CN106215867B - Preparation of surface roughened magnetic nano-microsphere and composite material thereof - Google Patents
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Abstract
The invention relates to a preparation technology of magnetic nano-microspheres with roughened (micro-porous) surfaces and composite materials thereof, belonging to the field of nano-materials. The technology takes a series of phthalonitrile with different structures as organic monomer and FeCl3·6H2O is an iron source, ethylene glycol is a solvent and a reducing agent, and the iron phthalocyanine/Fe is prepared by one-step solvothermal oxidation-reduction self-assembly3O4Magnetic nano-microspheres. The surface of the microsphere is etched to obtain the nano microsphere with roughened and porous surface, and the nano microsphere is uniformly dispersed into the aromatic nitrile-based polymer to prepare the polymer-based nano composite material with good thermal stability, excellent interface compatibility and excellent magnetic property. The invention prepares the surface roughened and porous iron phthalocyanine/Fe by a simple method3O4The magnetic nano-microsphere has potential application value in catalyst carriers, adsorption materials and other aspects. In addition, the roughened surface effectively improves the interface compatibility of the matrix and the filler, and can be widely applied to the material fields of magnetic composite materials, capacitors, semiconductor thin-film devices and the like.
Description
Technical Field
The invention relates to a preparation technology of surface roughened (microporous) magnetic nano-microspheres and a composite material thereof. The technology comprises the preparation of magnetic nano microspheres under specific conditions, the roughening of the surfaces of the microspheres and the preparation of a composite material with high interface compatibility, and belongs to the field of nano materials. The surface of the obtained magnetic nano microsphere is rough and porous, and the specific surface area and the pore volume are large. The obtained composite material has the characteristics of high temperature resistance, good interface compatibility, magnetic functionalization and the like.
Background
The magnetic nano hybrid material is an organic functional material with certain magnetism and a special structure formed by combining inorganic magnetic nano particles and organic matters by a proper method. As a composite material with nanometer or molecular level components, the magnetic nanometer material contains inorganic and organic components which are combined together under a certain chemical bond effect, so that the magnetic nanometer material has the characteristics of both inorganic materials and organic materials. Meanwhile, the magnetic nano material has the performance which is not possessed by the common macro material due to the special nano effect of the magnetic nano material under the nano size. The magnetic nano material has the advantages of light weight, easy processing, good magnetic performance and the like, so that the magnetic nano material has wide application prospect in the field of functional materials.
The metal phthalocyanine polymer (oligomer) is a sixteen-membered ring compound formed by taking phthalonitrile as a raw material and metal salt as a metal source under the condition of a catalyst or high temperature and high pressure, and metal in a ring inner cavity and a large ring form an organic metal coordination compound. The material has excellent performances of heat resistance, acid and alkali resistance, conductivity, photocatalysis and the like, so that the material can be widely applied to the fields of photocatalysis, semiconductors and conductive materials.
In the last decade, nano-hybrid materials related to magnetism have been extensively studied, and a series of magnetic nano-materials with different organic and inorganic components have been invented in the meantime. For example: CN101698737B preparation method of an organic/inorganic nano-magnetic composite material; CN102086304B A Phthalocyanine iron prepolymer/Fe3O4Nanometer hybrid magnetic material and its preparation method; CN105348775A crosslinkable polyarylether nitrile/ferroferric oxide hybrid magnetic material and a manufacturing method thereof. However, the magnetic nano material prepared by the solvothermal method has a compact and smooth surface and poor interface compatibility when being compounded with a polymer matrix, and has obvious influence on various properties of the obtained composite material. Therefore, in order to enhance the interface compatibility between the matrix resin and the magnetic microspheres, the surfaces of the magnetic microspheres are effectively chemically modified, the surfaces of the microspheres are roughened (porous or surface organic layers are formed), and the composite material with improved functions is expected to be developed through the roughening compatibility and entanglement compatibility between the magnetic microspheres and the matrix resin.
Disclosure of Invention
The invention aims to prepare iron phthalocyanine/Fe with coarsened and porous surfaces and different phthalonitrile types3O4Magnetic nano-microsphere and its composite material. Wherein the magnetic nano-microsphere is subjected to surface roughening and porosification by a solvothermal method and a surface etching method. For the composite material, the invention adopts the aromatic nitrile polymer to be compounded with the obtained magnetic nano-microspheres, and the magnetic nano-microspheres are realized by ultrasonic stirringUniformly dispersing, and obtaining the nano microsphere reinforced composite material with good interface compatibility by a thermal flow forming mode. Different types of iron phthalocyanine/Fe prepared by the invention3O4The magnetic nano-microsphere has large specific surface area and high surface roughness, shows good interface compatibility and can realize interface compatibilization with a resin matrix in the preparation of a functional composite material.
The invention provides iron phthalocyanine/Fe3O4The one-step solvothermal preparation technology and the surface treatment method of the nano microspheres and the preparation technology of the aromatic nitrile-based polymer composite material have the following characteristics:
1. iron phthalocyanine/Fe3O4The preparation method comprises the steps of preparing nano microspheres by a one-step solvothermal method, adding different organic monomers (shown in figure 1) to prepare precursor solutions, and preparing the nano microspheres with different particle sizes and densities by regulating and controlling the temperature, the reaction time and the pressure of a reaction kettle;
2. the temperature of the reaction kettle is controlled to be 180-220 ℃, the reaction time is controlled to be 8-15h, the internal pressure of the reaction kettle is controlled by the filling amount of the precursor solution, wherein the filling amount of the solution is controlled to be 60-90%;
3. performing surface treatment on the nano microspheres, namely etching the microspheres obtained in the characteristic 1 by using an organic solvent to obtain rough-surface and porous nano microspheres, and obtaining the nano microspheres with different etching degrees by selecting the organic solvent, and regulating and controlling the etching time and the etching temperature;
4. the organic solvent described in the feature 3 is mainly N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC), or the like;
5. the etching time of the nano-microsphere is 5-40h and the etching temperature is 80-120 ℃ as shown in the characteristic 3;
6. washing the microspheres treated by the method in the characteristic 3 by using ethanol and deionized water, fully replacing residual organic solvent in the micro-mesopores of the nano microspheres by using the deionized water, and finally drying by using a freeze drying technology;
7. the specific surface area of the roughened nano-microspheres as described in feature 3 is characterized by its nitrogen desorption curve, as shown in fig. 2;
8. iron phthalocyanine/Fe with roughened and microporous surface3O4The magnetic nano-microsphere is characterized in that: specific surface area>30m2The surface roughness is large, and a large number of micropores and mesopores exist in the surface layer;
9. iron phthalocyanine/Fe3O4The preparation of the magnetic nano-microsphere and aromatic nitrile polymer composite material is characterized in that the uniform dispersion of microspheres in a polymer solution is realized through a continuous ultrasonic technology, a class of magnetic polymer-based composite films with good interface compatibility are prepared through a casting film forming method, and a solvent is volatilized through graded temperature control treatment;
10. the aromatic nitrile group described in feature 9 includes phthalonitrile resins (e.g., biphenol-type phthalonitrile resin, bisphenol A-type phthalonitrile resin, etc.) and polyarylene ether nitriles (e.g., bisphenol A-type polyarylene ether nitrile, biphenyl-type polyarylene ether nitrile, biphenol-and-hydroquinone-copolymerized polyarylene ether nitrile, etc.);
11. the step temperature control program is 80-1 h, 100-1 h, 120-1 h, 160-2 h and 200-2 h according to the characteristic 9;
the whole preparation process is schematically shown in figure 1. The innovation points of the invention are as follows: porous, high specific surface area, rough surface iron phthalocyanine/Fe prepared by simple method3O4The magnetic nano-microsphere has potential application value in catalyst carriers, adsorption materials and other aspects. Meanwhile, the obtained porous nano-microsphere with rough surface can effectively realize interface rough compatibility and interpenetrating compatibility between inorganic nano-particles and polymers (the SEM image of the section of the nano-microsphere is shown in figure 3), so that the functional nano-composite material with good interface compatibility can be obtained, and the functional nano-composite material can be widely applied to the fields of military industry and civil functional materials.
Drawings
FIG. 1 is a schematic diagram of formation of iron phthalocyanine/ferroferric oxide nano-microspheres
FIG. 2 shows the nitrogen adsorption and desorption curves of the nano-microspheres with different etching degrees
FIG. 3 is a scanning electron microscope photograph of a cross section of the polymer-based nanosphere composite material
Detailed Description
The following examples are presented to illustrate the present invention and should not be construed as limiting the claims.
Examples 1
Step one, weighing 6.75g FeCl3·6H2Dissolving O in 200mL of ethylene glycol, dissolving 1.0g of biphenol type bisphthalonitrile resin (BPh) in 3mL of NMP, adding the solution into the ethylene glycol solution, adding 5.0g of polyethylene glycol 2000, stirring for 30min, slowly adding 18g of crystalline sodium acetate, and reacting for 1h at normal temperature and pressure;
secondly, transferring the reaction solution into a polytetrafluoroethylene high-pressure reaction kettle, wherein the filling amount of the precursor solution is 80%, and reacting for 15 hours at 200 ℃;
step three, washing the nano-microspheres prepared in the step two with deionized water and ethanol for 2-3 times, transferring the nano-microspheres into 100mL of NMP, and reacting at 80 ℃ for 30 h;
step four, carrying out solid-liquid separation on the suspension obtained in the step three, washing the solid component for 3-4 times by using deionized water, and finally drying in a freeze dryer;
step five, adding 0.1g of microspheres obtained in the step four into 6mL of NMP, ultrasonically dispersing the microspheres uniformly and singly for 10min, dissolving 1.9g of poly (arylene ether nitrile) into 18mL of NMP, adding the dispersed microsphere suspension into the poly (arylene ether nitrile) solution, strongly stirring for 30min, and finally stirring for 30min in the ultrasonic process;
and step six, standing the suspension finally obtained in the step five to remove bubbles, pouring the suspension on a horizontal clean glass plate, and carrying out graded temperature control treatment in an oven for 80-1 h, 100-1 h, 120-1 h, 160-2 h and 200-2 h to form a film (remove the solvent).
The specific surface area of the porous microspheres prepared by the above steps is 50.14m2Specific volume of 0.14 cm/g3(ii)/g, saturation magnetization of 55.7 emu/g. The tensile strength of the composite film prepared by the steps is 110MPa, and the glass transition temperature is about 195 ℃.
EXAMPLES example 2
Step one, weighing 11.2g FeCl3·6H2Dissolving O in 200mL of ethylene glycol, dissolving 3.5g of trifunctional phthalonitrile resin (TPh) in 5mL of NMP, adding into the ethylene glycol solution, adding 5.6g of polyethylene glycol 2000, stirring for 30min, slowly adding 31.2g of crystalline sodium acetate, and reacting for 1h at normal temperature and pressure;
secondly, transferring the reaction solution into a polytetrafluoroethylene high-pressure reaction kettle, wherein the filling amount of the precursor solution is 80%, and reacting for 15 hours at 200 ℃;
step three, washing the nano-microspheres prepared in the step two with deionized water and ethanol for 2-3 times, transferring the nano-microspheres into 100mL of NMP, and reacting at 80 ℃ for 30 h;
step four, carrying out solid-liquid separation on the suspension obtained in the step three, washing the solid component for 3-4 times by using deionized water, and finally drying in a freeze dryer;
step five, adding 0.06g of microspheres obtained in the step four into 6mL of NMP, performing ultrasonic treatment for 10min to uniformly and singly disperse the microspheres, dissolving 1.94g of poly (arylene ether nitrile) into 18mL of NMP, adding dispersed microsphere suspension into poly (arylene ether nitrile) solution, performing strong stirring for 30min, and finally performing ultrasonic treatment for 30 min;
and step six, standing the suspension finally obtained in the step five to remove bubbles, pouring the suspension on a horizontal clean glass plate, and carrying out graded temperature control treatment in an oven for 80-1 h, 100-1 h, 120-1 h, 160-2 h and 200-2 h to form a film (remove the solvent).
The specific surface area of the porous microspheres prepared by the above steps was 63.12m2Specific volume of 0.16 cm/g3(ii)/g, saturation magnetization of 56.74 emu/g. The tensile strength of the composite film prepared by the steps is 106MPa, and the glass transition temperature is about 194 ℃.
EXAMPLE 3
Step one, weighing 7.3g FeCl3·6H2O was dissolved in 160mL of ethylene glycol, 2.0g of phthalonitrile resin (2PEN-Ph) containing bisphenol A ether nitrile segment was dissolved in 3mL of NMP and added to the ethylene glycol solution, 5.4g of polyethylene glycol 2000 was added thereto, and after stirring for 30min, 24.48g of nodules were slowly addedCrystallizing sodium acetate, and reacting for 1h at normal temperature and normal pressure;
secondly, transferring the reaction solution into a polytetrafluoroethylene high-pressure reaction kettle, wherein the filling amount of the precursor solution is 80%, and reacting for 12 hours at 200 ℃;
step three, washing the nano-microspheres prepared in the step two with deionized water and ethanol for 2-3 times, transferring the nano-microspheres into 100mL of NMP, and reacting at 80 ℃ for 30 h;
step four, carrying out solid-liquid separation on the suspension obtained in the step three, washing the solid component for 3-4 times by using deionized water, and finally drying in a freeze dryer;
step five, adding 0.1g of microspheres obtained in the step four into 6mL of NMP, performing ultrasonic treatment for 10min to uniformly and singly disperse the microspheres, dissolving 1.9g of poly (arylene ether nitrile) into 18mL of NMP, adding dispersed microsphere suspension into poly (arylene ether nitrile) solution, performing strong stirring for 30min, and finally performing ultrasonic treatment for 30 min;
and step six, standing the suspension finally obtained in the step five to remove bubbles, pouring the suspension on a horizontal clean glass plate, and carrying out graded temperature control treatment in an oven for 80-1 h, 100-1 h, 120-1 h, 160-2 h and 200-2 h to form a film (remove the solvent).
The specific surface area of the nano-porous microspheres prepared by the steps is 68.4m2Specific volume of 0.17 cm/g3(ii)/g, saturation magnetization of 53.61 emu/g. The composite film prepared by the steps has the tensile strength of 112.3MPa and the glass transition temperature of about 193 ℃.
Claims (6)
1. Iron phthalocyanine/Fe with roughened and microporous surface3O4The preparation method of the magnetic nano-microsphere is characterized in that the magnetic nano-microsphere is prepared from iron phthalocyanine/Fe3O4Etching the magnetic nano-microspheres with an organic solvent, regulating and controlling the selection of the organic solvent, the etching time and the etching temperature, then cleaning with ethanol and deionized water, fully replacing the residual organic solvent in the micro-mesopores of the nano-microspheres with the deionized water, and finally drying by adopting a freeze-drying technology to obtain the surface-roughened and microporous iron phthalocyanine/Fe3O4Magnetic nano microA ball; the organic solvent is one of N-methyl pyrrolidone, N-dimethylformamide or N, N-dimethylacetamide; the etching time is 5-40h, and the etching temperature is 80-120 ℃;
the iron phthalocyanine/Fe3O4The magnetic nano-microsphere is prepared by adopting a one-step solvothermal method, a precursor solution is prepared by adding different organic monomers, and the iron phthalocyanine/Fe is prepared by regulating and controlling the temperature, the reaction time and the pressure of a reaction kettle3O4Magnetic nano-microspheres; the internal pressure of the reaction kettle is controlled by the filling amount of the precursor solution, wherein the filling amount of the solution is controlled to be 60-90%;
the structural formula of the iron phthalocyanine is as follows:
wherein
2. A surface roughened, microvoided iron phthalocyanine/Fe according to claim 13O4The preparation method of the magnetic nano-microsphere is characterized in that the temperature of the reaction kettle is controlled at 180-220 ℃, the reaction time is controlled at 8-15h, and the internal pressure of the reaction kettle is controlled by the filling amount of the precursor solution, wherein the filling amount of the solution is controlled at 60-90%.
3. Iron phthalocyanine/Fe with roughened and microporous surface3O4Magnetic nanospheres characterized by the use of the roughened, microvoided iron phthalocyanine/Fe according to claim 13O4The magnetic nano-microsphere is prepared by the preparation method, and has specific surface area>30m2Table of,/gThe surface roughness is large, and micropores and mesopores exist on the surface layer.
4. Iron phthalocyanine/Fe3O4The preparation method of the magnetic nano-microsphere and arylnitrile-based polymer composite material is characterized in that the iron phthalocyanine/Fe3O4The magnetic nanospheres are the surface roughened and microporous iron phthalocyanine/Fe as claimed in claim 33O4The magnetic nano-microsphere is uniformly dispersed in a polymer solution by a continuous ultrasonic technology, a magnetic polymer-based composite film with good interface compatibility is prepared by a casting film forming method, and a solvent is volatilized by graded temperature control treatment.
5. Iron phthalocyanine/Fe according to claim 43O4The preparation method of the magnetic nano-microsphere and aromatic nitrile polymer composite material comprises the following steps of (1) preparing aromatic nitrile including phthalonitrile resin and polyarylether nitrile; the phthalonitrile resin is one of biphenyl phthalonitrile resin or bisphenol A phthalonitrile resin, and the polyaryl ether nitrile is one of bisphenol A polyaryl ether nitrile, biphenyl polyaryl ether nitrile or copolymer polyaryl ether nitrile of biphenyl diphenol and hydroquinone.
6. Iron phthalocyanine/Fe according to claim 43O4The preparation method of the magnetic nano-microsphere and aromatic nitrile polymer composite material comprises the steps of controlling the temperature in a grading manner for 80-1 h, 100-1 h, 120-1 h, 160-2 h and 200-2 h.
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| CN102086304A (en) * | 2010-12-19 | 2011-06-08 | 电子科技大学 | Iron phthalocyanine prepolymer/Fe3O4 nanometer hybrid magnetic material and preparation method thereof |
| CN102492131A (en) * | 2011-11-28 | 2012-06-13 | 电子科技大学 | Polyaryl ether nitrile resin, polyaryl ether nitrile film and preparation method thereof |
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| JPH11176686A (en) * | 1997-12-09 | 1999-07-02 | Ricoh Co Ltd | Anisotropic film and formation method thereof |
| CN101692366A (en) * | 2009-09-14 | 2010-04-07 | 深圳市康源新通信技术有限公司 | Composite electromagnetic medium material containing dicyclopentadienyl iron phthalocyanine metal organic magnetic body and preparation method thereof |
| CN102086304A (en) * | 2010-12-19 | 2011-06-08 | 电子科技大学 | Iron phthalocyanine prepolymer/Fe3O4 nanometer hybrid magnetic material and preparation method thereof |
| CN102492131A (en) * | 2011-11-28 | 2012-06-13 | 电子科技大学 | Polyaryl ether nitrile resin, polyaryl ether nitrile film and preparation method thereof |
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