CN112920463B - Monodisperse core-shell particle capable of being magnetically discolored in oleoresin and preparation method thereof - Google Patents

Monodisperse core-shell particle capable of being magnetically discolored in oleoresin and preparation method thereof Download PDF

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CN112920463B
CN112920463B CN202110127351.9A CN202110127351A CN112920463B CN 112920463 B CN112920463 B CN 112920463B CN 202110127351 A CN202110127351 A CN 202110127351A CN 112920463 B CN112920463 B CN 112920463B
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oleoresin
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CN112920463A (en
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罗巍
蒲宇洋
李刚
马会茹
官建国
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Wuhan Photochemical Technology Research Institute
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Wuhan University of Technology WUT
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Abstract

The invention relates to the field of photonic crystal materials, in particular to monodisperse core-shell particles capable of being magnetically discolored in oleoresin and a preparation method thereof. Compared with the existing similar products, the monodisperse core-shell particles capable of changing color by magnetic change solve the problem of dispersibility of magnetic photonic crystal materials in oleoresin, can be used as fillers to be dispersed in the oleoresin, the core-shell particles can be arranged into an ordered structure under the action of an external magnetic field, and the lattice spacing of the ordered structure can be changed along with the change of the magnetic field intensity.

Description

Monodisperse core-shell particle capable of being magnetically discolored in oleoresin and preparation method thereof
Technical Field
The invention relates to the field of photonic crystal materials, in particular to monodisperse core-shell particles capable of being magnetically discolored in oleoresin and a preparation method thereof.
Background
Due to the unique periodic structure of the one-dimensional magnetic photonic crystal, the one-dimensional magnetic photonic crystal generates a bright structural color under the action of light refraction or diffraction and an external magnetic field. By changing the intensity of the applied magnetic field, the lattice spacing of the magnetic nano core-shell particles dispersed in the liquid is changed, so that different structural colors are diffracted. And the diameter of the core-shell structure is in the nanometer level, and the smaller size is beneficial to improving the modulation resolution of the photonic crystal to light. In addition, the magnetic nano core-shell particles are simple and convenient to manufacture and high in color saturation, so that the magnetic nano core-shell particles show attractive application prospects in the fields of energy-saving display, bragg reflectors, microenvironment sensing, imaging and the like.
But the hitherto developed magnetically assemblable one-dimensional magneticsThe outer layer of the core-shell particle of the photonic crystal is limited to a few materials, including SiO 2 Carbon, polyelectrolytes, polyvinylpyrrolidone, and the like. Their hydrophilicity, results in their generally being only magnetically discolored in a few more polar hydrophilic solutions or monomers, but not in most less polar oily polymer monomers or resins, such as most oily acrylates, epoxies, polyurethanes, and the like. Such oily polymer monomers or resins are commonly used as raw materials in the fields of coatings, inks, adhesives and the like. Therefore, there is a trend toward development of magnetic photonic crystals capable of possessing a magnetochromic ability in oleoresins.
Disclosure of Invention
The invention aims to provide monodisperse core-shell particles which can be used as fillers to be dispersed in oleoresin and can be magnetically discolored in oleoresin, and structural colors of different wave bands can be diffracted under the action of external magnetic fields with different intensities.
The second purpose of the invention is to provide a preparation method of monodisperse core-shell particles which can be magnetically discolored in oleoresin, and the preparation method is simple and convenient in preparation process and easy to adjust.
The scheme adopted by the invention for realizing one purpose is as follows: the monodisperse core-shell particles can be magnetically changed in oleoresin, the cores of the core-shell particles are magnetic particles, the shells of the core-shell particles are oily polymer layers, and the core-shell particles can be dispersed in the oleoresin and diffract structural colors of different wave bands along with the change of magnetic field intensity.
Preferably, the magnetic field strength is more than or equal to 100GS.
Preferably, the particle size of the core-shell particles is 60 to 300nm; the oily polymer layer is a lipophilic homopolymer or copolymer at least containing one ester group.
Preferably, the magnetic particles contain at least any one element selected from iron, cobalt, and nickel.
Preferably, the oily resin is at least one of an epoxy resin, an acrylate resin and a polyurethane resin.
The second scheme adopted by the invention for realizing the purpose is as follows: a preparation method of the monodisperse core-shell particles capable of being magnetically discolored in oleoresin comprises the following steps:
(1) Uniformly mixing magnetic particles with an oily polymerizable shell raw material, an initiator and a dispersion medium solvent to obtain a pre-polymerization solution;
(2) And initiating polymerization by using the pre-polymerization solution to enable the polymer to be coated on the surfaces of the magnetic particles, and obtaining the core-shell particles after the reaction is finished.
Preferably, in the step (1), the pre-polymerization solution containing the magnetic particles can change the structural color with the change of the magnetic field intensity, and the concentration of the magnetic particles in the pre-polymerization solution is 0.1-200mg/mL.
Preferably, in the step (1), the oily polymerizable shell raw material at least comprises an oily monomer or prepolymer with an ester group; at room temperature, the solubility of the oily polymerizable shell raw material in water is less than 1g/100mL, and the concentration of the oily polymerizable shell raw material in the prepolymerization solution is 0.01-1.0mmol/mL.
Preferably, in the step (1), the initiator is a photoinitiator or a thermal initiator, and the amount of the initiator is 0.5-10% of the molar weight of the oily polymerizable shell raw material; the solvent of the dispersion medium is at least one of dimethyl sulfoxide, N, N dimethylformamide, alcohols, water, alcohol ethers, halogenated hydrocarbon and ethyl lactate.
The invention has the following advantages and beneficial effects: compared with the prior similar products, the monodisperse core-shell particles with the magnetic discoloration function can be used as filler to be dispersed in oleoresin, the core-shell particles can be arranged into an ordered structure under the action of an external magnetic field, and the lattice spacing of the ordered structure can be changed along with the change of the magnetic field intensity, so that structural colors of different wave bands can be diffracted under the action of external magnetic fields with different intensities.
The monodisperse core-shell particle capable of changing the magnetic color solves the problem of dispersibility of the magnetic photonic crystal material in the oleoresin, and has the capability of changing the magnetic color in the oleoresin.
Drawings
FIG. 1 is a spectrum (a) of a monodisperse core-shell particle that is photochromically changeable and prepared in example 1 under different magnetic fields and digital photographic images (b) and (c) of the dispersion thereof in an epoxy resin with different applied magnetic field strengths;
FIG. 2 is a spectrum of the dispersed, magnetically variable monodisperse core-shell particles prepared in example 2 in an acrylic resin after application of magnetic fields of different strengths;
FIG. 3 is a spectrum of the dispersed monodisperse core-shell particles of the magnetochromic material prepared in example 3 in a polyurethane resin after application of magnetic fields of different strengths;
FIG. 4 is a spectrum of the dispersed, magnetically variable monodisperse core-shell particles prepared in example 4 in an epoxy resin after application of magnetic fields of different strengths;
FIG. 5 is a spectrum of the dispersed, magnetically variable monodisperse core-shell particles prepared in example 5 after application of magnetic fields of different strengths in an epoxy resin;
FIG. 6 is a spectrum of the dispersed, magnetically variable monodisperse core-shell particles prepared in example 6 after application of magnetic fields of different strengths in an epoxy resin;
FIG. 7 is a spectrum of the dispersed, magnetically variable monodisperse core-shell particles prepared in example 7 after application of magnetic fields of different strengths in an epoxy resin;
FIG. 8 is a spectrum of the dispersed, magnetically variable monodisperse core-shell particles prepared in example 8 after application of magnetic fields of different strengths in an epoxy resin;
fig. 9 is a spectrum of the magnetochromic monodisperse core-shell particles prepared in example 9 dispersed in an epoxy resin after applying magnetic fields of different strengths.
Detailed Description
The following examples are provided to further illustrate the present invention for better understanding, but the present invention is not limited to the following examples.
Example 1
(1) Magnetic particles (made of FeO) x The core and polyvinylpyrrolidone coated on the surface of the core (particle diameter is 100 nm) are dispersed in glycerol dimethacrylate and 2-hydroxy photoinitiatorForming a pre-polymerization liquid in a dispersion medium consisting of 2-methyl-1-phenyl acetone (HMPP), dimethyl sulfoxide and water, wherein the concentration of the glycerol dimethacrylate in the pre-polymerization liquid is 0.1mmol/ml, the concentration of the HMPP is 3% of the molar weight of the glycerol dimethacrylate, the concentration of the magnetic particles in the pre-polymerization liquid is 5mg/ml, and the molar ratio of the dimethyl sulfoxide to the water is 8:2;
(2) Curing the pre-polymerized liquid by using an ultraviolet lamp, centrifugally washing the prepared core-shell magnetic particles after the reaction is finished, dispersing the final product in epoxy resin, respectively applying a magnetic field with the strength of 100-1200Gs, and gradually performing blue shift on the resin color along with the increase of the magnetic field.
FIG. 1 is a spectrogram (a) and digital photographs (b) and (c) of the example 1 in which the monodisperse core-shell particles capable of changing colors are dispersed in an epoxy resin under different applied magnetic fields; it is known from the graph (a) that the peak positions of the magnetic particles change under different magnetic fields, the graphs (b) and (c) respectively correspond to the corresponding colors under the magnetic fields of 300Gs and 1200Gs, at 300Gs, the dispersed single-dispersed core-shell particles with the magnetic discoloration are orange red in the epoxy resin, and at 1200Gs, the dispersed single-dispersed core-shell particles with the magnetic discoloration are yellow green in the epoxy resin.
FeO in this example x Is ferroferric oxide, gamma-ferric oxide or a mixture of the ferroferric oxide and the gamma-ferric oxide in any mass ratio, and FeO is adopted in other embodiments x Or other magnetic cores in the prior art.
Example 2
(1) Magnetic particles (made of Fe) (1-y) Co y O x The magnetic particle pre-polymerization method comprises the following steps of (1) dispersing an inner core and polyvinylpyrrolidone (with the particle size of 120 nm) coated on the surface of the inner core into a dispersion medium consisting of pentaerythritol triacrylate, a photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone (HMPP), n-butanol and benzyl alcohol to form pre-polymerization liquid, and adding the pre-polymerization liquid into a three-neck flask, wherein the concentration of the pentaerythritol triacrylate in the pre-polymerization liquid is 0.1mmol/ml, the concentration of the HMPP is 3% of the pentaerythritol triacrylate, the concentration of the magnetic particles in the pre-polymerization liquid is 0.5mg/ml, and the molar ratio of the n-butanol to the benzyl alcohol is 8:2;
(2) Curing the pre-polymerization liquid by using an ultraviolet lamp, centrifugally washing the prepared core-shell magnetic particles after the reaction is finished, dispersing the final product in acrylic resin, respectively applying magnetic fields with the strength of 400-1200Gs, and gradually performing blue shift on the resin color along with the increase of the magnetic fields.
FIG. 2 is a spectrum of the dispersion of the magnetically variable monodisperse core-shell particles in the acrylic resin of example 2 after application of different magnetic fields; it is known from the figure that the peak position gradually moves blue as the magnetic field strength increases.
Fe in this example (1-y) Co y O x That is, a substance in which part of the Fe atoms were replaced with Co atoms, the other steps were the same as in example 1.
Example 3
(1) Magnetic particles (made of Fe) (1-y) Ni y O x The magnetic particle pre-polymerization solution comprises a core and polyvinylpyrrolidone (with the particle size of 200 nm) coated on the surface of the core, wherein the polyvinylpyrrolidone is dispersed into a dispersion medium consisting of bisphenol A glycerol dimethacrylate, a photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone (HMPP), diethylene glycol monomethyl ether and water to form a pre-polymerization solution, the concentration of the bisphenol A glycerol dimethacrylate in the pre-polymerization solution is 0.2mmol/ml, the concentration of the HMPP is 3% of that of the bisphenol A glycerol dimethacrylate, the concentration of the magnetic particle in the pre-polymerization solution is 0.5mg/ml, and the molar ratio of the diethylene glycol monomethyl ether to the water is 8.5;
(2) Curing the pre-polymerization liquid by using an ultraviolet lamp, centrifugally washing the prepared core-shell magnetic particles after the reaction is finished, dispersing the final product in polyurethane resin, respectively applying magnetic fields with the strength of 200-1200Gs, and gradually performing blue shift on the resin color along with the increase of the magnetic fields.
FIG. 3 is a spectrum of the dispersed, magnetically variable monodisperse core-shell particles of example 3 in an epoxy resin after application of different magnetic fields; it is known from the figure that the peak position gradually shifts blue as the magnetic field increases.
Fe in this example (1-y) Ni y O x That is, a substance in which a part of Fe atoms were replaced with Ni atoms, the other steps were the same as in example 1.
Example 4
(1) Magnetic particles (made of Fe) (1-y-z) Co z Ni y O x Core and claddingAnd (2) polyvinylpyrrolidone on the surface of the inner core (with the particle size of 240 nm) is dispersed into a dispersion medium consisting of Ethylene Glycol Dimethacrylate (EGDMA), photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone (HMPP), dimethyl sulfoxide and water to form a pre-polymerization solution, wherein the concentration of acrylic resin in the pre-polymerization solution is 0.1mmol/ml, the concentration of HMPP is 3% of the molar amount of the ethylene glycol dimethacrylate, the concentration of magnetic particles in the pre-polymerization solution is 0.5mg/ml, and the molar ratio of the dimethyl sulfoxide to the water is 7.5:2.5;
(2) Curing the pre-polymerization liquid by using an ultraviolet lamp, washing the prepared magnetic nano core-shell particles after the reaction is finished, dispersing the final product in epoxy resin, respectively applying a magnetic field with the strength of 200-1200Gs, and gradually performing blue shift on the resin color along with the increase of the magnetic field.
FIG. 4 is a spectrum of the dispersed, magnetically variable monodisperse core-shell particles of example 4 in an epoxy resin after application of different magnetic fields; it is known from the figure that the peak position gradually shifts blue as the magnetic field increases.
Fe in this example (1-y-z) Co z Ni y O x That is, the same as in example 1, except that part of the Fe atoms were replaced by Ni and Co atoms.
Example 5
(1) Magnetic particles (made of FeO) x The magnetic particle pre-polymerization solution comprises an inner core and polyvinylpyrrolidone (with the particle size of 180 nm) coated on the surface of the inner core, wherein the polyvinylpyrrolidone is dispersed into a dispersion medium consisting of 1- (acrylamide) -3- (methacryloyloxy) -2-propanol, azobisisobutyronitrile, 2-ethoxyethanol and water to form a pre-polymerization solution, the concentration of the pre-polymerization solution 1- (acrylamide) -3- (methacryloyloxy) -2-propanol is 0.2mmol/ml, the concentration of the azobisisobutyronitrile is 10% of the molar weight of the 1- (acrylamide) -3- (methacryloyloxy) -2-propanol, the concentration of the magnetic particles in the pre-polymerization solution is 10mg/ml, and the molar ratio of the 2-ethoxyethanol to the water is 8:2;
(2) And (3) directly heating the pre-polymerization solution, adopting a thermal initiation polymerization mode, washing the prepared magnetic nano core-shell particles after the reaction is finished, dispersing the final product in epoxy resin, respectively applying magnetic fields with the strength of 100-1200Gs, and gradually performing blue shift on the resin color along with the increase of the magnetic fields.
FIG. 5 is a spectrum of the dispersed, magnetically variable monodisperse core-shell particles of example 5 in an epoxy resin after application of different magnetic fields; it is known from the figure that the peak position gradually shifts blue as the magnetic field increases.
Example 6
(1) Magnetic particles (made of FeO) x The magnetic particle pre-polymerization solution comprises an inner core and a carbon shell layer (the particle size is 180 nm) coated on the surface of the inner core, the carbon shell layer is dispersed into a dispersion medium consisting of diethylene glycol diacrylate, ammonium persulfate, sodium bisulfite, dimethyl sulfoxide and water to form pre-polymerization solution, the concentration of the diethylene glycol diacrylate in the pre-polymerization solution is 1mmol/ml, the concentration of the ammonium persulfate and the sodium bisulfite is 10% of the molar weight of the diethylene glycol diacrylate, the concentration of the magnetic particle in the pre-polymerization solution is 20mg/ml, and the molar ratio of the dimethyl sulfoxide to the water is 9:1;
(2) And (3) directly heating the pre-polymerization solution, adopting a thermal initiation polymerization mode, washing the prepared magnetic nano core-shell particles after the reaction is finished, dispersing the final product in epoxy resin, respectively applying magnetic fields with the strength of 100-1200Gs, and gradually performing blue shift on the resin color along with the increase of the magnetic fields.
FIG. 6 is a spectrum of the dispersed monodisperse core-shell particles of example 6 after different magnetic fields are applied to the oleoresin; it can be known from the figure that the peak position changes under different magnetic fields.
Example 7
(1) Magnetic particles (made of FeO) x The inner core and the carbon shell layer coated on the surface of the inner core (the particle size is 120 nm) are dispersed into a dispersion medium consisting of diethylene glycol dimethacrylate, cyclohexanone peroxide, naphthenate, dimethyl sulfoxide and water to form a pre-polymerization solution, the concentration of the diethylene glycol dimethacrylate in the pre-polymerization solution is 0.1mmol/ml, the concentration of the cyclohexanone peroxide and the naphthenate is 0.5% of the molar weight of the diethylene glycol dimethacrylate, the concentration of magnetic particles in the pre-polymerization solution is 0.5mg/ml, and the molar ratio of the dimethyl sulfoxide to the water is 9:1;
(2) And (3) directly heating the pre-polymerization solution, adopting a thermal initiation polymerization mode, washing the prepared magnetic nano core-shell particles after the reaction is finished, dispersing the final product in epoxy resin, respectively applying magnetic fields with the strength of 200-1200Gs, and gradually performing blue shift on the resin color along with the increase of the magnetic fields.
FIG. 7 is a spectrum of the dispersed monodisperse core-shell particles of example 7 in oleoresin after application of different magnetic fields; it can be known from the figure that the peak position changes under different magnetic fields.
Example 8
(1) Magnetic particles (made of FeO) x The magnetic particle pre-polymerization solution comprises an inner core and polyvinylpyrrolidone (the particle size is 150 nm) coated on the surface of the inner core, the polyvinylpyrrolidone is dispersed into a dispersion medium consisting of 4,4-isopropylidenediphenol dimethacrylate, a photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone (HMPP), dimethyl sulfoxide and water to form a pre-polymerization solution, the concentration of 4,4-isopropylidenediphenol dimethacrylate in the pre-polymerization solution is 0.05mmol/ml, the concentration of HMPP is 2% of the molar weight of 4,4-isopropylidenediphenol dimethacrylate, the concentration of magnetic particles in the pre-polymerization solution is 0.5mg/ml, and the molar ratio of dimethyl sulfoxide to water is 9:1;
(2) Curing the pre-polymerization liquid by using an ultraviolet lamp, washing the prepared magnetic nano core-shell particles after the reaction is finished, dispersing the final product in epoxy resin, respectively applying magnetic fields with the strength of 100-1200Gs, and gradually performing blue shift on the resin color along with the increase of the magnetic fields.
FIG. 8 is a spectrum of the dispersed monodisperse core-shell particles of example 8 after different magnetic fields are applied to the oleoresin; it can be known from the figure that the peak position changes under different magnetic fields.
Example 9
(1) Magnetic particles (made of FeO) x The magnetic particle comprises an inner core and a carbon shell layer coated on the surface of the inner core, wherein the particle size is 150nm, the inner core is dispersed into a dispersion medium consisting of glycidyl methacrylate, ethylene glycol dimethacrylate, a photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone (HMPP), dimethyl sulfoxide and water to form a pre-polymerization liquid, the concentration of the glycidyl methacrylate in the pre-polymerization liquid is 0.02mmol/ml, the concentration of the ethylene glycol dimethacrylate is 0.01mmol/ml, the concentration of the HMPP is 2% of the molar weight of 2-acrylic acid-2-hydroxy-3-phenoxypropyl ester, and the magnetic particleThe concentration in the pre-polymerization liquid is 0.5mg/ml, and the molar ratio of the dimethyl sulfoxide to the water is 9:1;
(2) Curing the pre-polymerization liquid by using an ultraviolet lamp, washing the prepared magnetic nano core-shell particles after the reaction is finished, dispersing the final product in epoxy resin, respectively applying a magnetic field with the strength of 200-1200Gs, and gradually performing blue shift on the resin color along with the increase of the magnetic field.
FIG. 9 is a spectrum of the monodisperse core-shell particles which are magnetically variable in example 9 dispersed in an oleoresin after application of different magnetic fields; it can be known from the figure that the peak position changes under different magnetic fields.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

Claims (8)

1. Monodisperse core-shell particles which are capable of being magnetically induced to change colour in oleoresin characterised in that: the core of the core-shell particle is a magnetic particle, the shell of the core-shell particle is an oily polymer layer, and the core-shell particle can be dispersed in oily resin and diffract structural colors of different wave bands along with the change of magnetic field intensity; the particle size of the core-shell particles is 60 to 300nm; the oily polymer layer is a lipophilic homopolymer or copolymer at least containing one acrylate group.
2. Monodisperse core-shell particles, which are magnetically targetable in oleoresin according to claim 1, characterized in that: the magnetic field intensity is more than or equal to 100GS.
3. Monodisperse core-shell particles, which are magnetically targetable in oleoresin according to claim 1, characterized in that: the magnetic particles contain at least one element selected from iron, cobalt, and nickel.
4. Monodisperse core-shell particles, which are magnetically targetable in oleoresin according to claim 1, characterized in that: the oleoresin is at least one of epoxy resin, acrylate resin and polyurethane resin.
5. A process for the preparation of monodisperse core-shell particles magnetically metachromatic in oleoresin according to any one of claims 1-4, comprising the steps of:
(1) Uniformly mixing magnetic particles with an oily polymerizable shell raw material, an initiator and a dispersion medium solvent to obtain a pre-polymerization solution;
(2) And initiating polymerization by using the pre-polymerization solution to coat the polymer on the surfaces of the magnetic particles, and obtaining the core-shell particles after the reaction is finished.
6. The method for producing monodisperse core-shell particles capable of being magnetically discolored in an oleoresin according to claim 5, wherein: in the step (1), the pre-polymerization solution containing the magnetic particles can change the structural color along with the change of the magnetic field intensity, and the concentration of the magnetic particles in the pre-polymerization solution is 0.1-200mg/mL.
7. The process for preparing monodisperse core-shell particles which are capable of being magnetically discolored in an oleoresin according to claim 5, characterized in that: in the step (1), the oily polymerizable shell raw material at least comprises an oily monomer or prepolymer with an acrylate group; at room temperature, the solubility of the oily polymerizable shell raw material in water is less than 1g/100mL, and the concentration of the oily polymerizable shell raw material in the prepolymerization solution is 0.01-1.0mmol/mL.
8. The process for preparing monodisperse core-shell particles which are capable of being magnetically discolored in an oleoresin according to claim 5, characterized in that: in the step (1), the initiator is a photoinitiator or a thermal initiator, and the dosage of the initiator is 0.5-10% of the molar weight of the oily polymerizable shell raw material; the solvent of the dispersion medium is at least one of dimethyl sulfoxide, N, N dimethyl formamide, alcohol, water, alcohol ether, halogenated hydrocarbon and ethyl lactate.
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