CN110373030B - Magnetic-field-induced patterned assembled and erasable magnetic-control phase-change material and preparation method thereof - Google Patents
Magnetic-field-induced patterned assembled and erasable magnetic-control phase-change material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a magnetic control phase change material capable of being assembled and erased in a magnetic field induction patterning mode and a preparation method thereof. The magnetic control phase change material takes a polar or non-polar low-temperature phase change high polymer material as a base material, takes a surface polar or non-polar modified superparamagnetic nano material as a magnetic field response unit, and the mass ratio of the magnetic field response unit to the base material is 0.2-0.5: 1; wherein, the molecular polarity of the matrix material and the magnetic field response unit is the same. The surface of the superparamagnetic particles is modified to enable the superparamagnetic particles to have surface properties dissolved in corresponding phase change materials, and then the superparamagnetic particles are effectively and stably compounded with a phase change matrix and uniformly dispersed to obtain a magnetic control phase change material with quick response to a magnetic field; the material completes patterned assembly through a magnetic field array at high temperature, when the temperature is reduced to be below a melting point, the pattern has shape stability in the absence of a magnetic field, and when the temperature is increased to be above the melting point again, the material can realize pattern erasure through self-leveling under the action of the non-magnetic field.
Description
Technical Field
The invention relates to a magnetic control phase change material, in particular to a magnetic control phase change material capable of being assembled and erased in a magnetic field induced patterning mode and a preparation method thereof, and belongs to the field of surface pattern construction and surface functionalization application.
Background
Materials surface functionalization and patterning techniques have been receiving significant attention. The traditional surface preparation techniques mainly include printing, spraying, engraving and pressing. These techniques have extremely wide application in the fields of large area surface treatment and templated surface processing. Modern surface preparation techniques include chemical etching, self-assembly, and photolithography. The technologies can well make up for the defects of the traditional technology and have a huge effect on the surface modification of modern information materials and energy materials. From traditional to modern technology, many methods produce surfaces that are permanent, difficult to erase and rebuild, and the surface patterns are built for long periods of time.
In recent years, there are many methods of surface treatment using an electric field or a magnetic field. The most widely used method is to use charged particles or magnetic particles to self-assemble in an electric or magnetic field environment to build up a surface pattern. The surfaces of the particles are provided with active functional groups, so that the particles are firmly combined with the surfaces and can quickly form patterns under the induction of a field environment (for example, Chinese patent application with the application number of 201310297744.X discloses a method for self-assembling creatinine molecular imprinting films under the induction of a magnetic field and preparing an electrochemical sensor by the method; Chinese patent application with the application number of CN201811135321.7 discloses a method for fine 3D printing by using electric field induction assisted electrospray).
But these patterns cannot be erased once they are formed. In addition, although patterned assembly can be performed under magnetic field induction using a conventional magnetic fluid, the shape stability is lost immediately after the magnetic field is removed.
Therefore, there is a need for a material that can be patterned under magnetic field induction and that is stable after removal of the magnetic field, while being erasable when necessary.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems that the existing magnetic field induced patterning assembly cannot keep the shape of a pattern stable and the pattern cannot be erased after being formed, the application provides a magnetic control phase change material capable of being subjected to magnetic field induced patterning assembly and erasing, and simultaneously, the invention also provides a preparation method of the magnetic control phase change material.
The technical scheme is as follows: the magnetic field induced patterned assembled and erasable magnetic control phase change material is a magnetic control phase change material compounded by fusing magnetic particles in a low-temperature phase change material, takes a polar or non-polar low-temperature phase change high polymer material as a base material and takes a surface polar or non-polar modified superparamagnetic nano material as a magnetic field response unit, wherein the mass ratio of the magnetic field response unit to the base material is 0.2-0.5: 1.
In the magnetic control phase change material, the molecular polarity of the matrix material is the same as that of the magnetic field response unit, namely the magnetic control phase change material can be divided into two types:
the first is a composite material of a surface polarity modified superparamagnetic nano material and a polar low-temperature phase change polymer material, wherein the surface polarity modified superparamagnetic nano material is a superparamagnetic nano material with a surface grafted with a polar long-chain polymer, and the polar low-temperature phase change polymer can be a hydrophilic low-temperature phase change polymer such as polyethylene glycol, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, double-end amino polyethylene glycol or double-end carboxyl polyethylene glycol.
The second is a composite material of a surface nonpolar modified superparamagnetic nano material and a nonpolar low-temperature phase change high polymer material: the surface nonpolar modified superparamagnetic nano material is a superparamagnetic nano material with a surface grafted with nonpolar long-chain macromolecules, and the nonpolar low-temperature phase change macromolecules can be hydrophobic low-temperature phase change macromolecules such as various levels of long-chain fatty alkanes and modified bodies thereof, such as solid paraffin, docosane, octadecane, octadecylamine, tetracosane, octadecanol and the like; preferably, paraffin is selected.
In the two magnetic control phase change materials, the superparamagnetic nano material is selected from nano iron powder, nano ferroferric oxide, nano iron oxide, nano nickel powder, nano cobalt powder and the like, and is preferably nano ferroferric oxide.
The invention relates to a preparation method of a magnetic control phase change material capable of being erased and assembled in a magnetic field induction patterning mode, which comprises the following steps:
(1) preparing a surface polar or non-polar modified superparamagnetic nano material;
(2) adding the surface polarity or non-polarity modified superparamagnetic nano material into corresponding polarity or non-polarity low-temperature phase change macromolecules, and grinding to uniformly disperse the magnetic field response units in the matrix material.
In the first magnetic control phase change material, the preparation method of the surface polarity modified superparamagnetic nano material comprises the following steps: pretreating the surface of the superparamagnetic nano material, and introducing quaternary ammonium salt ion groups on the surface of the superparamagnetic nano material; and grafting the polar long-chain polymer anion salt to the surface of the pretreated particles to obtain the surface polarity modified superparamagnetic nano material. The preparation method specifically comprises the following steps:
adding a superparamagnetic nano material into water, taking dimethyl octadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride as a modifier, aging and reacting at room temperature for 12-24 hours, or reacting at 60-80 ℃ for 1-3 hours, washing and separating the obtained product with water and methanol for multiple times to obtain a superparamagnetic nano material with a quaternary ammonium salt ion group introduced to the surface;
in this step, the aging reaction time at room temperature is preferably 24 hours; the reaction can be accelerated by heating, for example, the reaction is carried out for 1 to 3 hours at 60 to 80 ℃, and the optimal reaction condition is that the reaction is carried out for 2 hours at 75 ℃.
And secondly, continuously reacting the polyethylene glycol-based polymer sulfonate with the pretreated superparamagnetic nano material at 65-80 ℃ for 12-24 hours, washing the product after reaction by using a mixed solution of water and methanol, and removing the superparamagnetic nano material with the unmodified surface in the product to obtain the superparamagnetic nano material with the modified surface polarity. The optimal reaction condition for the grafting reaction process in the step is that the reaction is carried out for 24 hours at 75 ℃.
The polyethylene glycol-based high-molecular sulfonate is prepared by sulfonating a polyethylene glycol-based high-molecular material and reacting a terminal hydroxyl functional group of the polyethylene glycol-based high-molecular material into a terminal sulfonate functional group; the polyethylene glycol-based high polymer material is selected from polyethylene glycol monomethyl ether, polyethylene glycol monooleate, fatty alcohol-polyoxyethylene ether and the like, and the molecular weight range of the polyethylene glycol-based high polymer material is 500-4000. Preferably, the preparation method of the polyethylene glycol-based polymer sulfonate comprises the following steps: adding sulfamic acid and urea into polyethylene glycol-based high polymer materials with different molecular weights, heating to 120 ℃ for reaction for 4-5 hours, dissolving with a large amount of ethanol after the reaction is finished, filtering, and volatilizing to obtain the product.
In the second magnetic control phase change material, the preparation method of the surface nonpolar modified superparamagnetic nano material comprises the following steps: pretreating the surface of the superparamagnetic nano material, and introducing an epoxy group on the surface of the superparamagnetic nano material; and then grafting the non-polar long chain modified by the end amino group to the surface of the particle obtained by pretreatment to obtain the surface non-polar modified superparamagnetic nano material. The preparation method specifically comprises the following steps:
adding a superparamagnetic nano material into an ethanol solution, reacting for 2-3 hours at 65-80 ℃ by taking gamma-glycidyl ether oxypropyl trimethoxy silane as a modifier, washing with ethanol after the reaction is finished, and drying to obtain a superparamagnetic nano material with epoxy groups introduced to the surface; the optimal reaction condition of the step is that the reaction is carried out for 2 hours at 70 ℃;
adding the dried product into N, N-dimethylformamide, adding long-paraffin amine, reacting for 3-5 hours at 60-80 ℃, carrying out magnetic separation after the reaction is finished, washing with a carbon tetrachloride solution, and removing the superparamagnetic nano material with the unmodified surface in the product to obtain the superparamagnetic nano material with the nonpolar surface. The optimum reaction conditions for this step were 65 ℃ for 4 hours.
After the surface polar or non-polar superparamagnetic nano material is prepared, preferably, the polar or non-polar low-temperature phase change polymer is heated to a temperature higher than the melting point of the polar or non-polar low-temperature phase change polymer by more than 10 ℃, and then the surface polar or non-polar modified superparamagnetic nano material is added; preferably, the addition amount of the surface polar or non-polar modified superparamagnetic nano material is 20-50% of the mass of the polar or non-polar low-temperature phase change polymer; preferably 30% of the mass of the polar or non-polar low-temperature phase-change polymer.
The method for carrying out magnetic field induced patterned assembly by adopting the magnetic control phase-change material and the erasing method respectively comprise the following steps:
(1) magnetic field induced patterned assembly process
Adopting a permanent magnet cylinder as a pixel point, adopting an array template to construct different patterns, and adopting a non-magnetic heating plate as a bearing plane of the magnetic control phase change material: placing a heating plate above the permanent magnet array, raising the temperature to be above the melting point of the magnetic control phase change material, and enriching the molten magnetic control phase change material to the surface of the permanent magnet array under the action of a magnetic field; and reducing the temperature below the melting point of the magnetic control phase change material to shape the constructed pattern.
The permanent magnet material can be a neodymium iron boron magnet cylinder, the diameter is generally 2-100 mm, and the magnetic field intensity is 200-500 mT; the array template can be prepared by casting, injection molding or 3D printing; the non-magnetic heating plate is composed of glass or plastic plate.
(2) Erasing process
When the erasing is needed, the heating plate with the magnetic control phase change material pattern is moved away from the permanent magnet array, the temperature is raised to be higher than the melting point of the magnetic control phase change material, and the automatic erasing of the pattern is realized by the phase change material through self-leveling.
Has the advantages that: compared with the prior art, the invention has the advantages that: (1) the magnetic control phase change material can realize patterned enrichment on different surfaces through the induction of a patterned magnetic field when the temperature is increased to be higher than the melting point, realize pattern stabilization under the condition of no magnetic field through crystallization, and realize self-leveling erasure of the patterns by increasing the temperature to be higher than the melting point under the action of no magnetic field; (2) the superparamagnetic nano material is modified and compounded with different low-temperature phase-change high-molecular materials to prepare the magnetic field induced patterned assembled erasable high-molecular composite material with two different matrixes of polarity and non-polarity, so that the method is simple and convenient, and the material cost is low; furthermore, the phase transition temperature, the liquid fluidity and the solid mechanical property of the material can be easily adjusted by controlling the molecular weight of the phase transition polymer material.
Drawings
FIG. 1 is a TEM image and an infrared spectrum of the surface non-polar modified superparamagnetic nanomaterial prepared in example 1;
FIG. 2 is a TEM image and an infrared spectrum of the surface polarity-modified superparamagnetic nanomaterial prepared in example 2;
FIG. 3 is a diagram illustrating the change of physical properties of the magnetically controlled phase change material prepared in example 1 during the reversible erasure process;
FIG. 4 is a schematic structural diagram of a permanent magnet magnetic array template prepared during a magnetic field induced patterned assembly experiment;
fig. 5 is a response pattern obtained by using the magnetic phase change material prepared in example 1 on the permanent magnet array template in fig. 4 under the induction of a magnetic field.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
The magnetic control phase change material capable of being assembled and erased in a magnetic field induction patterning mode is a magnetic control phase change material compounded by fusing magnetic particles in a low-temperature phase change material, the surface of the magnetic control phase change material is modified by utilizing the existing superparamagnetic particles, so that the magnetic control phase change material has surface properties fused in the corresponding phase change material, and then the modified magnetic particles and a phase change matrix are effectively and stably compounded and uniformly dispersed, so that the phase change material capable of quickly responding to a magnetic field can be obtained.
The magnetic control phase change material is a composite material, a polar or non-polar low-temperature phase change high polymer material is used as a base material, a surface polar or non-polar modified superparamagnetic nano material is used as a magnetic field response unit, and the mass ratio of the magnetic field response unit to the base material is 0.2-0.5: 1. In the magnetic control phase change material, the molecular polarity of the matrix material is the same as that of the magnetic field response unit, namely the magnetic control phase change material can be divided into two types: the first is a composite material of a surface polarity modified superparamagnetic nano material and a polar low-temperature phase change high polymer material, and the second is a composite material of a surface nonpolar modified superparamagnetic nano material and a nonpolar low-temperature phase change high polymer material.
The surface polarity modified superparamagnetic nano material is a superparamagnetic nano material with a surface grafted with a polar long-chain macromolecule, the surface nonpolar modified superparamagnetic nano material is a superparamagnetic nano material with a surface grafted with a nonpolar long-chain macromolecule, and the superparamagnetic nano material is selected from nano iron powder, nano ferroferric oxide, nano iron oxide, nano nickel powder, nano cobalt powder and the like. The polar low-temperature phase change polymer can be hydrophilic low-temperature phase change polymers such as polyethylene glycol, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, double-end amino polyethylene glycol or double-end carboxyl polyethylene glycol; the nonpolar low-temperature phase change polymer can be hydrophobic low-temperature phase change polymers such as various levels of long-chain aliphatic alkanes and modified bodies thereof, such as solid paraffin, docosane, octadecane, octadecylamine, tetracosane, octadecanol and the like.
Example 1
Preparation of surface non-polar modified superparamagnetic nano material/low-temperature phase change non-polar polymer composite material
(1) 0.5g of nano Fe is weighed3O4Adding the mixture into 80mL of anhydrous N, N-Dimethylformamide (DMF), performing ultrasonic treatment for half an hour to ensure stable dispersion, dropwise adding 1mL of ethanol solution containing 20% of gamma-glycidoxypropyltrimethoxysilane surfactant, adding the solution into a three-neck flask, performing mechanical stirring reaction at 70 ℃ for 2 hours, washing with ethanol after the reaction is finished, and drying;
(2) adding the dried product into 100mL of DMF, adding 0.8g of octadecylamine, reacting for 5 hours at 80 ℃, carrying out magnetic separation after the reaction is finished, washing with a DMF hot solution, removing residual octadecylamine, dissolving a superparamagnetic nano material with carbon tetrachloride, removing an insoluble body by suction filtration, and volatilizing the solution to obtain a modified superparamagnetic nano material, wherein a TEM picture and an infrared spectrum of the modified superparamagnetic nano material are shown in a picture 1;
(3) and (2) melting the prepared superparamagnetic nano material containing the octadecylamine long chain into a paraffin phase, wherein the mass of the superparamagnetic nano material containing the octadecylamine long chain is 0.5g, and the mass of the paraffin is 2.5g, and grinding is carried out to ensure that the superparamagnetic nano material is uniformly dispersed in a paraffin matrix, so as to prepare the paraffin-based magnetic-control phase-change material.
The paraffin-based magnetic control phase change material prepared by the embodiment is adopted to perform reversible erasure experiment and magnetic field induced patterning assembly experiment:
experiment-reversible Erasure experiment
FIG. 3 is a liquid-solid state transformation diagram of the magnetically controlled phase change material prepared in example 1 during the whole processes of patterning, pattern stabilization and pattern erasure in sequence from the original state, wherein (a) is the magnetically controlled phase change material in a planar solid state form, in which the magnetic response manipulation cannot be performed; (b) the figure is a diagram of a magnetically controlled phase change material in the form of a planar liquid, which is formed by heating the solid plane of figure (a), while the surface is in a fluid state, having magnetically responsive properties; (c) the liquid-phase magnetic control phase-change material in the figure is driven by a permanent magnet below a bearing plate to converge to the strongest position of a magnetic field, is in a steamed bun peak shape, and is still in a liquid phase after convergence; (d) the figure is formed by cooling and solidifying the material in the figure (c), wherein the magnetic control phase change material keeps the shape of the figure (c), but the phase state of the magnetic control phase change material is converted into a solid state, the magnetic control operation can not be carried out, and the shape is kept unchanged after the magnetic field is removed; (e) the picture is (d) the picture of the steamed bun peak after melting, the material is in a liquid state after heating and temperature rise, the shape is removed through self-leveling, the material is restored to a plane liquid state again, and next magnetic control writing can be carried out. These five figures illustrate a complete process of reversible erasure of a magnetically controlled surface.
Experiment two magnetic field induced patterning assembly experiment
Determining an array with the display precision of 15 times 15 of the required magnetic array, constructing a magnetic control array template prototype through 3dmax modeling software, wherein the size of the template is 16cm times 16cm, the thickness of the template is 1.5cm, the circular diameter of each jack is 4.2mm, the distance between the jacks is 8mm, the depth of each jack is 6mm, implementing the construction of an entity through 3D printing, finally printing the obtained permanent magnet array template as shown in figure 4, the array points of the permanent magnet array template can be similar to pixel points, and the pattern change can be effectively controlled through the arrangement of the inserted permanent magnets.
The size of a purchased neodymium iron boron permanent magnet is 4mm in circle diameter and 12mm in length, the neodymium iron boron permanent magnet is used as magnetic field generating units, the total number of the neodymium iron boron permanent magnet is 225, the neodymium iron boron permanent magnet is inserted into corresponding template gaps according to pattern requirements, a three-dimensional magnetic field array based on a plane pattern is constructed, and once magnetic fluid passes through the vicinity of the magnetic field array units, the magnetic fluid is attracted and accumulated, so that a three-dimensional material array is prepared. The magnetic control operation technology is that two permanent magnets are linearly combined to be used as a traction device to be carried on a plane electric moving device, magnetic fluid is drawn to a specified position under the operation of a computer end, and the magnetic strength is regulated and controlled through the distance between the magnets and a fluid flat plate.
Fig. 5 shows the magnetic control surface pattern obtained by magnetic field induced patterned assembly under the permanent magnet array template shown in fig. 4, the pattern configuration is accurate, and the center point of each peak coincides with the center of the template permanent magnet, which illustrates that the magnetic control phase change material can rapidly construct the surface pattern under the action of the magnetic field array.
Example 2
Preparation of surface polarity modified superparamagnetic nano material/low-temperature phase change polar polymer composite material
(1) 0.5g of nano Fe is weighed3O4Adding to 10mL of water, 3mL of dimethyloctadecyl [ 3-trimethoxysilylpropyl ] group]Adding 40% ammonium chloride methanol solution (mass fraction), dropwise adding ammonia water solution with pH of 12, adjusting pH to 10, stirring and aging at room temperature for 24 hours, washing with water and methanol for multiple times, performing magnetic separation, dissolving with tetrahydrofuran, performing suction filtration to remove insoluble matters, and volatilizing the solution to obtain a superparamagnetic nano material with a quaternary ammonium salt function on the surface;
(2) weighing 10g of polyethylene glycol monomethyl ether with molecular weight of 2000, adding 0.5g of sulfamic acid and 0.08g of urea, heating to 120 ℃ for reaction for 5 hours, dissolving with 100mL of ethanol after the reaction is finished, filtering, and volatilizing to obtain a macromolecular salt with a sulfonate end group;
(3) weighing 0.5g of quaternary ammonium salt superparamagnetic nano material and 10mL of polyethylene glycol monomethyl ether sulfonate aqueous solution (mass fraction is 20%) and stirring at 75 ℃ for 24 hours, magnetically separating the product, washing with toluene, carrying out suction filtration, and removing insoluble matters to finally obtain a superparamagnetic nano material modified by a super-long polyethylene glycol chain segment, wherein a TEM picture and an infrared spectrum of the superparamagnetic nano material are shown in a picture 2;
(4) weighing 1g of superparamagnetic nano material modified by a super-long polyethylene glycol chain segment, adding the superparamagnetic nano material into a polyethylene glycol matrix with the mass of 2g and the molecular weight of 4000, and grinding and dispersing to prepare the polyethylene glycol-based magnetically controlled phase change material.
Referring to the method in example 1, the magnetic field induced patterned assembly experiment and the reversible erasure experiment are performed on the polyethylene glycol-based magnetically controlled phase change material prepared in this example, and the results show that the polar polyethylene glycol-based magnetically controlled phase change material prepared in this example can also achieve magnetic field induced patterned assembly, and the pattern can be stably and reversibly erased in the absence of a magnetic field.
Example 3
Referring to example 1, a surface non-polar modified superparamagnetic nanomaterial/low temperature phase transition non-polar polymer composite is prepared, except that, in the step (2), the reaction temperature of the nanomagnetic material with epoxy groups and the alkane amine is 65 ℃, and the reaction time is 4 hours.
Example 4
The surface polarity modified superparamagnetic nano material/low temperature phase transition polar polymer composite material is prepared by the method of the embodiment 2, and the difference is that: in the step (1), the aging reaction is accelerated by heating: 0.5g of nano Fe3O4Adding into 80mL of water, heating to 75 deg.C, adding 3mL of dimethyl octadecyl [ 3-trimethoxysilylpropyl ] with mass fraction of 40%]Ammonium chloride in methanol, an aqueous ammonia solution having a pH of 12 was added dropwise thereto, the pH of the solution was adjusted to 10, and the reaction was stirred for 2 hours.
Claims (8)
1. The application of the magnetic control phase change material for magnetic field induced patterning assembly and erasure is characterized in that the magnetic control phase change material takes a polar or non-polar low-temperature phase change high polymer material as a base material and takes a surface polar or non-polar modified superparamagnetic nano material as a magnetic field response unit, and the mass ratio of the magnetic field response unit to the base material is 0.2-0.5: 1; in the magnetic control phase change material, the molecular polarities of the matrix material and the magnetic field response unit are the same; the polar low-temperature phase change polymer material is a hydrophilic low-temperature phase change polymer which is polyethylene glycol, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, double-end amino polyethylene glycol or double-end carboxyl polyethylene glycol; the non-polar low-temperature phase change polymer material is a hydrophobic low-temperature phase change polymer, and the hydrophobic low-temperature phase change polymer is selected from various levels of long-chain aliphatic alkanes and modified bodies thereof; the surface polarity or non-polarity modified superparamagnetic nano material is a superparamagnetic nano material with a surface grafted with a polarity or non-polarity long-chain macromolecule, wherein the superparamagnetic nano material is one or more of nano iron powder, nano ferroferric oxide, nano iron oxide, nano nickel powder and nano cobalt powder; when erasing, the non-magnetic heating plate with the magnetic control phase change material pattern is moved away from the permanent magnet array, the temperature is raised to be higher than the melting point of the magnetic control phase change material, and the magnetic control phase change material automatically erases the pattern through self-leveling.
2. The use according to claim 1, wherein the magnetically controlled phase change material is prepared by a method comprising:
(1) preparing a surface polar or non-polar modified superparamagnetic nano material;
(2) adding the surface polarity or non-polarity modified superparamagnetic nano material into a corresponding polarity or non-polarity low-temperature phase change polymer material, and grinding to uniformly disperse the magnetic field response units in the matrix material.
3. The use according to claim 2, wherein in the step (1), the surface polarity modified superparamagnetic nanomaterial is prepared by: pretreating the surface of the superparamagnetic nano material, and introducing quaternary ammonium salt ion groups on the surface of the superparamagnetic nano material; and grafting the polar long-chain polymer anion salt to the surface of the pretreated particles to obtain the surface polarity modified superparamagnetic nano material.
4. The use according to claim 3, wherein the preparation step of the surface polarity modified superparamagnetic nanomaterial comprises:
adding a superparamagnetic nano material into water, taking dimethyl octadecyl [ 3-trimethoxysilylpropyl ] ammonium chloride as a modifier, aging and reacting at room temperature for 12-24 hours, or reacting at 60-80 ℃ for 1-3 hours, washing and separating the obtained product with water and methanol for multiple times to obtain a superparamagnetic nano material with a quaternary ammonium salt ion group introduced to the surface;
and secondly, continuously reacting the polyethylene glycol-based polymer sulfonate with the pretreated superparamagnetic nano material at 65-80 ℃ for 12-24 hours, washing the product after reaction by using a mixed solution of water and methanol, and removing the superparamagnetic nano material with the unmodified surface in the product to obtain the product.
5. The application of claim 4, wherein in the step II, the polyethylene glycol-based polymer sulfonate is obtained by sulfonating a polyethylene glycol-based polymer material, wherein the polyethylene glycol-based polymer material is selected from polyethylene glycol monomethyl ether, polyethylene glycol monooleate and fatty alcohol polyoxyethylene ether, and the molecular weight range of the polyethylene glycol-based polymer material is 500-4000.
6. The use according to claim 2, wherein in the step (1), the surface non-polar modified superparamagnetic nanomaterial is prepared by: pretreating the surface of the superparamagnetic nano material, and introducing an epoxy group on the surface of the superparamagnetic nano material; and then grafting the non-polar long chain modified by the end amino group to the surface of the particle obtained by pretreatment to obtain the surface non-polar modified superparamagnetic nano material.
7. The use according to claim 6, wherein the surface non-polar modified superparamagnetic nanomaterial is prepared by:
adding a superparamagnetic nano material into an ethanol solution, reacting for 2-3 hours at 65-80 ℃ by taking gamma-glycidyl ether oxypropyl trimethoxy silane as a modifier, washing with ethanol after the reaction is finished, and drying to obtain a superparamagnetic nano material with epoxy groups introduced to the surface;
adding the dried product into N, N-dimethylformamide, adding long-paraffin amine, reacting for 3-5 hours at 60-80 ℃, carrying out magnetic separation after the reaction is finished, washing with a carbon tetrachloride solution, and removing the superparamagnetic nano material with the unmodified surface in the product to obtain the product.
8. The application of claim 2, wherein in the step (2), the polar or non-polar low-temperature phase-change polymer is heated to a temperature higher than the melting point of the polar or non-polar low-temperature phase-change polymer by more than 10 ℃, and then the surface polar or non-polar modified superparamagnetic nanomaterial is added, wherein the addition amount of the surface polar or non-polar modified superparamagnetic nanomaterial is 20-50% of the mass of the polar or non-polar low-temperature phase-change polymer.
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| Surface-Functionalized Nanoparticles with Liquid-Like Behavior;Athanasios B. Bourlinos等;《Advanced Materials》;20050125;第17卷(第2期);第234-237页 * |
| 纳米SiO2/Fe3O4磁性流体的制备及其性能表征;张均成等;《东北电力大学学报》;20180815;第35卷(第4期);第40-46页 * |
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