CN110835530A - Reversible light modulation and control fluorescent liquid crystal nano particle and reversible light modulation and control color fluorescent ink - Google Patents

Reversible light modulation and control fluorescent liquid crystal nano particle and reversible light modulation and control color fluorescent ink Download PDF

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CN110835530A
CN110835530A CN201810930147.9A CN201810930147A CN110835530A CN 110835530 A CN110835530 A CN 110835530A CN 201810930147 A CN201810930147 A CN 201810930147A CN 110835530 A CN110835530 A CN 110835530A
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郭金宝
李洁
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Beijing University of Chemical Technology
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Abstract

Hair brushThe reversible light-control fluorescent liquid crystal nanoparticles are prepared by a miniemulsion polymerization method, and comprise a stilbene structural monomer, a nematic liquid crystal monomer and a diarylethene compound which are uniformly mixed in the presence of a first organic solvent to obtain a liquid crystal mixture; mixing a thermal initiator, a stabilizer and the liquid crystal mixture to obtain an oil phase, mixing an emulsifier and water to obtain a water phase, and mixing and emulsifying the oil phase and the water phase to obtain a coarse emulsion; performing ultrasonic homogenization on the crude emulsion to obtain a fine emulsion; in the presence of protective gas, deoxidizing the miniemulsion, and then heating and polymerizing to obtain the reversible light-control fluorescent liquid crystal nanoparticles; wherein the cyanostilbene structural monomer is shown as a general formula I, M1Is R1、R2、R3Or R4A group shown, M2Selected from the group shown in formula II or formula III, n is an integer of 1-9;

Description

Reversible light modulation and control fluorescent liquid crystal nano particle and reversible light modulation and control color fluorescent ink
Technical Field
The invention belongs to the field of liquid crystal nanoparticle materials, and particularly relates to a reversible light control fluorescent liquid crystal nanoparticle and reversible light control color fluorescent ink.
Background
The liquid crystal is an intermediate phase between liquid and crystal, and generally, the liquid crystal has a slender and rigid molecular structure, so that the liquid crystal has a certain orientation in the arrangement of the liquid crystal molecules, and the liquid crystal has both the fluidity and the continuity of the liquid and the orderliness and the anisotropy of the crystal. The liquid crystal material has unique optical performance due to unique structure and characteristics, and the arrangement of liquid crystal molecules is easy to change under the action of external stimulation.
Under specific process conditions, liquid crystal materials are prepared into liquid crystal particles with the particle size less than or equal to 100nm, and the liquid crystal particles are called Liquid Crystal Nanoparticles (LCNPs). The microsphere has the characteristics of (1) easy preparation, particle size of 100nm or even smaller, monodisperse nano microsphere structure, (2) low toxicity, (3) good stability, (4) easy observation under specific conditions and the like. Based on the characteristics, the liquid crystal nanoparticles are expected to be applied to delivery of drugs and the like in organisms, storage, reproduction, visualization and the like of information.
Fluorescent materials can be widely applied to various aspects of production and life, such as: in agriculture, an agricultural light conversion film can be prepared, ultraviolet light which is not beneficial to the growth of crops is converted into red-orange light which is suitable for the growth of the crops, and the effect of increasing the yield is achieved; the color-changing agent can be industrially used for anti-counterfeiting printing, and can change color under the stimulation of external light; in the aspect of medical treatment, the fluorescent probe can be used as a fluorescent marker of biological molecules, and further can be used for the aspects of drug delivery and the like. However, the traditional organic fluorescent material [1] has the defects of short fluorescence life, easy photolysis and fading, most of photolysis products are toxic and harmful, and the like, so that the application of the organic fluorescent material is limited. The organic fluorescent material with the cyanostilbene structure is an organic material with a conjugated structure, has the advantages of strong fluorescence capability, easily modified structure, easily adjusted optical functional property, low toxicity, environmental protection and stable fluorescence, and avoids the fluorescence quenching effect (ACQ) of some linear organic conjugated fluorescent materials. Cyano-substituted stilbene-based derivatives, referred to as cyanostilbene-or cyanostilbene-based derivatives, have an aggregation-induced enhanced fluorescence (AIEE) property, and in general, fluorescent organic compounds have a much higher fluorescence intensity in dilute solution than in the solid or aggregated state due to a large number of non-radiative deactivations resulting from strong intermolecular interactions, while aggregation-induced enhanced luminescence (AIEE) compounds are the opposite. Their derivatives have very high fluorescence quantum yields in the solid state or in the aggregated state.
A diarylethene compound with a photoisomerization reaction is designed and synthesized by Jiangyanghao et al in 1988 on the basis of stilbene, and is a compound with the photoisomerization reaction, the compound can carry out ring opening and closing reaction under the condition of illumination to generate the conversion of isomers, and energy resonance transfer in molecules or among molecules occurs in the process, the compound has different performances in the aspects of photoabsorption property, color, conductivity, fluorescence, phosphorescence emission and the like, and the molecules keep good stability under the open-loop state or the closed-loop state.
Therefore, it is necessary to provide fluorescent liquid crystal nanoparticles.
Disclosure of Invention
The invention aims to provide fluorescent liquid crystal nano particles, and further provides color fluorescent ink capable of carrying out backlight regulation and control by 365nm ultraviolet-visible light.
In order to achieve the above object, one aspect of the present invention provides a reversible light-controllable fluorescent liquid crystal nanoparticle, which is prepared by a miniemulsion polymerization method, and specifically includes the following steps:
(1) in the presence of a first organic solvent, uniformly mixing a cyanostilbene structural monomer, a nematic liquid crystal monomer and a diarylethene compound to obtain a liquid crystal mixture;
(2) mixing a thermal initiator, a stabilizer and the liquid crystal mixture to obtain an oil phase, mixing an emulsifier and water to obtain a water phase, and mixing and emulsifying the oil phase and the water phase to obtain a coarse emulsion;
(3) carrying out ultrasonic homogenization on the coarse emulsion to obtain a fine emulsion;
(4) heating and polymerizing the miniemulsion in the presence of protective gas to obtain liquid crystal nanoparticles;
wherein the cyanostilbene structural monomer is shown as a general formula I, M1Is R1、R2、R3Or R4A group shown, M2Selected from the group shown in formula II or formula III, n is an integer of 1-9;
Figure BDA0001766389860000031
in another aspect of the present invention, there is provided a reversible light-controllable color fluorescent ink, comprising, based on the total weight of the reversible light-controllable color fluorescent ink: 3-10 wt% of the above-mentioned reversible light control fluorescent liquid crystal nano particle, 2-6 wt% of film forming agent, 5-45 wt% of water-soluble organic solvent, 2-4 wt% of emulsifying agent, 0.1-2 wt% of pH regulator and 0-70 wt% of water, and the sum of all the components is 100 wt%.
The technical scheme of the invention has the following advantages:
the invention provides a novel polymerizable stilbene structure monomer, which can respectively obtain red, blue and green fluorescent light under the excitation of ultraviolet light;
the fluorescent liquid crystal nano particle can perform reversible regulation and control on the fluorescence intensity under the alternate irradiation of ultraviolet light and visible light;
the fluorescent liquid crystal nano particles can be used for preparing colored fluorescent ink, and reversible change of a fluorescent image written with information from hidden to displayed can be realized after ink-jet printing.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
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The above and other objects, features and advantages of the present invention will become more apparent by describing in more detail exemplary embodiments thereof with reference to the attached drawings, in which like reference numerals generally represent like parts throughout.
FIG. 1 shows a scanning electron micrograph of a reversible light-controllable fluorescent liquid crystal nanoparticle according to one embodiment of the present invention.
FIG. 2a is a schematic diagram showing fluorescence emission spectra of reversible light-controllable fluorescent liquid crystal nanoparticles under 365nm UV lamp with power of 2mW in time according to one embodiment of the invention. In the figure, the curves from top to bottom represent fluorescence emission spectra at 0s, 5s, 10s, 15s, 20s, 25s, and 30s, respectively.
FIG. 2b is a schematic diagram showing the fluorescence emission spectrum of the reversible light-controllable fluorescent liquid crystal nanoparticles under irradiation of a visible light source as a function of time according to one embodiment of the present invention. Wherein the curves from bottom to top in the figure represent fluorescence emission spectra at 10s, 20s, 30s, 40s, 50s, 60s, 70s, 80s, 90s, 110s, respectively.
FIG. 3 is a schematic diagram showing the time-dependent change of the fluorescence intensity limit value of the reversible light-controllable fluorescent liquid crystal nanoparticles under the alternate irradiation of the ultraviolet-visible light source according to one embodiment of the invention.
Fig. 4 is a graph showing the change of fluorescence intensity of a pattern printed on printing paper by an inkjet printing technology using reversible light-controlled color fluorescent ink under alternate irradiation of ultraviolet-visible light according to an embodiment of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
The invention provides a reversible light control fluorescent liquid crystal nano particle, which is prepared by a miniemulsion polymerization method and specifically comprises the following steps:
(1) in the presence of a first organic solvent, uniformly mixing a cyanostilbene structural monomer, a nematic liquid crystal monomer and a diarylethene compound to obtain a liquid crystal mixture;
(2) mixing a thermal initiator, a stabilizer and the liquid crystal mixture to obtain an oil phase, mixing an emulsifier and water to obtain a water phase, and mixing and emulsifying the oil phase and the water phase to obtain a coarse emulsion;
(3) carrying out ultrasonic homogenization on the coarse emulsion to obtain a fine emulsion;
(4) heating and polymerizing the miniemulsion in the presence of protective gas to obtain liquid crystal nanoparticles;
wherein the cyanostilbene structural monomer is shown as a general formula I, M1Is R1、R2、R3Or R4A group shown, M2Selected from the group shown in formula II or formula III, n is an integer of 1-9;
Figure BDA0001766389860000051
Figure BDA0001766389860000061
the fluorescent liquid crystal nanoparticles are prepared by a miniemulsion polymerization method, and the composition of the cyanostilbene structural monomer, the diarylethene compound and the nematic liquid crystal monomer is encapsulated in the nanoparticles.
In the invention, the fluorescence wave band of the cyanogen stilbene structural monomer can be changed through the change of self molecular conjugate structure and aggregation state, and the cyanogen stilbene monomer with different fluorescence colors on the macroscopic scale can be obtained through the molecular structure design.
In the invention, a diarylethene compound is introduced into a fluorescent liquid crystal nanoparticle system, the compound can perform ring opening and closing reaction under the illumination condition, reversible regulation and control of fluorescence can be realized through energy resonance transfer effect (FRET) between the diarylethene compound and a monomer with a cyanostilbene structure, the compound can be used as a fluorescent molecular switch to realize reversible regulation and control of fluorescent liquid crystal nanoparticles, namely, the diarylethene compound performs ring opening and closing reaction through alternate irradiation of UV-Vis light (ultraviolet-visible light), and performs energy resonance transfer with the monomer with the cyanostilbene structure, so that reversible change of fluorescence is generated.
According to the invention, preferably, the monomer with a structure of the stilbene structure is selected from one or more compounds with a structure shown as general formulas a-1, a-2, a-3, a-4 and a-5, wherein n is an integer of 1-9;
Figure BDA0001766389860000071
Figure BDA0001766389860000081
according to the present invention, preferably, the preparation method of the cyanostilbene structural monomer is selected from the first preparation method, the second preparation method or the third preparation method;
wherein the first preparation method comprises the following steps:
(1) carrying out contact reaction on a compound I and a compound II in the presence of a second organic solvent, a first alkaline regulator and a first catalyst to obtain a compound III;
(2) in the presence of a third organic solvent and a second alkaline regulator, carrying out contact reaction on the compound III and the compound IV, and evaporating the solvent to obtain a compound V;
(3) in the presence of a fourth organic solvent and an acid-binding agent, carrying out contact reaction on the compound V and acryloyl chloride to prepare the stilbene structural monomer;
the second preparation method comprises the following steps:
(1) in the presence of a fifth organic solvent and a third alkaline regulator, carrying out contact reaction on the compound VI and the compound VII to obtain a compound VIII;
(2) in the presence of a sixth organic solvent and a second catalyst, carrying out contact reaction on the compound VIII and DMF to obtain a compound IX;
(3) carrying out contact reaction on the compound X and NBS in the presence of a seventh organic solvent to obtain a compound XI;
(4) carrying out contact reaction on the compound XI and the compound XII in the presence of an eighth organic solvent, a ninth organic solvent, a third catalyst and an aqueous solution of Na2CO3 to obtain a compound XIII;
(5) carrying out contact reaction on a compound XIII and a compound XIII in the presence of a second organic solvent, a first alkaline regulator and a first catalyst to obtain a compound XIV;
(6) in the presence of a third organic solvent and a second basic regulator, carrying out contact reaction on the compound XIV and the compound IX, and evaporating the solvent to obtain a compound XV;
(7) in the presence of a fourth organic solvent and an acid-binding agent, carrying out contact reaction on the compound XV and acryloyl chloride to prepare the stilbene structural monomer;
the third preparation method comprises the following steps:
(1) carrying out contact reaction on the compound X and NBS in the presence of a seventh organic solvent to obtain a compound XI;
(2) in an eighth organic solvent, a ninth organic solvent, a third catalyst and Na2CO3In the presence of an aqueous solution, the compounds XI and XIPerforming contact reaction on the compound XII to obtain a compound XIII;
(3) carrying out contact reaction on a compound XIII and a compound XIII in the presence of a second organic solvent, a first alkaline regulator and a first catalyst to obtain a compound XIV;
(4) in the presence of a third organic solvent and a second alkaline regulator, carrying out contact reaction on the compound XIV and the compound IV, and evaporating the solvent to obtain a compound XVI;
(5) in the presence of a fourth organic solvent and an acid-binding agent, carrying out contact reaction on the compound XVI and acryloyl chloride to prepare the stilbene structural monomer;
the structural formula of the compound I is as follows:
Figure BDA0001766389860000091
the structural formula of the compound II is as follows:
Figure BDA0001766389860000092
wherein n is an integer of 1 to 9, and X is selected from a bromine atom or an iodine atom;
the structural formula of the compound III is
Wherein n is an integer of 1 to 9;
the structural formula of the compound IV is as follows:
Figure BDA0001766389860000094
wherein R is selected from the group consisting of the R1、R2、R3Or R4The structural group shown in the specification,
the structural formula of the compound V is as follows:
in the formulaN is an integer of 1 to 9; the structural formula of the compound VI is as follows:
Figure BDA0001766389860000102
the structural formula of the compound VII is as follows:
Figure BDA0001766389860000103
the structural formula of the compound VIII is as follows:
Figure BDA0001766389860000104
the structural formula of the compound IX is as follows:
Figure BDA0001766389860000105
the compound X has the structural formula:
Figure BDA0001766389860000106
the compound XI has a structural formula as follows:
the structural formula of the compound XII is as follows:
Figure BDA0001766389860000108
the compound XIII has the structural formula:
Figure BDA0001766389860000111
the compound xiv has the structural formula:
Figure BDA0001766389860000112
wherein n is an integer of 1 to 9;
the compound XV has the structural formula:
Figure BDA0001766389860000113
wherein n is an integer of 1 to 9.
The compound XVI has the structural formula:
Figure BDA0001766389860000114
wherein n is an integer of 1 to 9.
According to the present invention, it is preferable that,
the reaction conditions of the steps in the first preparation method include the following:
in the step (1): the first alkaline regulator is anhydrous potassium carbonate, and the first catalyst is potassium iodide; the molar ratio of the compound I to the compound II to the anhydrous potassium carbonate to the potassium iodide is 1:3-10: 0.1-1, wherein the second organic solvent is a polar organic solvent, and the second organic solvent is preferably at least one of dimethylformamide, acetonitrile, tetrahydrofuran and acetone, and is further preferably acetone; the temperature of the contact reaction is 30-80 ℃, and the time is 12-24 h; as a preferable scheme, after the reaction is finished, the compound III can be obtained by washing with water, separating liquid, evaporating to remove an organic phase solvent and then purifying by column chromatography;
in the step (2): the second basic regulator is potassium tert-butoxide; the molar ratio of the compound III to the compound IV to the potassium tert-butoxide is 2-3: 1: 0.1-0.5, the temperature of the contact reaction is 30-80 ℃, and the time is 2-8 h; as a preferred scheme, after the reaction is finished, adding hydrochloric acid for neutralization to change the system into acidity, and performing suction filtration, cleaning and drying to obtain a compound V; the third organic solvent is ethanol;
in the step (3): the acid-binding agent is triethylamine; the molar ratio of the compound V to the acryloyl chloride to the triethylamine is 1: 3-4: 3-5, wherein the temperature of the contact reaction is 0-40 ℃, and the time is 12-24 h; as a preferred scheme, after the reaction is finished, adding water to quench the reaction, separating and drying, evaporating to remove an organic phase solvent, and then purifying by column chromatography to obtain the stilbene structural monomer; the fourth organic solvent is chloroform;
the reaction conditions of the steps in the second preparation method include the following:
in the step (1): the third alkaline regulator is NaH or NaOH; the molar ratio of the compound VI to the compound VII to the third basic regulator is 1: 1-3: 1-10, wherein the temperature of the contact reaction is 0-40 ℃, and the time is 1-2 hours; preferably, the fifth organic solvent is dimethyl sulfoxide; preferably, after the reaction is finished, the compound VIII can be obtained by washing with water, separating liquid, evaporating to remove the organic phase solvent and then purifying by column chromatography;
in the step (2): the molar ratio of the compound VIII to the DMF to the second catalyst is 1:2-5:0.1-1, the first catalyst is POCl3, the temperature of the contact reaction is 30-70 ℃, and the time is 12-24 h; preferably, after the reaction is finished, the compound IX can be obtained by washing with water, separating liquid, evaporating to remove the organic phase solvent and then purifying by column chromatography; the sixth organic solvent is dichloromethane;
in the step (3): the molar ratio of the compound X to the NBS is 1: 1-3, wherein the temperature of the contact reaction is 0-40 ℃, and the time is 1-5 h; preferably, the seventh organic solvent is N, N-dimethylformamide;
in the step (4): the molar ratio of the compound XI to the compound XII to the second catalyst is 1: 1-3: 0.1-1 percent, wherein the mass fraction of the Na2CO3 aqueous solution is 10-30 percent; preferably, the second catalyst is palladium tetratriphenylphosphine; preferably, the eighth organic solvent is tetrahydrofuran, and the ninth organic solvent is methanol;
the step (5) comprises the following steps: the first alkaline regulator is anhydrous potassium carbonate, and the first catalyst is potassium iodide; the molar ratio of the compound XIII to the compound II to the anhydrous potassium carbonate to the potassium iodide is 1:3-10: 0.1-1, wherein the second organic solvent is a polar organic solvent, preferably at least one of dimethylformamide, acetonitrile, tetrahydrofuran and acetone, and further preferably acetone; the temperature of the contact reaction is 30-80 ℃, and the time is 12-24 h; preferably, after the reaction is finished, the compound XIV can be obtained by washing with water, separating liquid, evaporating to remove the organic phase solvent and then purifying by column chromatography;
the step (6) comprises the following steps: the second basic regulator is potassium tert-butoxide; the molar ratio of the compound XIV to the compound IX to the potassium tert-butoxide is 2-4: 1: 0.2-1, wherein the temperature of the contact reaction is 30-80 ℃, and the time is 2-8 hours; as a preferred scheme, after the reaction is finished, adding hydrochloric acid for neutralization to change the system into acidity, and performing suction filtration, cleaning and drying to obtain a compound XV; the third organic solvent is ethanol;
the step (7) comprises the following steps: the third alkaline regulator is triethylamine; the molar ratio of the compound XV, acryloyl chloride and triethylamine is 1: 3-4: 3-5, wherein the temperature of the contact reaction is 0-40 ℃, and the time is 12-24 h. As a preferred scheme, after the reaction is finished, adding water to quench the reaction, separating and drying, evaporating to remove an organic phase solvent, and then purifying by column chromatography to obtain the stilbene structural monomer; the fourth organic solvent is chloroform;
the reaction conditions of the steps in the third preparation method include the following:
in the step (1): the molar ratio of the compound X to the NBS is 1: 1-3, wherein the temperature of the contact reaction is 0-40 ℃, and the time is 1-5 h;
in the step (2): the molar ratio of the compound XI to the compound XII to the second catalyst is 1: 1-3: 0.1-1, Na2CO3The mass fraction of the aqueous solution is 10-30%;
in the step (3): the first alkaline regulator is anhydrous potassium carbonate, the first catalyst is potassium iodide, and the molar ratio of the compound XIII to the compound II to the anhydrous potassium carbonate to the potassium iodide is 1:3-10: 0.1-1, wherein the second organic solvent is a polar organic solvent, the temperature of the contact reaction is 30-80 ℃, and the time is 12-24 h;
in the step (4): the second basic regulator is potassium tert-butoxide; the molar ratio of the compound XIV to the compound IV to the potassium tert-butoxide is 2-4: 1: 0.2-1, wherein the temperature of the contact reaction is 30-80 ℃, and the time is 2-8 h;
in the step (5): the acid-binding agent is triethylamine; the molar ratio of said compound xvii to acryloyl chloride is 1: 3-4: 3-5, wherein the temperature of the contact reaction is 0-40 ℃, and the time is 12-24 h.
According to the present invention, preferably, the diarylethene compound has a structure shown as general formula IV, and is a ring-opening or ring-closing structure; wherein, X1、X2Each independently selected from R5、R6、R7、R8、R9Or R10Structural group shown, X1、X2The same or different;
Figure BDA0001766389860000151
according to the present invention, preferably, the diarylethene compound is selected from one or more diarylethene compounds having a structure represented by general formula b-1, b-2, b-3, b-4, b-5; and the following general structures are open-loop or closed-loop structures.
Figure BDA0001766389860000152
Figure BDA0001766389860000161
According to the present invention, preferably, the nematic liquid crystal monomer is at least one of C4M, C6M, and C8M.
According to the invention, preferably, in the preparation method of the reversible light-modulation fluorescent liquid crystal nanoparticle: in the step (1): the mass ratio of the nematic liquid crystal monomer to the cyanostilbene structural monomer is 70-200: 1; the mass ratio of the diarylethene compound to the cyanostilbene structural monomer is 1-9: 1; the first organic solvent is dichloromethane and/or chloroform, and the mass ratio of the first organic solvent to the nematic liquid crystal monomer is (2-10): 1;
in the step (2): based on the total weight of the mixture of the cyanostilbene structural monomer and the nematic liquid crystal monomer, the content of the thermal initiator is 0.1 to 2 weight percent, and the content of the stabilizer is 1 to 10 weight percentThe addition amount of the emulsifier is 10-20 wt%; the volume ratio of water to the first organic solvent is 30-50: 1, the emulsifier is Sodium Dodecyl Sulfate (SDS) or 11- (acryloyloxy) sodium undecanoate (AC)10COONa), wherein the thermal initiator is at least one of Azobisisobutyronitrile (AIBN), Azobisisovaleronitrile (AMBN) and Benzoyl Peroxide (BPO), the stabilizer is at least one of Cetyl Alcohol (CA), n-Hexadecane (HD), Stearyl Methacrylate (SMA) and Stearyl Acrylate (SA), and the emulsifying time is 1-6 h;
in the step (3): the power of the ultrasonic homogenization is 120-450W, and the time is 5-30 min;
in the step (4): the temperature of the heating polymerization is 60-80 ℃, and the time is 12-24 h.
In another aspect of the present invention, there is provided a reversible light-controllable color fluorescent ink, comprising, based on the total weight of the reversible light-controllable color fluorescent ink: 3-10 wt% of the above-mentioned reversible light control fluorescent liquid crystal nano particle, 2-6 wt% of film forming agent, 5-45 wt% of water-soluble organic solvent, 2-4 wt% of emulsifying agent, 0.1-2 wt% of pH regulator and 0-70 wt% of water, and the sum of all the components is 100 wt%.
The reversible light-control color fluorescent ink can write information on paper by an ink-jet printing method, can realize the change of a fluorescent image of the written information from hidden to displayed by the alternate irradiation of UV-Vis light, and provides important reference value for the reproduction, identification and application in the technical field of visualization of information such as printed document text content.
According to the present invention, preferably, the film forming agent is at least one of polyvinyl alcohol, aqueous polyurethane, polyethylene glycol, chitosan and gelatin; the water-soluble organic solvent is at least one of ethylene glycol, glycerol, diethylene glycol monomethyl ether, propylene glycol methyl ether and dipropylene glycol dimethyl ether; the pH regulator is ammonia water or NaHCO3、Na2CO3And triethanolamine; the emulsifier is Sodium Dodecyl Sulfate (SDS) and 11- (acryloyloxy) sodium undecanoate (AC)10COONa) and polyvinyl alcohol (PVA).
The invention is further illustrated by the following examples:
1. preparing a cyanostilbene structural monomer:
preparation example 1
(1) 3g of p-hydroxyphenylacetonitrile and 4.08g of 6-bromohexanol are taken for feeding, 6.23g of anhydrous potassium carbonate and 0.56g of potassium iodide are added, and stirring and refluxing are carried out in acetone at 60 ℃ for 12 hours. After the reaction is finished, carrying out vacuum filtration, removing filter residues, carrying out rotary evaporation on the concentrated filtrate, and then carrying out chromatographic column separation by using a mixed solution prepared by a volume ratio of chloroform to ethyl acetate of 3:1 as a solvent to obtain a compound III;
(2) adding 6.9g of compound III and 1.24g of 2, 5-dialdehyde furan into ethanol, stirring, dissolving, adding 0.22g of equivalent weight of potassium tert-butoxide to make the system be strong alkaline, stirring and refluxing at 70 ℃ for 4h, then adding about 1ml of hydrochloric acid for neutralization to make the system become acidic, carrying out vacuum filtration, cleaning filter residue with ethanol, and drying the filter residue in a vacuum oven to obtain compound V;
(3) adding 5.5g of a compound V, 2.7g of acryloyl chloride and 4.4g of triethylamine into trichloromethane, then transferring to a normal-temperature environment, stirring for 12h, adding 50ml of water to quench the reaction after the reaction is completed, separating by using a separating funnel, taking a lower organic phase, adding anhydrous sodium sulfate to dry, standing for 12h in a dark place, carrying out rotary evaporation to concentrate the organic phase, and then carrying out chromatographic column separation by using a mixed solution prepared by a volume ratio of trichloromethane to ethyl acetate of 15:1 as a solvent to obtain the stilbene structural monomer with the structure shown in the compound 1 in the table 1.
Preparation example 2
(1) The compound I was charged with an initial mass of 3g, 4.08g of 6-bromohexanol, and 6.23g of anhydrous potassium carbonate and 0.56g of potassium iodide were added, followed by stirring and refluxing in acetone at 60 ℃ for 12 hours. After the reaction is finished, carrying out vacuum filtration, removing filter residues, carrying out rotary evaporation on the concentrated filtrate, and then carrying out chromatographic column separation by using a mixed solution prepared by a volume ratio of chloroform to ethyl acetate of 3:1 as a solvent to obtain a compound III;
(2) adding 6.9g of compound III and 1.3g of terephthalaldehyde into ethanol, stirring, adding 0.22g of potassium tert-butoxide after dissolution to make the system be strongly alkaline, stirring and refluxing for 4 hours at 70 ℃, then adding about 1ml of hydrochloric acid for neutralization to make the system become acidic, performing vacuum filtration, cleaning filter residue with ethanol, and drying the filter residue in a vacuum oven to obtain a compound V, wherein n is 6;
(3) adding compound V5.6g, acryloyl chloride 2.7g and triethylamine 4.4g into trichloromethane, then transferring to a normal temperature environment, stirring for 12h, adding 50ml of water to quench the reaction after the reaction is completed, separating by using a separating funnel, taking a lower organic phase, adding anhydrous sodium sulfate to dry, standing for 12h in a dark place, carrying out rotary evaporation to concentrate the organic phase, and then carrying out chromatographic column separation by using a mixed solution prepared by a volume ratio of trichloromethane to ethyl acetate of 15:1 as a solvent to obtain the stilbene structural monomer with the structure shown in the compound 2 in the table 1.
Preparation example 3
(1) Adding 2.0g of a compound VI, 1.2g of 1-bromopropane and 0.24g of NaH into dimethyl sulfoxide, reacting for 1h at room temperature, performing rotary evaporation and concentration after the reaction is finished, and performing chromatographic column separation by using a mixed solution prepared by a volume ratio of chloroform to ethyl acetate of 3:1 as a solvent to obtain a compound VIII;
(2) 2.5g of compound VIII, 2.5g of anhydrous DMF2.5g and POCl3Adding 0.15g of the mixture into dichloromethane, reacting for 12 hours at 50 ℃, washing with water after the reaction is finished, concentrating an organic phase by rotary evaporation, and then performing chromatographic column separation by using a mixed solution prepared by a volume ratio of chloroform to ethyl acetate of 3:1 as a solvent to obtain a compound IX;
(3) reacting 1.23g of compound X with 1.8g of NBS1 in DMF at room temperature for 3h, washing with water after the reaction is finished, extracting with dichloromethane, concentrating an organic phase by rotary evaporation, and performing chromatographic column separation by using dichloromethane as a solvent to obtain a compound XI;
(4) 2g of the compound XI, 1.4g of the compound XII and 0.9g of palladium tetratriphenylphosphine were added to THF, methanol and NaCO3Reacting in a mixed solution of an aqueous solution at the temperature of 80 ℃ for 24 hours, washing a product after the reaction with water, extracting with ethyl acetate, concentrating, and performing chromatographic column separation by using a mixed solution prepared by using a volume ratio of dichloromethane to ethyl acetate of 1:2 as a solvent to obtain XIII;
(5) 2.2g of the compound XIII and 1.8g of 6-bromohexanol were charged, and 2.8g of anhydrous potassium carbonate and 0.33g of potassium iodide were added, followed by stirring and refluxing in acetone at 60 ℃ for 12 hours. After the reaction is finished, carrying out vacuum filtration, removing filter residues, carrying out rotary evaporation on the concentrated filtrate, and then carrying out chromatographic column separation by using a mixed solution prepared by the volume ratio of chloroform to ethyl acetate of 3:1 as a solvent to obtain a compound XIV;
(6) adding 6.3g of compound XIV and 3.0g of compound IX into ethanol, stirring, dissolving, adding 0.22g of potassium tert-butoxide to make the system be strongly alkaline, stirring and refluxing for 4h at 70 ℃, then adding about 1ml of hydrochloric acid for neutralization to make the system become acidic, carrying out vacuum filtration, cleaning the filter residue with ethanol, and placing the filter residue in a vacuum oven for drying to obtain a compound XV;
(7) adding 4.4g of compound XV, 0.9g of acryloyl chloride and 1.5g of triethylamine into trichloromethane, then transferring to a normal temperature environment, stirring for 12h, adding 50ml of water to quench and react after the reaction is completed, separating liquid by using a separating funnel, taking a lower layer organic phase, adding anhydrous sodium sulfate to dry, standing for 12h in a dark place, carrying out rotary evaporation and concentration on the organic phase, and then carrying out chromatographic column separation by using a mixed solution prepared by a volume ratio of trichloromethane to ethyl acetate of 15:1 as a solvent to obtain the cyanostilbene structural monomer with the structure shown in the compound 3 in the table 1.
TABLE 1
Figure BDA0001766389860000201
2. Preparing the reversible light-controlled fluorescent nanoparticles:
example 1
(1)0.1g C6M g, 0.001g of a stilbene structural monomer (compound 1 in Table 1) and 0.005g of BTE (structure shown by b-3) to total 0.106g of raw materials, and then adding 300 mu l of trichloromethane to fully dissolve the raw materials to obtain a liquid crystal mixture;
(2) adding 0.0018g of thermal initiator AIBN and 0.005g of stabilizer octadecyl acrylate into the liquid crystal mixture, and fully mixing to obtain an oil phase; adding an emulsifier AC10COONa0.02g into 10ml of deionized water, fully mixing to obtain a water phase, dropwise adding an oil phase into the water phase while stirring by magnetic force, and stirring for 3 hours at room temperature for emulsification to obtain a crude emulsion with an oil-in-water structure;
(3) homogenizing the coarse emulsion in an ultrasonic cell disruptor under ice bath for 15min under the power of 400w ultrasound to obtain fine emulsion;
(4) and (3) placing the miniemulsion into a three-neck flask, stirring for 15min to remove oxygen while introducing N2 and introducing water for condensation, then heating in a water bath with 70 ℃ of aqueous solution, stirring at a certain stirring speed, and reacting for 24 hours to obtain the backlight-controllable fluorescent liquid crystal nanoparticles.
3. Preparing the reversible light control color fluorescent ink:
example 2
The embodiment provides a reversible light-control color fluorescent ink, which is prepared by the following specific steps:
(1) drying the green reversible light control fluorescent liquid crystal nanoparticles prepared in the embodiment 1 in a vacuum oven to obtain a dried green fluorescent dye;
(2) weighing 5.0g of dry green fluorescent dye, 100g of polyvinyl alcohol aqueous solution with the mass concentration of 5 wt%, 30g of glycerol and 3.5g of AC10COONa, and stirring for 20min under the condition that a stirring paddle is 3000 r/min;
(3) 0.8g of Na was added2HCO3And adjusting the pH value to 8.4 to obtain the reversible light-control color fluorescent ink.
Test example 1
Scanning the reversible light-control fluorescent liquid crystal nanoparticles prepared in example 1 by an electron microscope.
As shown in FIG. 1, a distinct spherical structure can be seen, illustrating that the combination of a cyanostilbene structural monomer, a diarylethene compound, and a nematic liquid crystal monomer is encapsulated in the nanoparticles.
Test example 2
The reversible light-control fluorescent liquid crystal nanoparticles prepared in example 1 were irradiated under 365nm UV light with 2mW power and visible light, and the change of fluorescence intensity was observed.
As shown in FIG. 2a, the fluorescence intensity of the reversible light-controlled fluorescent liquid crystal nanoparticles is reduced under the irradiation of a 365nm UV lamp with the power of 2mW, and the fluorescence intensity reaches a stable value after 30 s; as shown in FIG. 2b, the fluorescence intensity of the reversible light-controllable fluorescent liquid crystal nanoparticle of the present invention recovers under the irradiation of a visible light source, and reaches a stable value after 110s, as shown in FIG. 3, the fluorescence intensity can reversibly change under multiple alternate irradiation of UV-visible light.
Test example 3
The pattern of the reversible light-control color fluorescent ink prepared in example 2 is printed by using an EPSON-L383 ink chamber type, so as to obtain the pattern shown in FIG. 4 (left); the resulting pattern was irradiated for 30s with 2mW of a 365nm wavelength Ultraviolet (UV) lamp, and the fluorescence intensity was reduced to obtain the pattern as shown in FIG. 4 (right); then the pattern is irradiated for 110s under visible light to recover the fluorescence intensity, and the pattern as shown in figure 4 (left) is obtained; therefore, the fluorescence intensity of the fluorescent ink can be reversibly changed, and the reversible light regulation can be realized.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

Claims (10)

1. The reversible light control fluorescent liquid crystal nanoparticle is characterized in that the reversible light control fluorescent liquid crystal nanoparticle is prepared by a miniemulsion polymerization method, and the method specifically comprises the following steps:
(1) in the presence of a first organic solvent, uniformly mixing a cyanostilbene structural monomer, a nematic liquid crystal monomer and a diarylethene compound to obtain a liquid crystal mixture;
(2) mixing a thermal initiator, a stabilizer and the liquid crystal mixture to obtain an oil phase, mixing an emulsifier and water to obtain a water phase, and mixing and emulsifying the oil phase and the water phase to obtain a coarse emulsion;
(3) carrying out ultrasonic homogenization on the coarse emulsion to obtain a fine emulsion;
(4) in the presence of protective gas, heating and polymerizing the miniemulsion after removing oxygen to obtain the reversible light-control fluorescent liquid crystal nanoparticles;
wherein the cyanostilbene structural monomer is shown as a general formula IShow, M1Is R1、R2、R3Or R4A group shown, M2Selected from the group shown in formula II or formula III, n is an integer of 1-9;
Figure 2
。
2. the reversible light-modulation fluorescent liquid crystal nanoparticle as claimed in claim 1, wherein the monomer with a stilbene structure is selected from one or more compounds with a stilbene structure shown in general formulas a-1, a-2, a-3, a-4 and a-5, wherein n is an integer of 1-9;
Figure FDA0001766389850000021
Figure FDA0001766389850000031
3. the reversible light-modulation fluorescent liquid crystal nanoparticle according to claim 1 or 2, wherein the preparation method of the stilbene structural monomer is selected from a first preparation method or a second preparation method;
wherein the first preparation method comprises the following steps:
(1) carrying out contact reaction on a compound I and a compound II in the presence of a second organic solvent, a first alkaline regulator and a first catalyst to obtain a compound III;
(2) in the presence of a third organic solvent and a second alkaline regulator, carrying out contact reaction on the compound III and the compound IV, and evaporating the solvent to obtain a compound V;
(3) in the presence of a fourth organic solvent and an acid-binding agent, carrying out contact reaction on the compound V and acryloyl chloride to prepare the stilbene structural monomer;
the second preparation method comprises the following steps:
(1) in the presence of a fifth organic solvent and a third alkaline regulator, carrying out contact reaction on the compound VI and the compound VII to obtain a compound VIII;
(2) in the presence of a sixth organic solvent and a second catalyst, carrying out contact reaction on the compound VIII and DMF to obtain a compound IX;
(3) carrying out contact reaction on the compound X and NBS in the presence of a seventh organic solvent to obtain a compound XI;
(4) in an eighth organic solvent, a ninth organic solvent, a third catalyst and Na2CO3Carrying out contact reaction on the compound XI and the compound XII in the presence of an aqueous solution to obtain a compound XIII;
(5) carrying out contact reaction on a compound XIII and a compound XIII in the presence of a second organic solvent, a first alkaline regulator and a first catalyst to obtain a compound XIV;
(6) in the presence of a third organic solvent and a second basic regulator, carrying out contact reaction on the compound XIV and the compound IX, and evaporating the solvent to obtain a compound XV;
(7) and in the presence of a fourth organic solvent and an acid-binding agent, carrying out contact reaction on the compound XV and acryloyl chloride to obtain the stilbene structural monomer.
Wherein the structural formula of the compound I is as follows:
Figure FDA0001766389850000041
the structural formula of the compound II is as follows:
Figure FDA0001766389850000042
wherein n is an integer of 1 to 9, and X is selected from a bromine atom or an iodine atom;
the structural formula of the compound III is
Figure FDA0001766389850000043
Wherein n is an integer of 1 to 9;
the structural formula of the compound IV is as follows:
Figure FDA0001766389850000044
wherein R is selected from the group consisting of the R1、R2、R3Or R4The structural group shown in the specification,
the structural formula of the compound V is as follows:
Figure FDA0001766389850000045
wherein n is an integer of 1 to 9;
the structural formula of the compound VI is as follows:
Figure FDA0001766389850000046
the structural formula of the compound VII is as follows:
Figure FDA0001766389850000051
the structural formula of the compound VIII is as follows:
the structural formula of the compound IX is as follows:
the compound X has the structural formula:
Figure FDA0001766389850000054
the compound XI has a structural formula as follows:
Figure FDA0001766389850000055
the structural formula of the compound XII is as follows:
Figure FDA0001766389850000056
the compound XIII has the structural formula:
Figure FDA0001766389850000057
the compound xiv has the structural formula:
Figure FDA0001766389850000061
wherein n is an integer of 1 to 9;
the compound XV has the structural formula:
Figure FDA0001766389850000062
wherein n is an integer of 1 to 9.
4. The reversible light-modulating fluorescent liquid crystal nanoparticle of claim 3,
the reaction conditions of the steps in the first preparation method include the following:
in the step (1): the first alkaline regulator is anhydrous potassium carbonate, and the first catalyst is potassium iodide; the molar ratio of the compound I to the compound II to the anhydrous potassium carbonate to the potassium iodide is 1:3-10: 0.1-1, wherein the second organic solvent is a polar organic solvent, the temperature of the contact reaction is 30-80 ℃, and the time is 12-24 h;
in the step (2): the second basic regulator is potassium tert-butoxide; the molar ratio of the compound III to the compound IV to the potassium tert-butoxide is 2-3: 1: 0.1-0.5, the temperature of the contact reaction is 30-80 ℃, and the time is 2-8 h;
in the step (3): the acid-binding agent is triethylamine; the molar ratio of the compound V to the acryloyl chloride to the triethylamine is 1: 3-4: 3-5, wherein the temperature of the contact reaction is 0-40 ℃, and the time is 12-24 h;
the reaction conditions of the steps in the second preparation method include the following:
in the step (1): the third alkaline regulator is NaH or NaOH; the molar ratio of the compound VI to the compound VII to the third basic regulator is 1: 1-3: 1-10, wherein the temperature of the contact reaction is 0-40 ℃, and the time is 1-2 hours;
in the step (2): the molar ratio of the compound VIII to the DMF to the second catalyst is 1:2-5:0.1-1, the first catalyst is POCl3, the temperature of the contact reaction is 30-70 ℃, and the time is 12-24 h;
in the step (3): the molar ratio of the compound X to the NBS is 1: 1-3, wherein the temperature of the contact reaction is 0-40 ℃, and the time is 1-5 h;
in the step (4): the molar ratio of the compound XI to the compound XII to the third catalyst is 1: 1-3: 0.1 to 1, the Na2CO3The mass fraction of the aqueous solution is 10-30%;
the step (5) comprises the following steps: the first alkaline regulator is anhydrous potassium carbonate, and the first catalyst is potassium iodide; the molar ratio of the compound XIII to the compound II to the anhydrous potassium carbonate to the potassium iodide is 1:3-10: 0.1-1, wherein the second organic solvent is a polar organic solvent, the temperature of the contact reaction is 30-80 ℃, and the time is 12-24 h;
the step (6) comprises the following steps: the second basic regulator is potassium tert-butoxide; the molar ratio of the compound XIV to the compound IX to the potassium tert-butoxide is 2-4: 1: 0.2-1, wherein the temperature of the contact reaction is 30-80 ℃, and the time is 2-8 hours;
the step (7) comprises the following steps: the acid-binding agent is triethylamine; the molar ratio of the compound XV, acryloyl chloride and triethylamine is 1: 3-4: 3-5, wherein the temperature of the contact reaction is 0-40 ℃, and the time is 12-24 h.
5. The reversible light-modulating fluorescent liquid crystal nanoparticle according to claim 1, wherein the diarylethene compound has a structure represented by general formula IV; wherein, X1、X2Each independently selected from R5、R6、R7、R8、R9Or R10Structural group shown, X1、X2The same or different；
Figure FDA0001766389850000081
6. The reversible light-modulating fluorescent liquid crystal nanoparticle according to claim 1, wherein the diarylethene compound is selected from one or more diarylethene compounds having a structure represented by general formulas b-1, b-2, b-3, b-4, and b-5;
Figure FDA0001766389850000082
Figure FDA0001766389850000091
7. the reversible light-modulating fluorescent liquid crystal nanoparticle of claim 1, wherein the nematic liquid crystal monomer is at least one of C4M, C6M, and C8M.
8. The reversible light-modulating fluorescent liquid crystal nanoparticle of claim 1,
in the step (1): the mass ratio of the nematic liquid crystal monomer to the cyanostilbene structural monomer is 70-200: 1; the mass ratio of the diarylethene compound to the cyanostilbene structural monomer is 1-9: 1; the first organic solvent is dichloromethane and/or chloroform, and the mass ratio of the first organic solvent to the nematic liquid crystal monomer is (2-10): 1;
in the step (2): based on the total weight of the mixture of the cyanostilbene structural monomer and the nematic liquid crystal monomer, the content of the thermal initiator is 0.1-2 wt%, the content of the stabilizer is 1-10 wt%, and the addition amount of the emulsifier is 10-20 wt%; the volume ratio of water to the first organic solvent is 30-50: 1, the emulsifier is sodium dodecyl sulfate or 11- (acryloyloxy) sodium undecanoate, the thermal initiator is at least one of azobisisobutyronitrile, azobisisovaleronitrile and benzoyl peroxide, the stabilizer is at least one of cetyl alcohol, n-hexadecane, stearyl methacrylate and stearyl acrylate, and the emulsifying time is 1-6 h;
in the step (3): the power of the ultrasonic homogenization is 120-450W, and the time is 5-30 min;
in the step (4): the temperature of the heating polymerization is 60-80 ℃, and the time is 12-24 h.
9. The reversible light-control color fluorescent ink is characterized by comprising the following components in percentage by weight based on the total weight of the reversible light-control color fluorescent ink: 3-10 wt% of the reversible light control fluorescent liquid crystal nano particle as claimed in any one of claims 1-8, 2-6 wt% of film forming agent, 5-45 wt% of water soluble organic solvent, 2-4 wt% of emulsifier, 0.1-2 wt% of pH regulator and 0-70 wt% of water, and the sum of the components is 100 wt%.
10. The reversible light-regulating color fluorescent ink according to claim 9, wherein the film-forming agent is at least one of polyvinyl alcohol, aqueous polyurethane, polyethylene glycol, chitosan, and gelatin; the water-soluble organic solvent is at least one of ethylene glycol, glycerol, diethylene glycol monomethyl ether, propylene glycol methyl ether and dipropylene glycol dimethyl ether; the pH regulator is ammonia water, NaHCO3, Na2CO3And triethanolamine; the emulsifier is at least one of sodium dodecyl sulfate, 11- (acryloyloxy) sodium undecanoate and polyvinyl alcohol.
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