CN109046191B - Core-shell structure nano material with hetero atom doped polymer as shell and preparation method thereof - Google Patents
Core-shell structure nano material with hetero atom doped polymer as shell and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a core-shell structure nano material taking a heteroatom doped polymer as a shell and a preparation method thereof; the method comprises the steps of dissolving arylamine and a compound shown in a general formula I in water at a mild reaction temperature (10-50 ℃) under a stirring condition, adding nanoparticles or nano emulsion serving as cores, uniformly dispersing the nanoparticles or nano emulsion in an aqueous solution system, adding an ammonia aqueous solution, and uniformly stirring; adding aldehyde, generating Schiff base by the aldehyde and the compound shown in the general formula I, adding arylamine and the generated Schiff base, gradually forming the material by taking the heteroatom doped polymer as a shell and taking nano microspheres or nano particles as a core, and then centrifuging and drying to obtain the target material. The core-shell structure nanoparticle prepared by the method has the advantages of obvious core-shell structure, good affinity among core shells, uniform and controllable shell thickness, good material dispersibility, high yield and good application prospect.
Description
Technical Field
The invention belongs to the technical field of new nano materials, and particularly relates to a core-shell structure nano material taking a heteroatom doped polymer as a shell and a preparation method thereof.
Background
The nano material with the core-shell structure not only has the properties of core and shell materials, but also has the special properties of composite materials, and is widely concerned by people. The core-shell structure nano material prepared by coating organic substance nano microspheres on an organic polymer shell layer has more applications in the aspects of phase transformation, drug controlled release and the like; the core-shell structure nano material prepared by coating inorganic nano microspheres or nano particles with the organic polymer shell layer has the advantages of thermal stability and mechanical strength of inorganic materials, easy processability and flexibility of organic polymer materials and the like, can improve the compatibility of the inorganic nano core when being compounded with other high polymer materials, and can effectively prevent the loss and agglomeration of the inorganic nano particles caused by high surface energy. For example: the magnetic composite material is prepared by coating the magnetic core material with the organic polymer shell layer, and can be applied to the fields of electronics, biomedicine, food sanitation and the like; the organic polymer shell is used for coating inorganic flame-retardant materials such as magnesium hydroxide, aluminum hydroxide and the like, and can be applied to flame-retardant modification of polymer materials; the organic polymer shell is used for coating the silicon dioxide, so that the silicon dioxide can be used for modifying high molecular materials, and the strength, elasticity, wear resistance, weather resistance, ultraviolet aging resistance and heat aging resistance of the materials are improved; the organic polymer is used for coating the phase change energy storage material, so that the problems of phase separation, flowing and corrosion of the phase change material and the like can be solved, and the application performance of the phase change material is improved; the organic polymer is used for coating the nano carbon black, so that the compatibility and the dispersibility of the nano carbon black in the polymer can be improved, and the properties such as the strength of the material can be improved. However, organic polymer coating still has certain problems, such as that the stability of an emulsion system is influenced by excessively high coating reaction temperature, so that the coating of inorganic or organic materials is influenced; the high coating reaction temperature is used for desorption of dispersing agents for dispersing nano particles such as carbon black and the like, so that the aggregation tendency of the nano particles such as carbon black and the like to be dispersed is increased, the prepared coated carbon black has large particle size and poor heat-resistant stability, and meanwhile, the dropped dispersing agents also bring negative influence on a reaction system; in addition, the preparation process of the organic polymer is complex, the price of the organic raw material is high, and the controllability of the reaction process is low.
Disclosure of Invention
The invention aims to provide a preparation method of a core-shell structure nano material taking a heteroatom-doped polymer as a shell, which has the advantages of simple process, mild condition, quick reaction and low cost; the method comprises the steps of dissolving arylamine and a compound shown in a general formula I in water at a mild reaction temperature (10-50 ℃) under a stirring condition, adding nanoparticles or nano emulsion serving as cores, uniformly dispersing the nanoparticles or nano emulsion in an aqueous solution system, adding aldehyde, generating Schiff base by the aldehyde and the compound shown in the general formula I, adding arylamine and the generated Schiff base, gradually forming a material taking a heteroatom doped polymer as a shell and nano microspheres or nanoparticles as cores, centrifuging and drying to obtain the target material. The core-shell structure nanoparticle prepared by the method has the advantages of obvious core-shell structure, good affinity among core shells, uniform and controllable shell thickness, good material dispersibility and high yield.
Specifically, the preparation method of the core-shell structure nano material with the heteroatom doped polymer as the shell comprises the following steps:
(1) at the temperature of 10-50 ℃, dissolving arylamine and a compound shown in a general formula I in water, wherein the compound shown in the general formula I is as follows:
R1selected from H, NH2；
R2Selected from H, COOH, SO3H,B(OH)2,OPO(OH)2,Cl,OCH3,CN,OH,SH,NO2；
(2) Adding the nano-core to be coated into the system, and stirring until the system is uniform and the particles are completely dispersed;
(3) adding an ammonia water solution into the system, and uniformly stirring;
(4) and adding aldehyde into the solution, and stirring for reaction to obtain the core-shell structure nano material.
Wherein the arylamine in the step (1) comprises: melamine, 1, 3-phenylenediamine, 1, 4-phenylenediamine, 1, 3-xylylenediamine, 1, 4-xylylenediamine, tris (4-aminophenyl) amine, 2,4, 6-triaminopyrimidine, 2, 6-diaminopyridine, 1, 5-diaminonaphthalene, and mixtures thereof in a certain ratio;
in the above technical solution, it is further preferable that the concentration of the aromatic amine solution is 0.015 to 1.0 mol/L; wherein the preferable range of the concentration of the arylamine solution is 0.02-0.5 mol/L; the optimal concentration of the arylamine solution is 0.03-0.2 mol/L; when a melamine solution is preferred, a concentration of 0.005mol/L is the optimum condition.
In the above-described embodiments, it is further preferred that the compound represented by the general formula I in step (1) comprises: 2, 4-diaminobenzenesulfonic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3, 5-diaminobenzoic acid, p-aminobenzene, p-anisidine, p-aminobenzonitrile, p-aminophenol, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, aniline, o-phenylenediamine, m-phenylenediamine, p-aminobenzothiophenol, p-nitroaniline;
in the above technical solution, it is further preferable that the concentration of the solution formed by the compound represented by the general formula I is 0.015 to 0.2 mol/L; the preferable concentration range is 0.004-0.1 mol/L; the optimal solution concentration is 0.006-0.008 mol/L; when the 2, 4-diaminobenzene sulfonic acid solution is preferred, the concentration of 0.0076mol/mL is the most preferred condition.
In the above technical solution, it is further preferable that the core-shell structured nano-core in step (2) is an organic polymer microsphere and other inorganic nano-microspheres or nano-particles of inorganic oxides, sulfides, hydroxides, etc., and is, for example, selected from one or more of the following: PS (polystyrene) and SiO2、Fe3O4、CdS、ZnS、TiO2、Al2O3、MgO、Al(OH)3、Mg(OH)2、AgO、CeO2、Co2O3、CuO、Fe2O3、V2O5、SnO、Y2O3、ZnO、ZrO2、Ce2S3CuS, carbon black nanoparticles, dodecanol emulsion, and the like. The grain diameter is nano-scale.
In the above technical solution, preferably, the ammonia solution is added in the step (2) dropwise, and the stirring time is 1-10 minutes to gradually form a clear and transparent solution.
In the above-mentioned technical solutions, it is further preferred that the aldehyde used in step (3) comprises: formaldehyde or fatty dialdehydes; wherein, the formaldehyde is a commercial formaldehyde aqueous solution product; the fatty dialdehyde comprises glyoxal, malondialdehyde, succindialdehyde, glutaraldehyde, hexandialdehyde and the like;
in the above-mentioned technical solution, it is further preferable that the aldehyde in the step (3) is added dropwise, and the amount of the aldehyde is 5 to 12 times the amount of the aromatic amine. Preferably, the amount of the aldehyde is 8-10 times of the equivalent of the aldehyde group relative to the aromatic amine. Most preferably, the aldehyde is used in an amount of 9 times equivalent to the amount of aldehyde group with respect to the aromatic amine.
In the above-mentioned technical solution, under a further preferable condition, in the step (3), 1 to 10 minutes after the aldehyde is added, the shell layer starts to be generated on the surface of the nano-core and starts to be coated, and the stirring reaction is performed for 1 to 6 hours, so as to obtain the nano-material with an obvious core-shell structure, uniform shell layer thickness, good affinity between the core-shells and good dispersibility.
In the above-mentioned technical solutions, it is further preferable that the temperature in the steps (1) to (4) is in a range of 20 to 35 ℃; the further preferable temperature range is 20-25 ℃; the optimum temperature range is 25 ℃.
Has the advantages that:
1. the method adopts a brand new process route, can be produced at a mild operation temperature (10-50 ℃), and is beneficial to the stability of the product; the relatively harsh hydrothermal reaction condition of 70-100 ℃ used in the traditional process is avoided; is particularly suitable for being rapidly carried out at normal temperature (15-25 ℃) and is more beneficial to popularization and application.
2. The method has the advantages of simple process, easy operation and high yield, and the melamine formaldehyde nanospheres with controllable sizes can be obtained by controlling the ratio of the amino aromatic derivatives to the arylamine, the ratio of the arylamine to the aldehyde, the concentration of the arylamine, the addition amount of different nanoparticle cores and different reaction temperatures (10-50 ℃) according to use requirements.
3. The method has quick reaction, 1-10 minutes after the aldehyde is added in the step (3), a shell layer starts to be generated on the surface of the nano-core and starts to be coated; stirring and reacting for 1-6 hours to obtain the core-shell structure nano material with obvious core-shell structure, uniform shell thickness and good dispersibility. And after the reaction is finished, the residual reaction solution after all the polymer nano microspheres are centrifugally taken out is not required to be discarded, and can be recycled.
4. The method of the invention can expand the use of high carbon number fatty dialdehyde, thereby avoiding the use of harmful substance formaldehyde.
5. The core-shell structure nano-particles prepared by the method have obvious core-shell structure, good affinity among the core shells and no desorption phenomenon among the core shells.
Drawings
FIG. 1: TEM image of PS (polystyrene) nano-microsphere coated by 2, 4-diaminobenzene sulfonic acid participating in reaction;
FIG. 2: 2, 4-diaminobenzene sulfonic acid participates in reaction to coat SiO2TEM images of the nanospheres; wherein A, B are observations at different magnifications, respectively;
FIG. 3: 2, 4-diaminobenzene sulfonic acid participates in reaction to coat Fe3O4TEM images of the nanoparticles;
FIG. 4: TEM image of CdS nano-microsphere coated by 2, 4-diaminobenzene sulfonic acid participating in reaction;
FIG. 5: TEM image of 2, 4-diaminobenzene sulfonic acid participating in reaction to coat ZnS particles;
FIG. 6: TEM image of melamine-formaldehyde-2, 4-diaminobenzene sulfonic acid polymer/dodecanol phase-change microcapsule;
Detailed Description
The following non-limiting examples will allow one of ordinary skill in the art to more fully understand the present invention, but are not intended to limit the invention in any way.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
Dissolving 0.19g (0.0015mol) of melamine and 0.058g (0.0003mol) of 2, 4-diaminobenzene sulfonic acid in 50mL of water at 25 ℃, dropwise adding 0.1mL of ammonia water (which is helpful for dissolution), stirring at a rotating speed of 500rpm by magnetic stirring until the solution is uniform and transparent, adding a certain amount of PS (polystyrene) nano microspheres, adding 1.2mL of 40% aqueous formaldehyde solution when the PS nano microspheres are uniformly dispersed in the system, continuously stirring for 2 hours to complete the reaction, centrifuging, washing and drying to obtain the target nano core-shell material. TEM electron microscope observation shows that as shown in FIG. 1, the core-shell nano material is uniformly dispersed, the particle size distribution is uniform, and the core-shell structure is obvious.
Example 2
Dissolving 0.19g (0.0015mol) of melamine and 0.058g (0.0003mol) of 2, 4-diaminobenzene sulfonic acid in 50mL of water at 25 ℃, dropwise adding 0.1mL of ammonia water (for facilitating dissolution), stirring at a rotating speed of 500rpm by magnetic stirring until the solution is uniform and transparent, and adding a certain amount of SiO2Nano microsphere water solution (two kinds: 120nm, 30nm) to be SiO2The nano microspheres are uniformly dispersed in the system, 1.2mL of 40% formaldehyde aqueous solution is added, the stirring is continued for 2 hours, the reaction is completed, and the target nano core-shell material is obtained through centrifugation, washing and drying, wherein the target nano core-shell material is observed by a TEM (transmission electron microscope), as shown in figure 2, the core-shell nano material is uniformly dispersed, and the core-shell structure is obvious.
Example 3
Dissolving 0.19g (0.0015mol) of melamine and 0.058g (0.0003mol) of 2, 4-diaminobenzene sulfonic acid in 50mL of water at 25 ℃, dropwise adding 0.1mL of ammonia water (for facilitating dissolution), stirring at a rotating speed of 500rpm by magnetic stirring until the solution is uniform and transparent, and adding a certain amount of Fe3O4Nanospheres of Fe3O4The nano microspheres are uniformly dispersed in the system, 1.2mL of 40% formaldehyde aqueous solution is added, the reaction is completed after continuously stirring for 2 hours, and the target nano core-shell material is obtained through centrifugation, washing and drying, wherein the core-shell nano material is uniformly dispersed, the particle size distribution is uniform, and the core-shell structure is obvious as shown in FIG. 3.
Example 4
Dissolving 0.19g (0.0015mol) of melamine and 0.058g (0.0003mol) of 2, 4-diaminobenzene sulfonic acid in 50mL of water at 25 ℃, dropwise adding 0.1mL of ammonia water (which is helpful for dissolving), stirring at the rotating speed of 500rpm by magnetic stirring until the solution is uniform and transparent, adding a certain amount of CdS nano microspheres, adding 1.2mL of 40% formaldehyde aqueous solution after the CdS nano microspheres are uniformly dispersed in the system, continuously stirring for 2 hours to complete the reaction, centrifuging, washing and drying to obtain the target nano core-shell material, and observing by a TEM electron microscope, wherein the core-shell nano material is uniformly dispersed, the particle size distribution is uniform and the core-shell structure is obvious as shown in FIG. 4.
Example 5
Dissolving 0.19g (0.0015mol) of melamine and 0.058g (0.0003mol) of 2, 4-diaminobenzene sulfonic acid in 50mL of water at 25 ℃, dropwise adding 0.1mL of ammonia water (which is helpful for dissolution), stirring at the rotating speed of 500rpm by magnetic stirring until the solution is uniform and transparent, adding a certain amount of ZnS nanoparticles, adding 1.2mL of 40% formaldehyde aqueous solution when the ZnS nanoparticles are uniformly dispersed in the system, continuously stirring for 2 hours to complete the reaction, centrifuging, washing and drying to obtain the target nano core-shell material, wherein the core-shell nano material is uniformly dispersed, the particle size distribution is uniform and the core-shell structure is obvious as shown in FIG. 5.
Example 6
Dissolving 0.19g (0.0015mol) of melamine and 0.058g (0.0003mol) of 2, 4-diaminobenzene sulfonic acid in 50mL of water at 25 ℃, dropwise adding 0.1mL of ammonia water (for facilitating dissolution), stirring at a rotating speed of 500rpm by magnetic stirring until the solution is uniform and transparent, and adding a certain amount of TiO2Nanoparticles of TiO 22And (3) uniformly dispersing the nano particles in the system, adding 1.2mL of 40% formaldehyde water solution, continuously stirring for 2 hours to complete the reaction, and centrifuging, washing and drying to obtain the target nano core-shell material.
Example 7
Dissolving 0.19g (0.0015mol) of melamine and 0.058g (0.0003mol) of 2, 4-diaminobenzene sulfonic acid in 50mL of water at 25 ℃, dropwise adding 0.1mL of ammonia water (for facilitating dissolution), stirring at a rotating speed of 500rpm by magnetic stirring until the solution is uniform and transparent, and adding a certain amount of Al2O3Nanoparticles of Al2O3And (3) uniformly dispersing the nano particles in the system, adding 1.2mL of 40% formaldehyde water solution, continuously stirring for 2 hours to complete the reaction, and centrifuging, washing and drying to obtain the target nano core-shell material.
Example 8
Dissolving 0.19g (0.0015mol) of melamine and 0.058g (0.0003mol) of 2, 4-diaminobenzene sulfonic acid in 50mL of water at 25 ℃, dropwise adding 0.1mL of ammonia water (which is helpful for dissolution), stirring at the rotating speed of 500rpm by magnetic stirring until the solution is uniform and transparent, adding a certain amount of MgO nano-particles, adding 1.2mL of 40% formaldehyde aqueous solution when the MgO nano-particles are uniformly dispersed in the system, continuously stirring for 2 hours to complete the reaction, centrifuging, washing and drying to obtain the target nano core-shell material.
Example 9
Dissolving 0.19g (0.0015mol) of melamine and 0.058g (0.0003mol) of 2, 4-diaminobenzene sulfonic acid in 50mL of water at 25 ℃, dropwise adding 0.1mL of ammonia water (for facilitating dissolution), stirring at a speed of 500rpm by magnetic stirring until the solution is uniform and transparent, and adding a certain amount of Al (OH)3Nanoparticles of Al (OH)3And (3) uniformly dispersing the nano particles in the system, adding 1.2mL of 40% formaldehyde water solution, continuously stirring for 2 hours to complete the reaction, and centrifuging, washing and drying to obtain the target nano core-shell material.
Example 10
Dissolving 0.19g (0.0015mol) of melamine and 0.058g (0.0003mol) of 2, 4-diaminobenzene sulfonic acid in 50mL of water at 25 ℃, dropwise adding 0.1mL of ammonia water (for facilitating dissolution), stirring at a speed of 500rpm by magnetic stirring until the solution is uniform and transparent, and adding a certain amount of Mg (OH)2Nanoparticles of (i) Mg (OH)2And (3) uniformly dispersing the nano particles in the system, adding 1.2mL of 40% formaldehyde water solution, continuously stirring for 2 hours to complete the reaction, and centrifuging, washing and drying to obtain the target nano core-shell material.
Example 11
Dissolving 0.19g (0.0015mol) of melamine and 0.058g (0.0003mol) of 2, 4-diaminobenzene sulfonic acid in 50mL of water at 25 ℃, dropwise adding 0.1mL of ammonia water (which is helpful for dissolution), stirring at a magnetic stirring speed of 500rpm until the solution is uniform and transparent, adding a certain amount of AgO nanoparticles, adding 1.2mL of 40% formaldehyde aqueous solution when the AgO nanoparticles are uniformly dispersed in the system, continuously stirring for 2 hours to complete the reaction, centrifuging, washing and drying to obtain the target nano core-shell material.
Example 12
Dissolving 0.19g (0.0015mol) of melamine and 0.058g (0.0003mol) of 2, 4-diaminobenzene sulfonic acid in 50mL of water at 25 ℃, dropwise adding 0.1mL of ammonia water (for facilitating dissolution), stirring at a rotating speed of 500rpm by magnetic stirring until the solution is uniform and transparent, and adding a certain amount of CeO2Nanoparticles of CeO2And (3) uniformly dispersing the nano particles in the system, adding 1.2mL of 40% formaldehyde water solution, continuously stirring for 2 hours to complete the reaction, and centrifuging, washing and drying to obtain the target nano core-shell material.
Example 13
Dissolving 0.19g (0.0015mol) of melamine and 0.058g (0.0003mol) of 2, 4-diaminobenzene sulfonic acid in 50mL of water at 25 ℃, dropwise adding 0.1mL of ammonia water (for facilitating dissolution), stirring at a rotating speed of 500rpm by magnetic stirring until the solution is uniform and transparent, and adding a certain amount of Co2O3Nanoparticles of Co2O3And (3) uniformly dispersing the nano particles in the system, adding 1.2mL of 40% formaldehyde water solution, continuously stirring for 2 hours to complete the reaction, and centrifuging, washing and drying to obtain the target nano core-shell material.
Example 14
Dissolving 0.19g (0.0015mol) of melamine and 0.058g (0.0003mol) of 2, 4-diaminobenzene sulfonic acid in 50mL of water at 25 ℃, dropwise adding 0.1mL of ammonia water (which is helpful for dissolution), stirring at the rotation speed of 500rpm by magnetic stirring until the solution is uniform and transparent, adding a certain amount of CuO nanoparticles, adding 1.2mL of 40% formaldehyde aqueous solution when the CuO nanoparticles are uniformly dispersed in the system, continuously stirring for 2 hours to complete the reaction, centrifuging, washing and drying to obtain the target nano core-shell material.
Example 15
Dissolving 0.19g (0.0015mol) of melamine and 0.058g (0.0003mol) of 2, 4-diaminobenzene sulfonic acid in 50mL of water at 25 ℃, dropwise adding 0.1mL of ammonia water (for facilitating dissolution), stirring at a rotating speed of 500rpm by magnetic stirring until the solution is uniform and transparent, and adding a certain amount of Fe2O3Nanoparticles of Fe2O3And (3) uniformly dispersing the nano particles in the system, adding 1.2mL of 40% formaldehyde water solution, continuously stirring for 2 hours to complete the reaction, and centrifuging, washing and drying to obtain the target nano core-shell material.
Example 16
Dissolving 0.19g (0.0015mol) of melamine and 0.058g (0.0003mol) of 2, 4-diaminobenzene sulfonic acid in 50mL of water at 25 ℃, dropwise adding 0.1mL of ammonia water (for facilitating dissolution), stirring at a rotating speed of 500rpm by magnetic stirring until the solution is uniform and transparent, and adding a certain amount of V2O5Nanoparticles of formula V2O5The nano particles are evenly dispersed in the system, and 1.2mL of 40 percent formaldehyde is added for dissolving in waterAnd continuously stirring the solution for 2 hours to complete the reaction, and centrifuging, washing and drying to obtain the target nano core-shell material.
Example 17
Dissolving 0.19g (0.0015mol) of melamine and 0.058g (0.0003mol) of 2, 4-diaminobenzene sulfonic acid in 50mL of water at 25 ℃, dropwise adding 0.1mL of ammonia water (which is helpful for dissolution), stirring at the rotating speed of 500rpm by magnetic stirring until the solution is uniform and transparent, adding a certain amount of SnO nano-particles, adding 1.2mL of 40% formaldehyde aqueous solution when the SnO nano-particles are uniformly dispersed in the system, continuously stirring for 2 hours to complete the reaction, centrifuging, washing and drying to obtain the target nano core-shell material.
Example 18
Dissolving 0.19g (0.0015mol) of melamine and 0.058g (0.0003mol) of 2, 4-diaminobenzene sulfonic acid in 50mL of water at 25 ℃, dropwise adding 0.1mL of ammonia water (for facilitating dissolution), stirring at a rotating speed of 500rpm by magnetic stirring until the solution is uniform and transparent, and adding a certain amount of Y2O3Nanoparticles of Yb2O3And (3) uniformly dispersing the nano particles in the system, adding 1.2mL of 40% formaldehyde water solution, continuously stirring for 2 hours to complete the reaction, and centrifuging, washing and drying to obtain the target nano core-shell material.
Example 19
Dissolving 0.19g (0.0015mol) of melamine and 0.058g (0.0003mol) of 2, 4-diaminobenzene sulfonic acid in 50mL of water at 25 ℃, dropwise adding 0.1mL of ammonia water (which is helpful for dissolution), stirring at a rotating speed of 500rpm by magnetic stirring until the solution is uniform and transparent, adding a certain amount of ZnO nanoparticles, adding 1.2mL of 40% formaldehyde aqueous solution when the ZnO nanoparticles are uniformly dispersed in the system, continuously stirring for 2 hours to complete the reaction, centrifuging, washing and drying to obtain the target nano core-shell material.
Example 20
Dissolving 0.19g (0.0015mol) of melamine and 0.058g (0.0003mol) of 2, 4-diaminobenzene sulfonic acid in 50mL of water at 25 ℃, dropwise adding 0.1mL of ammonia water (for facilitating dissolution), stirring at a rotating speed of 500rpm by magnetic stirring until the solution is uniform and transparent, and adding a certain amount of ZrO2Nanoparticles of ZrO2The nanoparticles are dispersed in the systemAnd (3) uniformly adding 1.2mL of 40% formaldehyde aqueous solution, continuously stirring for 2 hours to complete the reaction, and centrifuging, washing and drying to obtain the target nano core-shell material.
Example 21
Dissolving 0.19g (0.0015mol) of melamine and 0.058g (0.0003mol) of 2, 4-diaminobenzene sulfonic acid in 50mL of water at 25 ℃, dropwise adding 0.1mL of ammonia water (for facilitating dissolution), stirring at a rotating speed of 500rpm by magnetic stirring until the solution is uniform and transparent, and adding a certain amount of Ce2S3Nanoparticles of Ce2S3And (3) uniformly dispersing the nano particles in the system, adding 1.2mL of 40% formaldehyde water solution, continuously stirring for 2 hours to complete the reaction, and centrifuging, washing and drying to obtain the target nano core-shell material.
Example 22
Dissolving 0.19g (0.0015mol) of melamine and 0.058g (0.0003mol) of 2, 4-diaminobenzene sulfonic acid in 50mL of water at 25 ℃, dropwise adding 0.1mL of ammonia water (which is helpful for dissolution), stirring at the rotation speed of 500rpm by magnetic stirring until the solution is uniform and transparent, adding a certain amount of CuS nanoparticles, adding 1.2mL of 40% formaldehyde water solution when the CuS nanoparticles are uniformly dispersed in the system, continuously stirring for 2 hours to complete the reaction, centrifuging, washing and drying to obtain the target nano core-shell material.
Example 23
Dissolving 0.19g (0.0015mol) of melamine and 0.058g (0.0003mol) of 2, 4-diaminobenzene sulfonic acid in 50mL of water at 25 ℃, dropwise adding 0.1mL of ammonia water (which is helpful for dissolution), stirring at a rotating speed of 500rpm by magnetic stirring until the solution is uniform and transparent, adding a certain amount of carbon black nanoparticles, adding 1.2mL of 40% formaldehyde aqueous solution when the carbon black nanoparticles are uniformly dispersed in the system, continuously stirring for 2 hours to complete the reaction, centrifuging, washing and drying to obtain the target nano core-shell material.
Example 24
Mixing 0.1g of dodecanol, 10mL of deionized water and 0.04g of lauryl sodium sulfate, and stirring and emulsifying by using a high-speed emulsifier; dissolving 0.19g of melamine and 0.058g of 2, 4-diaminobenzene sulfonic acid in 50mL of deionized water, mixing with the previously obtained dodecanol emulsion, magnetically stirring at room temperature, and adding ammonia water to adjust the pH value to be alkalescent; adding 1.5mL of formaldehyde water solution, magnetically stirring for 5 hours, centrifugally washing, and vacuum drying for 12 hours to obtain melamine-formaldehyde-2, 4-diaminobenzene sulfonic acid polymer/dodecanol phase change microcapsules; the results are shown in FIG. 6;
the melamine-formaldehyde-2, 4-diaminobenzene sulfonic acid polymer/dodecanol phase change microcapsule prepared by the method is still in a solid state when placed in an environment of 40 ℃ for 3 hours, and dodecanol is in a liquid state at room temperature, so that the melamine-formaldehyde-2, 4-diaminobenzene sulfonic acid polymer/dodecanol phase change microcapsule has a good shaping effect.
It will be apparent to those skilled in the art from this disclosure that many changes and modifications can be made, or equivalents modified, in the embodiments of the invention without departing from the scope of the invention. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention shall still fall within the protection scope of the technical solution of the present invention, unless the contents of the technical solution of the present invention are departed.
Claims (11)
1. A preparation method of a core-shell structure nano material taking a heteroatom doped polymer as a shell comprises the following steps:
(1) under the condition of 10-50 ℃; dissolving arylamine and a compound shown in a general formula I in water, wherein the compound shown in the general formula I is as follows:
R1selected from H, NH2；
R2Selected from H, COOH, SO3H,B(OH)2,OPO(OH)2,Cl,OCH3,CN,OH,SH,NO2；
(2) Adding the nano-core to be coated into the system in the step (1), and stirring until the system is uniform and the particles are completely dispersed;
(3) adding an ammonia water solution into the system in the step (2), and uniformly stirring;
(4) adding aldehyde into the system in the step (3), and stirring for reaction to obtain the core-shell structure nano material;
wherein, the arylamine in the step (1) is selected from one or more of the following: melamine, 1, 3-phenylenediamine, 1, 4-phenylenediamine, 1, 3-xylylenediamine, 1, 4-xylylenediamine, tris (4-aminophenyl) amine, 2,4, 6-triaminopyrimidine, 2, 6-diaminopyridine, 1, 5-diaminonaphthalene.
2. The method of claim 1, wherein: the compound shown in the general formula I in the step (1) comprises: 2, 4-diaminobenzenesulfonic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3, 5-diaminobenzoic acid, p-aminobenzene, p-anisidine, p-aminobenzonitrile, p-aminophenol, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, aniline, o-phenylenediamine, m-phenylenediamine, p-aminobenzothiophenol, p-nitroaniline, o-aminobenzeneboronic acid, m-aminobenzeneboronic acid, p-aminophenol phosphate monoester.
3. The production method according to claim 1 or 2, characterized in that: the concentration of the compound solution shown in the general formula I is 0.015-1.0 mol/L.
4. The production method according to any one of claims 1 to 2, characterized in that: in the step (1), the concentration of the arylamine solution is 0.015-0.2 mol/L.
5. The production method according to claim 3, characterized in that: in the step (1), the concentration of the arylamine solution is 0.015-0.2 mol/L.
6. The production method according to any one of claims 1 to 2 and 5, characterized in that: the aldehyde used in the step (4) is selected from formaldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde or adipaldehyde.
7. The production method according to any one of claims 1 to 2 and 5, characterized in that: and (4) adding the aldehyde in the step (4) in a dropwise adding mode, wherein the using amount of the aldehyde is 5-12 times of the equivalent of the arylamine.
8. The production method according to any one of claims 1 to 2 and 5, characterized in that: the temperature conditions of the steps (1) - (4) are 20-35 ℃.
9. The production method according to any one of claims 1 to 2 and 5, characterized in that: the nano core in the step (2) is selected from one or more of the following: polystyrene, SiO2、Fe3O4、CdS、ZnS、TiO2、Al2O3、MgO、Al(OH)3、Mg(OH)2、AgO、CeO2、Co2O3、CuO、Fe2O3、V2O5、SnO、Y2O3、ZnO、ZrO2、Ce2S3CuS, carbon black nano-particles and dodecanol emulsion.
10. The production method according to any one of claims 1 to 2 and 5, characterized in that: and (4) adding the ammonia water solution obtained in the step (3) in a dropwise manner, wherein the stirring time is 1-10 minutes.
11. The core-shell structure nano material with the shell being the heteroatom-doped polymer obtained by the preparation method according to any one of claims 1 to 10, characterized in that: the core-shell structure of the nano material is obvious, the shell layer thickness is uniform, the affinity between the core shells is good, and the dispersibility is good.
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