CN110804127A - Flexible photonic crystal element nano-microsphere and preparation method thereof - Google Patents
Flexible photonic crystal element nano-microsphere and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of a nano microsphere, in particular to a flexible photonic crystal element nano microsphere and a preparation method thereof. The nano-microsphere is prepared from the following raw materials in percentage by weight: 0.02-0.04 wt% of emulsifier, 4-7 wt% of inner-layer hard monomer, 5-15 wt% of inner-layer cross-linking agent, 9-15 wt% of outer-layer monomer, 0.1-1 wt% of outer-layer cross-linking agent, and 1-3 wt% of initiator, wherein the total amount of the inner-layer hard monomer and the outer-layer monomer is the same as that of the outer-layer cross-linking agent; the balance being water. The invention can effectively prepare the soft nanometer microsphere by two-step emulsion polymerization, and the hardness of the outer layer can be very simply and conveniently regulated by a mode of soft and hard monomer copolymerization. The inner-layer cross-linking agent can enable double bonds to exist on the surface of the inner core, and the outer-layer monomer can be anchored on the surface of the inner core under the action of the outer-layer cross-linking agent, so that the structure of the inner-layer cross-linking agent is more stable.
Description
Technical Field
The invention relates to a preparation method of a nano microsphere, in particular to a flexible photonic crystal element nano microsphere and a preparation method thereof.
Background
The photonic crystal is a dielectric material with highly ordered structure, and due to the existence of a photonic forbidden band of the photonic crystal, visible light equivalent to the forbidden band can be prevented from passing through the photonic crystal to be selectively reflected, and constructive interference is formed on the surface of the photonic crystal. The color-generating material with the photonic crystal structure has attracted wide attention in the fields of intelligent response, intelligent display, sensing, printing, textile coloring and the like. However, the currently commonly used photonic crystal building blocks are typically silicon oxide (SiO)2) Hard nano-microspheres such as Polystyrene (PS) and polymethyl methacrylate (PMMA) cannot construct a flexible photonic crystal structure, and practical application of the nano-microspheres is limited to a great extent. Therefore, the design and preparation of the elementary nano-microsphere capable of constructing the photonic crystal film with high flexibility, high toughness, bright color and remarkable iridescence effect have important significance.
In recent years, researchers at home and abroad have conducted certain exploration on the preparation of soft nano microspheres for constructing a flexible photonic crystal structure, and the method mainly comprises the following steps: one-step emulsion polymerization (Wang J, Wen Y, Ge H, et al. SimpleFabrication of Full Color crystalline Films with Tough mechanical Strength [ J ]. Macromolecular Chemistry & Physics, 2006, 207(6): 596-. The one-step emulsion polymerization method is to add monomers of a nuclear layer and a shell layer and required various emulsifiers, initiators and other auxiliaries into a reactor together to complete one-step reaction. Although the method is simple and easy to operate, the prepared core-shell nano-microspheres are formed spontaneously completely depending on the difference of hydrophilicity and hydrophobicity of the monomers, the hydrophobic monomers are mainly positioned in a core layer, and the hydrophilic monomers are mainly positioned in a shell layer. However, in the reaction process, monomers of the core layer and the shell layer will have a certain copolymerization reaction, and it is difficult to controllably adjust the hardness of the obtained nano-microsphere. The pre-emulsification-semi-batch emulsion polymerization is to precisely control the composition of the core and the shell of the nano microsphere in a step-by-step feeding manner so as to obtain the required soft nano microsphere, but the monomer to be reacted is pre-emulsified and then added in four times in the reaction process, the prepared nano microsphere consists of three parts, namely the core, a transition layer and a shell, the soft shell needs to be bridged by the transition layer so as to be anchored on the surface of a hard core, and the preparation process and the technology are complex, so that the preparation efficiency of the nano microsphere is limited to a great extent. Therefore, the development of a preparation method of the hard core-soft shell type nano-microsphere with simple method and good hardness controllability has important significance for promoting the practical application of the photonic crystal.
Disclosure of Invention
The invention aims to provide a preparation method of flexible photonic crystal element nano microspheres, which has the advantages of good controllability on the hardness of the nano microspheres, simple preparation method, high polymerization efficiency, high reaction rate and the like.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a flexible photonic crystal element nano microsphere is prepared from the following raw materials in percentage by weight:
0.02-0.04 wt% of emulsifier,
4-7 wt% of inner hard monomer,
an inner layer cross-linking agent, wherein the inner layer cross-linking agent accounts for 5-15 wt% of the hard monomer content of the inner layer,
9 to 15 weight percent of outer layer monomer,
an outer layer cross-linking agent, wherein the outer layer cross-linking agent accounts for 0.1-1 wt% of the outer layer monomer content,
the initiator is 1-3 wt% of the total amount of the inner layer hard monomer and the outer layer monomer;
the balance being water.
The inner-layer cross-linking agent can enable double bonds to exist on the surface of the inner core, and the outer-layer monomer can be anchored on the surface of the inner core under the action of the outer-layer cross-linking agent, so that the structure of the nano microsphere is more stable. The core cross-linking agent can increase the refractive index of the core, so as to increase the difference of the refractive index of the inner layer and the outer layer, and the subsequent photonic crystal constructed by the assembly element has bright structural color.
Preferably, the inner layer cross-linking agent is divinylbenzene or ethylene glycol dimethacrylate.
Preferably, the outer-layer cross-linking agent is one or more of allyl methacrylate, N-methylene bisacrylamide or ethylene glycol dimethacrylate.
Preferably, the inner hard monomer is one of styrene, methyl methacrylate or methacrylic acid; the outer layer monomer is copolymerized by one or more of soft monomers and hard monomers; the soft monomer is selected from butyl acrylate, hydroxyethyl acrylate, ethyl acrylate or isooctyl acrylate, and the hard monomer is selected from acrylic acid, methacrylic acid, methyl methacrylate, methyl acrylate or hydroxyethyl methacrylate.
Preferably, the emulsifier is one or two of Sodium Dodecyl Sulfate (SDS) or Sodium Dodecyl Benzene Sulfonate (SDBS); the initiator is one or more of potassium persulfate, sodium persulfate or ammonium persulfate.
Preferably, the hard monomer in the outer layer monomer: the weight ratio of the soft monomers is 1: 1-5.
A preparation method of the flexible photonic crystal element nano-microsphere comprises the following steps:
(1) respectively washing and purifying the inner hard monomer, the inner cross-linking agent, the outer monomer and the outer cross-linking agent, and then carrying out drying pretreatment;
(2) firstly, adding an emulsifier and water into a reactor, mechanically stirring uniformly, and heating to 70-90 ℃;
(3) adding an inner-layer hard monomer and an inner-layer cross-linking agent into the reactor in the step (2), introducing inert gas to protect a reaction monomer, uniformly stirring, adding an initiator to initiate polymerization reaction, and keeping the temperature of 70-90 ℃ for polymerization reaction till the reaction is complete;
(4) slowly adding an outer-layer monomer and an outer-layer cross-linking agent into the reactor in the step (3) to react for 2-4 hours;
(5) and obtaining the soft nano microsphere emulsion after the reaction is finished.
The invention adopts two-step emulsion polymerization to prepare the soft nano-microspheres, does not need to pre-emulsify reactants, can directly anchor the outer soft monomer on the inner layer under the action of the inner and outer crosslinking agents, saves the preparation of a transition layer, and greatly shortens the preparation process of the nano-microspheres on the premise of ensuring the controllable hardness. The preparation method can conveniently regulate and control the size (100nm-500nm) of the nano-microsphere, and the prepared nano-microsphere has good monodispersity (PDI < 0.08), and can construct flexible photonic crystals with good optical properties and structural color.
Preferably, in the step (1), the washing alkali liquor is one or a mixture of sodium hydroxide or potassium hydroxide aqueous solution with the mass concentration of 5-10 wt%; the alkaline alumina for purification is selected from one or a mixture of 100-200 meshes, 200-300 meshes or 300-400 meshes; the desiccant is one or more of anhydrous calcium chloride, anhydrous magnesium sulfate and anhydrous calcium sulfate.
Preferably, in the step (2), the rotation speed of the mechanical stirring is 200 to 500 rmp, and the time is 10 to 20 min.
Preferably, in the step (3), the inert gas is nitrogen or argon, and the polymerization reaction time is 30-60 minutes.
The invention has the beneficial effects that:
1. the invention can effectively prepare the soft nanometer microsphere by two-step emulsion polymerization, and the hardness of the outer layer can be very simply and conveniently regulated by a mode of soft and hard monomer copolymerization. The inner-layer cross-linking agent can enable double bonds to exist on the surface of the inner core, and the outer-layer monomer can be anchored on the surface of the inner core under the action of the outer-layer cross-linking agent, so that the structure of the inner-layer cross-linking agent is more stable. And the refractive index of the inner core can be increased through the action of the inner core cross-linking agent, so that the refractive index difference of the inner layer and the outer layer is increased, and the photonic crystal constructed by the assembly element has bright structural color. By regulating and controlling the dosage of the outer layer monomer and the cross-linking agent, the photonic crystal film with higher stress can be prepared.
2. The invention prepares the soft nanometer microsphere by two-step emulsion polymerization, and the method is simple and convenient, and only needs to carry out gradual polymerization of the inner layer and the outer layer. When the outer monomer is dripped in the second step, because the free radicals in the reaction system are more and the reaction monomers are less, the reaction system is in a hunger state, the reaction speed can be greatly accelerated, and the reaction efficiency is improved.
3. The invention prepares the nano microspheres by emulsion polymerization in two steps, not only can regulate and control the hardness of the nano microspheres, but also has good sphericity, controllable particle size and good monodispersity. The obtained product has high purity, and the flexible photonic crystal can be directly prepared without further processing.
4. The soft nano-microsphere prepared by the invention can be used for constructing a flexible photonic crystal structure, the stability of the photonic crystal structure is improved, and the applicability of the color-generating material with the photonic crystal structure is further widened.
Drawings
FIG. 1 is a distribution diagram of the particle size of the soft nanospheres of examples 1 and 2 of the present invention;
FIG. 2 is a stress-strain curve diagram of the photonic crystal film obtained by self-assembly of the soft nano-microspheres prepared in example 1 and example 4;
FIG. 3 is an SEM photograph (50000X) of nanospheres prepared in example 2;
FIG. 4 is an SEM photograph (50000X) of nanospheres prepared in example 3;
FIG. 5 is a SEM photograph (50000X) of the three-dimensional photonic crystal structure obtained by self-assembly of the nano-microspheres prepared in example 5;
fig. 6 is a structural color film photo of the nano-microspheres prepared in examples 1 and 2 and 3 by self-assembly.
FIG. 7 is a bending test of the structural color film obtained by self-assembly of the nanospheres of example 1.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples. It is to be understood that the practice of the invention is not limited to the following examples, and that any variations and/or modifications may be made thereto without departing from the scope of the invention.
In the present invention, all parts and percentages are by weight, unless otherwise specified, and the equipment and materials used are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1
A flexible photonic crystal element nano microsphere is prepared from the following raw materials: 0.1g of SDS, 20g of styrene, 3g of divinylbenzene, 25g of butyl acrylate, 10g of methyl methacrylate, 0.1g of allyl methacrylate, 0.55g of potassium persulfate and 300mL of water.
A preparation method of flexible photonic crystal element nano microspheres comprises the following specific steps:
(1) respectively washing and purifying an inner hard monomer, an inner cross-linking agent, an outer monomer and an outer cross-linking agent, and then carrying out drying pretreatment, wherein the specific process comprises the following steps: washing the monomer or the cross-linking agent with 5 wt% of sodium hydroxide aqueous solution respectively, purifying by an alkaline alumina chromatographic column, adding a proper amount of anhydrous calcium chloride into the purified material for drying treatment, refrigerating at 0 ℃ for 1 hour, taking out calcium chloride particles, and keeping the purified and dried monomer and cross-linking agent for later use.
(2) 0.1g of emulsifier SDS and 300mL of water are added into a reactor, the mechanical stirring speed is 350r/min, and the temperature is raised to 85 ℃.
(3) 20g of styrene and 3g of divinylbenzene were introduced into the reactor and the monomers were protected by continuous nitrogen. After stirring for 10min, 0.55g of potassium persulfate was added to initiate polymerization, and the reaction time was 30min at 85 ℃.
(4) After 25g of butyl acrylate, 10g of methyl methacrylate and 0.1g of allyl methacrylate were uniformly mixed, the mixture was added dropwise to the reactor at a rate of 2 drops/sec for 2 hours using a constant pressure dropping funnel.
(5) And obtaining the soft nano microsphere emulsion after the reaction is finished.
Example 2
A flexible photonic crystal element nano microsphere is prepared from the following raw materials: 0.071g of SDS, 20g of methyl methacrylate, 2.5g of ethylene glycol dimethacrylate, 25g of butyl acrylate, 10g of methyl methacrylate, 0.1g of allyl methacrylate, 0.7g of sodium persulfate and 300mL of water.
A preparation method of flexible photonic crystal element nano microspheres comprises the following specific steps:
(1) the inner hard monomer, the inner crosslinking agent, the outer hard monomer and the outer crosslinking agent were washed and purified, respectively, and then subjected to a drying pretreatment in the same manner as in example 1.
(2) 0.071g of emulsifier SDS and 300mL of water are added into a reactor, the mechanical stirring speed is 200r/min, and the temperature is raised to 85 ℃.
(3) 20g of methyl methacrylate and 2.5g of ethylene glycol dimethacrylate were charged into the reactor and the monomers were protected by continuous nitrogen. After stirring for 10min, 0.7g of sodium persulfate is added to initiate polymerization, and the reaction time is kept for 60 min.
(4) After 25g of butyl acrylate, 10g of methyl methacrylate and 0.1g of allyl methacrylate were uniformly mixed, the mixture was added dropwise to the reactor at a rate of 2 drops/sec using a constant pressure dropping funnel and reacted for 4 hours.
(5) And obtaining the soft nano microsphere emulsion after the reaction is finished.
Example 3
A flexible photonic crystal element nano microsphere is prepared from the following raw materials: 0.1g of SDS, 15g of styrene, 1.5g of divinylbenzene, 25g of isooctyl acrylate, 5g of methacrylic acid, 0.35g of N, N-methylene-bisacrylamide, 1g of potassium persulfate and 300mL of water.
A preparation method of flexible photonic crystal element nano microspheres comprises the following specific steps:
(1) the inner hard monomer, the inner crosslinking agent, the outer hard monomer and the outer crosslinking agent were washed and purified, respectively, and then subjected to a drying pretreatment in the same manner as in example 1.
(2) 0.1g of emulsifier SDS and 300mL of water are added into a reactor, the mechanical stirring speed is 400r/min, and the temperature is raised to 70 ℃.
(3) 15g of styrene and 1.5g of divinylbenzene were introduced into the reactor and the monomers were protected by continuous nitrogen. Stirring for 15min, adding 1g of potassium persulfate to initiate polymerization, and keeping the temperature for 40 min.
(4) After 25g of isooctyl acrylate, 5g of methacrylic acid and 0.35g N, N-methylenebisacrylamide were mixed uniformly, they were added dropwise to the reactor at a rate of 2 drops/sec using a constant pressure dropping funnel and reacted for 2 hours.
(5) And obtaining the soft nano microsphere emulsion after the reaction is finished.
Example 4
A flexible photonic crystal element nano microsphere is prepared from the following raw materials: 0.1g of SDBS, 20g of styrene, 2.5g of divinylbenzene, 20g of hydroxyethyl acrylate, 15g of hydroxyethyl methacrylate, 0.3g of allyl methacrylate, 1.65g of potassium persulfate and 300mL of water.
A preparation method of flexible photonic crystal element nano microspheres comprises the following specific steps:
(1) the inner hard monomer, the inner crosslinking agent, the outer hard monomer and the outer crosslinking agent were washed and purified, respectively, and then subjected to a drying pretreatment in the same manner as in example 1.
(2) 0.1g of emulsifier SDBS and 300mL of water are added into a reactor, the mechanical stirring speed is 400r/min, and the temperature is increased to 80 ℃.
(3) 20g of styrene and 2.5g of divinylbenzene were added to the reactor and the monomer was protected by continuous argon. After stirring for 15min, 1.65g of potassium persulfate was added to initiate polymerization, and the reaction time was kept at 50 min.
(4) After 20g of hydroxyethyl acrylate, 15g of hydroxyethyl methacrylate and 0.3g of allyl methacrylate were uniformly mixed, the mixture was added dropwise into the reactor at a rate of 2 drops/sec using a constant pressure dropping funnel and reacted for 3 hours.
(5) And obtaining the soft nano microsphere emulsion after the reaction is finished.
Example 5
A flexible photonic crystal element nano microsphere is prepared from the following raw materials: 0.14g of SDBS, 24g of methacrylic acid, 2.4g of divinylbenzene, 25g of butyl acrylate, 10g of methyl methacrylate, 0.35g of allyl methacrylate, 0.55g of ammonium persulfate and 300mL of water.
A preparation method of flexible photonic crystal element nano microspheres comprises the following specific steps:
(1) the inner hard monomer, the inner crosslinking agent, the outer hard monomer and the outer crosslinking agent were washed and purified, respectively, and then subjected to a drying pretreatment in the same manner as in example 1.
(2) 0.14g of emulsifier SDBS and 300mL of water are added into a reactor, the mechanical stirring speed is 250r/min, and the temperature is increased to 75 ℃.
(3) 24g of methacrylic acid and 2.4g of divinylbenzene were introduced into the reactor and the monomers were protected by continuous argon. Stirring for 20min, adding 0.55g ammonium persulfate to initiate polymerization, and keeping the temperature for 40 min.
(4) After 25g of butyl acrylate, 10g of methyl methacrylate and 0.035g of allyl methacrylate were mixed uniformly, they were added dropwise to the reactor at a rate of 2 drops/sec for 4 hours using a constant pressure dropping funnel.
(5) And obtaining the soft nano microsphere emulsion after the reaction is finished.
Example 6
A flexible photonic crystal element nano microsphere is prepared from the following raw materials: 0.1g of SDBS, 20g of styrene, 1g of divinylbenzene, 25g of ethyl acrylate, 10g of acrylic acid, 15g of methyl methacrylate, 0.1g of ethylene glycol dimethacrylate, 0.7g of potassium persulfate and 300mL of water.
A preparation method of flexible photonic crystal element nano microspheres comprises the following specific steps:
(1) the inner hard monomer, the inner crosslinking agent, the outer hard monomer and the outer crosslinking agent were washed and purified, respectively, and then subjected to a drying pretreatment in the same manner as in example 1.
(2) 0.1g of emulsifier SDBS and 300mL of water are added into a reactor, the mechanical stirring speed is 250r/min, and the temperature is increased to 90 ℃.
(3) 20g of styrene and 1g of divinylbenzene were added to the reactor and the monomer was protected by continuous argon. After stirring for 20min, 0.7g of potassium persulfate is added to initiate polymerization, and the reaction time is kept at 40 min.
(4) After 25g of ethyl acrylate, 10g of acrylic acid, 15g of methyl methacrylate and 0.1g of ethylene glycol dimethacrylate were uniformly mixed, they were added dropwise to the reactor at a rate of 2 drops/sec for 2 hours using a constant pressure dropping funnel.
(5) And obtaining the soft nano microsphere emulsion after the reaction is finished.
The particle size distribution of the soft nanospheres of examples 1 and 2 is shown in figure 1. As can be seen from FIG. 1, the nanoparticles with different particle sizes can be obtained by adjusting the dosages of the emulsifier and the initiator, and the particle size distribution is concentrated and the peak is sharp, so that the nanoparticles have good monodispersity. The stress-strain curves of the photonic crystal films obtained by self-assembling the soft nano-microspheres prepared in examples 1 and 4 are shown in fig. 2, which can illustrate that the hardness and softness of the nano-microspheres can be adjusted by the action of the outer layer cross-linking agent, so as to obtain strong and tough photonic crystal films, and when the amount of the outer layer cross-linking agent is increased, the degree of cross-linking network formed by the copolymerization of the outer layer monomers is large, so that the formed films are hard and brittle. SEM photographs of the nanospheres prepared in example 2 and example 3 are shown in fig. 3 and 4. The SEM photograph of the three-dimensional photonic crystal structure obtained by self-assembling the nano-microspheres prepared in example 5 is shown in FIG. 5, and it can be observed from FIG. 5 that the soft nano-microspheres are taken as elements to prepare continuous three-dimensional photonic crystals with highly ordered structures. The structural color film photo of the nano-microsphere prepared in the examples 1 and 2 and 3 by self-assembly is shown in fig. 6, which can form independent film and has vivid color. The bending test of the structural color film obtained by self-assembling the nano microspheres in example 1 is shown in fig. 7, and it can be seen that the structural color film does not damage the structure after being bent, and has good structural stability.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (10)
1. A flexible photonic crystal element nano microsphere is characterized in that the nano microsphere is prepared from the following raw materials in percentage by weight:
0.02-0.04 wt% of emulsifier,
4-7 wt% of inner hard monomer,
an inner layer cross-linking agent, wherein the inner layer cross-linking agent accounts for 5-15 wt% of the hard monomer content of the inner layer,
9 to 15 weight percent of outer layer monomer,
an outer layer cross-linking agent, wherein the outer layer cross-linking agent accounts for 0.1-1 wt% of the outer layer monomer content,
the initiator is 1-3 wt% of the total amount of the inner layer hard monomer and the outer layer monomer;
the balance being water.
2. The flexible photonic crystal-based nanosphere of claim 1, wherein: the inner layer cross-linking agent is divinylbenzene or ethylene glycol dimethacrylate.
3. The flexible photonic crystal-based nanosphere of claim 1, wherein: the outer-layer cross-linking agent is one or more of allyl methacrylate, N-methylene bisacrylamide or ethylene glycol dimethacrylate.
4. The flexible photonic crystal-based nanosphere of claim 1, wherein: the inner hard monomer is one of styrene, methyl methacrylate or methacrylic acid; the outer layer monomer is copolymerized by one or more of soft monomers and hard monomers; the soft monomer is selected from butyl acrylate, hydroxyethyl acrylate, ethyl acrylate or isooctyl acrylate, and the hard monomer is selected from acrylic acid, methacrylic acid, methyl methacrylate, methyl acrylate or hydroxyethyl methacrylate.
5. The flexible photonic crystal-based nanosphere of claim 1, wherein: the emulsifier is one or two of Sodium Dodecyl Sulfate (SDS) or Sodium Dodecyl Benzene Sulfonate (SDBS); the initiator is one or more of potassium persulfate, sodium persulfate or ammonium persulfate.
6. The flexible photonic crystal-based nanosphere of claim 4, wherein: the hard monomer in the outer layer monomer: the weight ratio of the soft monomers is 1: 1-5.
7. A method for preparing the flexible nano-microsphere with photonic crystal elements as claimed in claim 1, wherein the method comprises the following steps:
(1) respectively washing and purifying the inner hard monomer, the inner cross-linking agent, the outer monomer and the outer cross-linking agent, and then carrying out drying pretreatment;
(2) firstly, adding an emulsifier and water into a reactor, mechanically stirring uniformly, and heating to 70-90 ℃;
(3) adding an inner-layer hard monomer and an inner-layer cross-linking agent into the reactor in the step (2), introducing inert gas to protect a reaction monomer, uniformly stirring, adding an initiator to initiate polymerization reaction, and keeping the temperature of 70-90 ℃ for polymerization reaction till the reaction is complete;
(4) slowly adding an outer-layer monomer and an outer-layer cross-linking agent into the reactor in the step (3) to react for 2-4 hours;
(5) and obtaining the soft nano microsphere emulsion after the reaction is finished.
8. The method of claim 7, wherein: in the step (1), the washing alkali liquor is one or a mixture of sodium hydroxide or potassium hydroxide aqueous solution with the mass concentration of 5-10 wt%; the alkaline alumina for purification is selected from one or a mixture of 100-200 meshes, 200-300 meshes or 300-400 meshes; the desiccant is one or more of anhydrous calcium chloride, anhydrous magnesium sulfate and anhydrous calcium sulfate.
9. The method of claim 7, wherein: in the step (2), the rotation speed of the mechanical stirring is 200-500 rmp, and the time is 10-20 min.
10. The method of claim 7, wherein: in the step (3), the inert gas is nitrogen or argon, and the polymerization reaction time is 30-60 minutes.
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