claim 6 in dye sewage treatment.
8. The use of the porous cross-linked polyurea microspheres according to claim 7 for adsorbing iodine and methyl orange dyes in dye sewage.
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