CN109880149B - Preparation method of large-size polyurea hollow microspheres - Google Patents
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Abstract
The invention relates to a preparation method of large-size polyurea hollow microspheres. The aqueous solution containing aliphatic amine or stabilizer is used as aqueous phase, diisocyanate compound or the mixed solution of diisocyanate compound and organic solvent is used as oil phase, the oil phase is added into a pipeline carrying flowing aqueous phase through a needle head to prepare the large-size polyurea hollow microsphere through interfacial polymerization, and the particle size of the obtained microsphere and the size of the inner cavity thereof can be adjusted by simply regulating and controlling the reaction time, the using amount of the organic solvent, the aperture of the needle head, the flow rate of the two phases and the like. The method has the advantages of single system component, simple process steps, continuous operation, easy separation of the microspheres and low production cost, and is beneficial to large-scale production and application of the microspheres.
Description
Technical Field
The invention relates to a preparation method of a polymer hollow microsphere, in particular to a method for preparing a large-size polyurea hollow microsphere by an interfacial polymerization method, and belongs to the field of functional polymer materials.
Background
By polymeric hollow microspheres is meant microspheres having an outer shell comprised of a polymer and an interior containing one or more hollow structures. Compared with a solid microsphere material, the polymer hollow microsphere has the characteristics of low density, high specific surface area, capability of accommodating guest molecules and the like, and has wide application prospects in the fields of drug controlled release, chemical catalysis, electronic ink, biological imaging, coating industry and the like.
At present, the methods for preparing the polymer hollow microspheres mainly comprise a template method, a self-assembly method, an emulsion polymerization method, a suspension polymerization method and the like. The template method is the most common method for preparing hollow polymer microspheres, and is characterized in that a layer of polymer shell is formed on the surface of template particles, and then the template particles are removed by etching and other methods, so that the hollow polymer microspheres are obtained. Japanese patent laid-open No. 2002-241448 provides a method for preparing polymeric hollow microspheres, which comprises preparing polymeric microspheres having a 3-layer structure by three-step radical polymerization, and preparing the polymeric hollow microspheres after removing the inner core by neutralization with a base. Du et al (Journal of the American Chemical Society,2005, 127 vol., 12800-12801) reported a method for preparing hollow microspheres of polymers by self-assembly of block copolymer PEO-b-P (DEA-s-TMSPMA), in which hydrophobic P (DEA-s-TMSPMA) blocks self-assemble to form a shell layer of the hollow microspheres, and then TMSPMA is crosslinked in the microsphere shell layer by in situ sol-gel reaction, and the resulting hollow microspheres have controllable permeability at different pH. Chinese patent CN105482602A discloses a method for preparing hollow polymer microspheres by suspension polymerization, which comprises the steps of emulsifying a mixture of BPO, MMA, EGD-MA, BZ, HP, HD and the like, heating to 60-80 ℃, polymerizing for 2-6h, and heating to 75-100 ℃, and polymerizing for 12-20h to obtain the hollow polymer microspheres. CN103865010B discloses a method for preparing functional inorganic/polymer hollow microspheres, which comprises dispersing an inorganic precursor in monomer droplets by an in-situ miniemulsion polymerization method, limiting a liquid precursor in the center of the microspheres by utilizing phase separation between the inorganic precursor and a polymer after polymerization reaction, reducing the volume of the precursor after hydrolysis to form a hollow structure, and further dropwise adding a functional monomer to introduce a functional group on the surface of the microspheres to obtain the functional inorganic/polymer hybrid hollow microspheres. CN108794721A discloses a preparation method of polyurethane hollow microspheres, which comprises the steps of preparing polyurethane prepolymer through stepwise polymerization, homogenizing and emulsifying the polyurethane prepolymer with a mixture of a hydrophobic solvent and water, carrying out emulsion polymerization, and finally adding a cross-linking agent to cross-link polyurethane to obtain the polyurethane hollow microspheres.
The different preparation methods can endow the microspheres with different sizes or specific internal structures, but the methods have some defects, for example, template substances are required to be prepared in advance when the microspheres are prepared by a template method, the steps of removing the template at the later stage are complex, and the hollow microspheres can be obtained generally by calcining, dissolving or etching; the block copolymer required by the self-assembly method needs to be elaborately designed, so that the preparation process is complex and the production cost is high; the emulsion polymerization and suspension polymerization methods for preparing the hollow polymer microspheres have complex system components, need multi-step polymerization processes, and have complicated operation steps. In addition, the sizes of the polymer hollow microspheres prepared by the prior art are all below 10 μm, and reports about polymer hollow microspheres with the sizes of more than tens of micrometers are not found at present. Because the size of the microsphere is larger, the separation can be realized through simple natural sedimentation, and the microsphere has potential application in the fields of chemical catalysis, drug and fertilizer controlled release and the like. In conclusion, the development of a method for preparing the large-size polymer hollow microspheres with simple system components, convenient operation and low cost has very important significance in scientific research and production.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a simple method for preparing large-size polymer hollow microspheres at low cost without template substances in one step, so as to solve the problems of complicated process steps, complex system components, high production cost and the like in the process of preparing the polymer hollow microspheres in the prior art.
The technical scheme of the invention is as follows:
a preparation method of large-size polyurea hollow microspheres comprises the following steps:
at room temperature, taking a diisocyanate compound monomer as an oil phase, or taking a mixed solution of a diisocyanate compound and an organic solvent as an oil phase, taking an aqueous solution containing aliphatic amine or/and a stabilizer as an aqueous phase, adding the oil phase into a channel B carrying a flowing aqueous phase through a channel A for interfacial polymerization, and reacting the effluent at 20-90 ℃ for 0.5-24 h after the material flows out of a channel B port; and (4) carrying out solid-liquid separation, and drying the obtained solid after cleaning to obtain the large-size polyurea hollow microspheres.
According to the present invention, preferably, the inner diameter of the passage a is smaller than the inner diameter of the passage B.
According to the present invention, preferably, the channel A is a needle or a capillary;
preferably, the inner diameter of the channel A is 80-800 μm.
According to the invention, preferably, the channel B is a silicone tube;
preferably, the inner diameter of the channel B is 0.2-3.0 mm.
According to the present invention, the rate of addition of the oil phase to the aqueous phase is preferably 1 to 600. mu.L/min, more preferably 10 to 200. mu.L/min.
According to the present invention, the flow rate of the aqueous phase is preferably 0.05 to 60.0mL/min, more preferably 0.5 to 50.0 mL/min.
According to the present invention, it is preferable that the diisocyanate compound monomer is toluene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, dimethylbiphenyl diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, methylcyclohexyl diisocyanate, or/and dicyclohexylmethane diisocyanate.
According to the present invention, the organic solvent is preferably an organic solvent capable of dissolving the diisocyanate compound monomer and insoluble in water, and cyclohexane, n-hexane, toluene or xylene is more preferable.
According to the present invention, when a mixed solution of a diisocyanate compound and an organic solvent is used as an oil phase, the organic solvent preferably accounts for 1 to 90% of the total mass of the oil phase.
According to the invention, the aliphatic amine is preferably a polyamine or/and tertiary amine compound containing 2-10 carbon atoms, and more preferably the aliphatic amine is triethylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or/and tetraethylenepentamine.
According to the present invention, preferably, the stabilizer is polyvinyl alcohol, polyvinylpyrrolidone, sodium poly (meth) acrylate or/and carboxymethyl cellulose.
According to the invention, the mass fraction of the fatty amine or the stabilizer in the water phase is preferably 0.01-3.0%.
According to the invention, the reaction temperature is preferably 30-70 ℃.
According to the invention, the reaction is preferably continued for 1 to 12 hours after the addition is completed.
According to the invention, preferably, the supernatant in the product is poured out, the obtained solid is washed with acetone or acetonitrile for 2 times and then dried in an oven at 80-120 ℃ for 2-12 h, and the large-size polyurea hollow microspheres are obtained.
The average particle size of the large-size polyurea hollow microsphere obtained by the method is 100-2000 mu m, the particle size polydispersity coefficient is 1.003-1.020, and the diameter of the inner cavity is adjustable within the range of 50-1500 mu m.
The invention has the technical characteristics and excellent effects that:
the invention takes aqueous solution containing fatty amine or/and stabilizer as aqueous phase, takes diisocyanate compound monomer as oil phase, or takes mixed solution of diisocyanate compound and organic solvent as oil phase, and the oil phase is added into a channel B carrying flowing aqueous phase at constant speed through a channel A such as a needle head to carry out interfacial polymerization to prepare the large-size polyurea hollow microspheres. When the diisocyanate monomer enters a mobile phase containing fatty amine, the diisocyanate monomer on the surface of the mobile phase is sheared to form liquid drops, and then the diisocyanate monomer on the surface of the mobile phase can quickly react with the polyamine to form a gel layer or a protective shell, so that the coalescence of particles can be prevented; the invention can also use the aqueous solution containing the stabilizer as the mobile phase, when the diisocyanate liquid drop enters the aqueous phase, the stabilizer molecule therein is adsorbed to the surface of the liquid drop to maintain the stability of the liquid drop, and simultaneously, the diisocyanate monomer on the surface of the liquid drop can react with water to form a gel layer.
The invention can prepare the hollow polyurea microspheres without adding pore-forming agent or template substance. Because polyurea is insoluble in the monomer of the polyurea and the polyurea in the microsphere is gradually formed from outside to inside, the shell of the microsphere formed in the reaction process is composed of the polyurea, and unreacted diisocyanate monomer is arranged inside the microsphere, namely the polyurea microcapsule coated with the diisocyanate monomer. The polyurea microcapsules in the reaction process are heated to remove unreacted diisocyanate monomers, so that the polyurea microspheres with hollow structures inside can be obtained, the drying process of the microspheres and the formation of internal cavities are synchronously carried out, and other post-treatment processes are omitted. Since the shell of the capsule becomes thicker gradually with the reaction time, the thickness of the shell of the hollow microsphere can be adjusted by simply controlling the reaction time. The invention can also prepare the hollow polyurea microspheres by a method of adding an organic solvent. The organic solvent used (including n-hexane, cyclohexane, toluene and xylene) dissolves the diisocyanate monomer and does not dissolve the polyurea and water. When droplets containing organic solvent and diisocyanate monomer are added to an aqueous solution containing a stabilizer or fatty amine, the diisocyanate on the surface of the droplets reacts with water or polyamine to form polyurea. Because polyurea can not be dissolved in an organic solvent and a monomer, the system is subjected to phase separation, the polyurea is positioned outside the microsphere, unreacted monomers and the organic solvent are arranged inside the microsphere, and the product is the polyurea microcapsule coated with diisocyanate monomers and the organic solvent. The post-treatment process is the same as that for preparing the hollow polyurea microspheres without using an organic solvent, and the hollow polyurea microspheres can be prepared by simply heating to remove the organic solvent.
The polymerization reaction can be carried out in a common silica gel or PVC pipeline, collision and adhesion among the microspheres are not easy to occur, complex process steps are not needed, the hollow polyurea microspheres can be prepared in one step, the preparation process of the hollow microspheres is simplified, continuous operation is realized, and the obtained microspheres have high monodispersity. The size of the internal cavity of the microsphere obtained by the invention can be adjusted by controlling the reaction time and the dosage of the organic solvent. Because the sizes of the liquid drops and the final polyurea microspheres depend on the flow velocity of two phases, the aperture of a needle, the concentration of an aqueous solution in a mobile phase and the like, the size of the obtained microspheres can be adjusted in a wide range (100-2000 mu m) by simply changing the operation conditions. The hollow polyurea microspheres obtained by the method have larger size, no separation equipment is needed or magnetic substances are introduced, the separation can be realized through simple natural sedimentation, and the operation procedures of the microspheres in post-treatment and use are simplified.
Compared with the prior art, the invention has the following advantages:
1. when the hollow polyurea microspheres are prepared by the method, only three components of diisocyanate monomer, water and fatty amine (or stabilizer) are needed, substances such as template particles, initiators, comonomers and the like are not needed, and the system components are simple; meanwhile, the drying process of the microspheres and the forming process of the internal hollow structure are synchronously carried out, the polyurea hollow microspheres can be obtained without additional etching or dissolution and the like, and the process method is simpler. Therefore, the method has obvious advantages compared with the existing method for preparing the hollow polymer microspheres.
2. The invention can adjust the thickness of the shell or the size of the inner cavity by simply controlling the reaction time and the dosage of the organic solvent, and adjust the particle size of the obtained microsphere by changing the conditions of the aperture of the needle, the reaction temperature, the flow rate of the water phase and the oil phase and the like, thereby meeting the requirements of different occasions on the polymer hollow microsphere.
3. The polymerization reaction is carried out in a common pipeline and a flask, no special reaction device and equipment are needed, the energy consumption and the production cost are reduced, and meanwhile, the continuous operation can be carried out, thereby being beneficial to the large-scale production of the hollow microspheres.
4. The microsphere obtained by the invention has larger grain diameter and is easy to separate. In the post-treatment and use processes of the microspheres, the clear liquid can be separated after the microspheres naturally settle, so that the microspheres have potential application in the fields of chemical catalysis, controlled release of medicines and chemical fertilizers and the like.
Drawings
FIG. 1 is an optical micrograph of hollow polyurea microspheres obtained in example 1.
FIG. 2 is a scanning electron micrograph of a cross section of the hollow polyurea microspheres obtained in example 1.
FIG. 3 is an optical micrograph of hollow polyurea microspheres obtained in example 5.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
The surface and section morphology of the hollow polyurea microspheres obtained was observed by using an Olympus BX-51 optical microscope and a Quanta FEG-250 scanning electron microscope. Measuring at least 200 particles from the optical microscope photograph, and calculating the average particle diameter (D) of the microspheres by the following formulan) And polydispersity index (D)w/Dn)：
Wherein D isnAnd DwNumber average and weight average particle diameter of the microspheres, DiIs the size of any group of microspheres with the same particle size, niHas a particle diameter of DiK is the total number of particles.
Cutting the hollow polyurea microspheres with a knife, observing the appearance of the section of the hollow polyurea microspheres by a scanning electron microscope, and adopting the average particle size (D)n) The same calculation method obtains the thickness of the shell layer.
Example 1.
At room temperature, adding isophorone diisocyanate monomer into a silica gel tube loaded with flowing diethylenetriamine aqueous solution through a needle with the inner diameter of 159 mu m at the speed of 20 mu L/min, wherein the concentration of the diethylenetriamine solution is 0.5 wt%, the flow rate is 0.1mL/min, and the inner diameter of the silica gel tube is 0.6 mm; adding the pipeline effluent into a reaction bottle, placing the reaction bottle in a constant-temperature water bath at 70 ℃, and continuing to preserve heat for 2 hours after the monomer is dropwise added; and pouring out the aqueous solution in the product, washing the obtained microsphere solid with acetone for 2 times, and drying in an oven at 120 ℃ for 10 hours to obtain the large-size polyurea hollow microsphere product.
The average particle diameter of the hollow polyurea microspheres is 498 mu m, the particle diameter polydispersity is 1.007, the size of the internal cavities of the microspheres is 360 mu m, the optical microscope photo of the hollow polyurea microspheres is shown in figure 1, and the scanning electron microscope photo of the sections of the microspheres is shown in figure 2.
Example 2.
At room temperature, toluene diisocyanate monomer is added into a silica gel tube loaded with flowing triethylene tetramine aqueous solution through a needle with the inner diameter of 159 mu m at the speed of 20 mu L/min, wherein the concentration of the triethylene tetramine solution is 0.2 wt%, the flow rate is 0.1mL/min, and the inner diameter of the silica gel tube is 0.6 mm; adding the pipeline effluent into a reaction bottle, placing the reaction bottle in a constant-temperature water bath at the temperature of 30 ℃, and continuing to preserve heat for 4 hours after the monomer is dropwise added; and (3) pouring out the aqueous solution in the product, washing the obtained microsphere solid with acetonitrile for 2 times, and then placing the washed microsphere solid in an oven at 100 ℃ for drying for 10 hours to obtain the large-size polyurea hollow microsphere product.
The average particle size of the hollow polyurea microspheres is 502 microns, the particle size polydispersity is 1.007, and the size of the internal cavities of the microspheres is 298 microns.
Example 3.
At room temperature, toluene diisocyanate monomer is added into a silica gel tube loaded with flowing ethylenediamine aqueous solution through a needle with the inner diameter of 159 mu m at the speed of 20 mu L/min, wherein the concentration of the ethylenediamine solution is 0.3 wt%, the flow rate is 0.1mL/min, and the inner diameter of the silica gel tube is 0.6 mm; adding the pipeline effluent into a reaction bottle, placing the reaction bottle in a constant-temperature water bath at the temperature of 30 ℃, and continuing to preserve heat for 6 hours after the monomer is dropwise added; and (3) pouring out the aqueous solution in the product, washing the obtained microsphere solid with acetone for 2 times, and drying in an oven at 80 ℃ for 10 hours to obtain the large-size polyurea hollow microsphere product.
The average particle diameter of the obtained polyurea hollow microsphere is 506 mu m, the particle diameter polydispersity index is 1.006, and the size of the inner cavity of the microsphere is 157 mu m.
Example 4.
At room temperature, a toluene/toluene diisocyanate monomer mixed solution with the mass ratio of 1/1 is added into a silicone tube loaded with flowing ethylenediamine aqueous solution through a needle with the inner diameter of 159 mu m at the speed of 20 mu L/min, wherein the concentration of the ethylenediamine solution is 0.3 wt%, the flow rate is 0.1mL/min, and the inner diameter of the silicone tube is 0.6 mm; adding the pipeline effluent into a reaction bottle, placing the reaction bottle in a constant-temperature water bath at 60 ℃, and continuing to preserve heat for 5 hours after the monomer is dropwise added; and (3) pouring out the aqueous solution in the product, washing the obtained microsphere solid with acetone for 2 times, and then placing the washed microsphere solid in an oven at 80 ℃ for drying for 8 hours to obtain the large-size polyurea hollow microsphere product.
The average particle diameter of the obtained polyurea hollow microsphere is 496 mu m, the particle diameter polydispersity index is 1.006, and the size of the inner cavity of the microsphere is 305 mu m.
Example 5.
At room temperature, a mixed solution of xylene/dimethyl diphenyl diisocyanate monomer with the mass ratio of 2/8 is added into a silicone tube carrying flowing polyvinyl alcohol aqueous solution through a needle with the inner diameter of 159 mu m at the speed of 20 mu L/min, wherein the concentration of the polyvinyl alcohol solution is 1.5 wt%, the flow rate is 6.0mL/min, and the inner diameter of the silicone tube is 0.6 mm; adding the pipeline effluent into a reaction bottle, placing the reaction bottle in a constant-temperature water bath at the temperature of 80 ℃, and continuing to preserve heat for 2 hours after the monomer is dropwise added; and (3) pouring out the aqueous solution in the product, washing the obtained microsphere solid with acetonitrile for 2 times, and then drying in an oven at 80 ℃ for 10 hours to obtain the large-size polyurea hollow microsphere product.
The average particle diameter of the hollow polyurea microspheres obtained was 170 μm, the polydispersity of the particle diameter was 1.007, and the size of the internal cavity of the microspheres was 55 μm, as shown in FIG. 3.
Example 6.
Adding a mixed solution of n-hexane/hexamethylene diisocyanate monomer with the mass ratio of 5/5 into a PVC pipe loaded with flowing polyethylene glycol aqueous solution at room temperature through a needle with the inner diameter of 350 mu m at the speed of 30 mu L/min, wherein the concentration of the polyethylene glycol solution is 2.5 wt%, the flow rate is 5.0mL/min, and the inner diameter of the PVC pipe is 1.5 mm; adding the pipeline effluent into a reaction bottle, placing the reaction bottle in a constant-temperature water bath at 70 ℃, and continuing to preserve heat for 5 hours after the monomer is dropwise added; and pouring out the aqueous solution in the product, cleaning the obtained microsphere solid with acetone for 2 times, and then placing the cleaned microsphere solid in an oven at 100 ℃ for drying for 6 hours to obtain the large-size polyurea hollow microsphere product.
The average particle diameter of the obtained polyurea hollow microsphere is 967 mu m, the particle diameter polydispersity index is 1.010, and the size of the internal cavity of the microsphere is 565 mu m.
Example 7.
At room temperature, adding isophorone diisocyanate monomer into a silicone tube loaded with flowing polyvinyl alcohol aqueous solution through a needle with the inner diameter of 750 mu m at the speed of 100 mu L/min, wherein the concentration of the polyvinyl alcohol aqueous solution is 2.0 wt%, the flow rate is 50.0mL/min, and the inner diameter of the silicone tube is 3.0 mm; adding the pipeline effluent into a reaction bottle, placing the reaction bottle in a constant-temperature water bath at the temperature of 30 ℃, and continuing to preserve heat for 12 hours after the monomer is dropwise added; and (3) pouring out the aqueous solution in the product, washing the obtained microsphere solid with acetonitrile for 2 times, and then placing the cleaned microsphere solid in an oven at 100 ℃ for drying for 6 hours to obtain the large-size polyurea hollow microsphere product.
The average particle diameter of the hollow polyurea microspheres is 830 micrometers, the particle diameter polydispersity index is 1.013, and the size of the internal cavities of the microspheres is 379 micrometers.
Example 8.
At room temperature, toluene diisocyanate monomer is added into a silica gel tube loaded with flowing sodium polyacrylate aqueous solution through a needle with the inner diameter of 750 mu m at the speed of 200 mu L/min, wherein the concentration of the sodium polyacrylate solution is 3.0 wt%, the flow rate is 20mL/min, and the inner diameter of the silica gel tube is 3.0 mm; adding the pipeline effluent into a reaction bottle, placing the reaction bottle in a constant-temperature water bath at the temperature of 30 ℃, and continuing to preserve heat for 5 hours after the monomer is dropwise added; and (3) pouring out the aqueous solution in the product, washing the obtained microsphere solid with water for 2 times, and then drying in an oven at 100 ℃ for 6 hours to obtain the large-size polyurea hollow microsphere product.
The average particle diameter of the hollow polyurea microspheres obtained was 1907 μm, the polydispersity of the particle diameter was 1.009, and the size of the internal cavity of the microspheres was 1057 μm.
Comparative example 1
As described in example 1, except that: the aqueous solution of diethylenetriamine in the silicone tube did not flow.
Or adding the isophorone diisocyanate monomer into a reaction bottle containing the diethylenetriamine aqueous solution directly through a needle head, and placing the reaction bottle in a constant-temperature water bath at 70 ℃ for reaction.
As a result: when the diethylenetriamine aqueous solution in the silicone tube does not flow, the oil phase can not form liquid drops when being spitted out by a needle head due to the absence of the shearing of the water phase and the stripping action of gravity, so the obtained product has irregular shape and does not have the structure of microspheres;
when the isophorone diisocyanate monomer (oil phase) is directly added into a reaction bottle containing a diethylenetriamine aqueous solution through a needle, because the reaction of isophorone diisocyanate and diethylenetriamine is slow, a protective shell formed on the surface of a liquid drop at the initial stage of the reaction is thin, so that microspheres are easy to coalesce after being stacked at the bottom of the reaction bottle, the final product is an aggregate of a plurality of microspheres, and the size distribution of single microspheres is also uneven.
Claims (10)
1. A preparation method of large-size polyurea hollow microspheres comprises the following steps:
at room temperature, taking a diisocyanate compound monomer as an oil phase, or taking a mixed solution of a diisocyanate compound and an organic solvent as the oil phase, taking an aqueous solution containing aliphatic amine and a stabilizer as a water phase, adding the oil phase into a channel B carrying a flowing water phase through a channel A for interfacial polymerization, and reacting the effluent at 20-90 ℃ for 0.5-24 h after the material flows out of a channel B port; performing solid-liquid separation, cleaning the obtained solid with acetone or acetonitrile for 2 times, and drying in an oven at 80-120 ℃ for 2-12 h to obtain large-size polyurea hollow microspheres;
the inner diameter of the channel A is smaller than that of the channel B;
the diisocyanate compound monomer is toluene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, dimethyl biphenyl diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, methyl cyclohexyl diisocyanate or/and dicyclohexylmethane diisocyanate;
the organic solvent is cyclohexane, normal hexane, toluene or xylene;
the aliphatic amine is triethylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or/and tetraethylenepentamine;
the stabilizer is polyvinyl alcohol, polyvinylpyrrolidone, sodium poly (meth) acrylate or/and carboxymethyl cellulose.
2. The preparation method of large-size polyurea hollow microspheres according to claim 1, wherein the inner diameter of the A channel is 80-800 μm.
3. The preparation method of large-size polyurea hollow microspheres according to claim 1, wherein the inner diameter of the B channel is 0.2-3.0 mm.
4. The method for preparing large-size polyurea hollow microspheres according to claim 1, wherein the rate of adding the oil phase to the water phase is 1 to 600 μ L/min.
5. The method for preparing large-size polyurea hollow microspheres according to claim 4, wherein the rate of adding the oil phase to the water phase is 10 to 200 μ L/min.
6. The method for preparing large-size polyurea hollow microspheres according to claim 1, wherein the flow rate of the aqueous phase is 0.05 to 60.0 mL/min.
7. The preparation method of the large-size polyurea hollow microspheres according to claim 6, wherein the flow rate of the aqueous phase is 0.5-50.0 mL/min.
8. The preparation method of the large-size polyurea hollow microspheres according to claim 1, wherein the mass fraction of the aliphatic amine or the stabilizer in the aqueous phase is 0.01-3.0%.
9. The method for preparing large-size polyurea hollow microspheres according to claim 1, wherein when a mixed solution of a diisocyanate compound and an organic solvent is used as an oil phase, the organic solvent accounts for 1-90% of the total mass of the oil phase.
10. The method for preparing large-size polyurea hollow microspheres according to claim 1, wherein the reaction temperature is 30-70 ℃.
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