CN115850080A - Fluorescent liquid crystal micromolecule with temperature-controlled optical texture and photoluminescence double anti-counterfeiting mechanisms and preparation method thereof - Google Patents
Fluorescent liquid crystal micromolecule with temperature-controlled optical texture and photoluminescence double anti-counterfeiting mechanisms and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a fluorescent liquid crystal micromolecule with a temperature control optical texture and photoluminescence double anti-counterfeiting mechanism and a preparation method thereof, wherein the structure of the fluorescent liquid crystal micromolecule is shown as a formula I; pyrenyl is used as a fluorescent chromophore, and pyrenyl is introduced into a liquid crystal structure through carbon chains with different chain segment lengths, so that the liquid crystal material not only maintains good liquid crystal performance, but also has the fluorescent characteristic of high color purity, and the fluorescent liquid crystal micromolecule anti-counterfeiting material is successfully prepared. The micromolecular fluorescent liquid crystal prepared by the invention can present a clear liquid crystal optical texture through temperature control, and can emit strong blue fluorescence under the excitation of 340nm ultraviolet light. The fluorescent liquid crystal micromolecule device prepared by the inventionHas clear and distinguishable temperature control optical texture and high color purity photoluminescence, and has wide application prospect in the anti-counterfeiting field.
Description
Technical Field
The invention belongs to the technical field of fluorescent liquid crystal anti-counterfeiting, and particularly relates to a fluorescent liquid crystal micromolecule with a temperature control optical texture and photoluminescence double anti-counterfeiting mechanism and a preparation method thereof.
Background
Fluorescent materials and liquid crystal materials are common anti-counterfeiting materials. The anti-counterfeiting mechanism of the fluorescent material is simple, the fluorescent material is extremely easy to copy, and the anti-counterfeiting safety is low; the liquid crystal anti-counterfeiting material is an anti-counterfeiting material with color and optical texture which can be reversibly regulated and controlled by temperature and pressure, and still faces the problem that an anti-counterfeiting mechanism is single and imitated. Fluorescent liquid crystal anti-counterfeiting materials with high safety are produced. The common fluorescent liquid crystal polymer anti-counterfeiting material is prepared by graft copolymerization of fluorescent micromolecules, liquid crystal micromolecules and polymethylhydrosiloxane, but has the problems of unclear optical texture and low fluorescent color purity. In order to solve the problem, a fluorescent chromophoric group is introduced into a liquid crystal structure to prepare a fluorescent liquid crystal micromolecule pure substance, and the fluorescent liquid crystal micromolecule pure substance is an important strategy for developing fluorescent liquid crystals with double anti-counterfeiting mechanisms. However, the fluorescent chromophore group often has large steric hindrance, and the introduction of the fluorescent chromophore group into a liquid crystal structure can often seriously damage the liquid crystal anti-counterfeiting property of the material, which is a main reason for hindering the research and development and application of the fluorescent liquid crystal small molecule anti-counterfeiting material.
Disclosure of Invention
The invention aims to provide fluorescent liquid crystal micromolecules with a temperature control optical texture and photoluminescence double anti-counterfeiting mechanism, which have wider liquid crystal interval, show the liquid crystal performance of a typical temperature control optical texture, have the fluorescence property of high color purity and have wide application prospect in the anti-counterfeiting field.
The invention also aims to provide a preparation method of the fluorescent liquid crystal micromolecule with the temperature-controlled optical texture and photoluminescence double anti-counterfeiting mechanism.
In order to achieve the purpose, the invention adopts the following technical scheme:
on one hand, the invention provides a fluorescent liquid crystal micromolecule with a temperature control optical texture and photoluminescence double anti-counterfeiting mechanism, and the chemical structure of the fluorescent liquid crystal micromolecule is shown as a formula I:
the value of n in formula I is as follows: 4,6,8, 10.
On the other hand, the invention also provides a preparation method of the fluorescent liquid crystal micromolecule with the temperature-controlled optical texture and photoluminescence double anti-counterfeiting mechanism, which comprises the following steps:
(1) Synthesis of liquid crystal nucleus
Sequentially adding 4,4-dihydroxybiphenyl and tetrahydrofuran into a reaction container to obtain a reaction solution II, stirring until 4,4-dihydroxybiphenyl is completely dissolved, adding an acid scavenger, slowly dropwise adding a certain amount of 4-butenyl benzoyl chloride into the reaction solution II, stirring and reacting for 2-3 hours at normal temperature, and heating and refluxing for reaction; after the reaction is finished, cooling the reaction liquid to room temperature, carrying out suction filtration, removing insoluble substances, carrying out rotary evaporation on the filtrate to remove the solvent to obtain a crude product, and recrystallizing the crude product with hot ethanol for 3-6 times to obtain a white powdery solid, namely the liquid crystal nucleus 4-butenyl benzoyloxy diphenol monoester; the molar ratio of the 4-butenyl benzoyl chloride to the 4,4-dihydroxybiphenyl to the acid scavenger is 1: (1.5-2): (1.1-1.5);
(2) Synthesis of liquid crystal intermediates
Weighing a certain amount of dibasic acid, placing the dibasic acid into a reaction container, adding 1- (3-dimethylaminopropyl) -3-Ethylcarbodiimide (EDCI) and 4-Dimethylaminopyridine (DMAP), taking tetrahydrofuran as a solvent, and stirring at normal temperature for 2 hours to obtain a reaction solution III; weighing the 4-butenyl benzoyloxy diphenol monoester prepared in the step (1), dissolving the 4-butenyl benzoyloxy diphenol monoester in tetrahydrofuran, slowly dripping the solution into the reaction solution III, and stirring the solution at normal temperature for reaction; dropwise adding 1mL of distilled water into the reaction system, reacting for 1h, filtering to remove insoluble substances, carrying out rotary evaporation on the filtrate to remove tetrahydrofuran to obtain a crude product, and carrying out recrystallization purification to obtain a liquid crystal intermediate; the dibasic acid is one of adipic acid, suberic acid, sebacic acid and dodecanedioic acid, and the molar ratio of the dibasic acid to EDCI to DMAP to the 4-butenyl benzoyloxy diphenol monoester is 72: (20-25): (1.5-2.5): 18;
(3) Synthesis of fluorescent liquid crystal small molecules
Weighing the liquid crystal intermediate prepared in the step (2), placing the liquid crystal intermediate into a reaction container, adding EDCI and DMAP, taking tetrahydrofuran as a solvent, and stirring at normal temperature for 2 hours to obtain a reaction liquid IV; weighing a certain amount of 1-pyrene methanol, dissolving in tetrahydrofuran, slowly dropping into the reaction liquid IV, and stirring at normal temperature for reaction; dropwise adding 0.5mL of distilled water into the reaction system, reacting for 2h, performing suction filtration to remove insoluble substances, performing rotary evaporation on the filtrate to remove tetrahydrofuran to obtain a crude product, and performing recrystallization purification to obtain fluorescent liquid crystal micromolecules; the molar ratio of the liquid crystal intermediate to EDCI to DMAP to pyrene methanol is 10: (10-11): (0.9-1): (10 to 11).
Preferably, in the step (1), the synthesis process of the 4-butenyl benzoyl chloride is as follows: sequentially adding 4-butenylbenzoic acid and thionyl chloride into a reaction vessel to obtain a reaction solution I, stirring and reacting for 2-3 h at normal temperature, heating the reaction solution I to 50-60 ℃, then continuously stirring and reacting for 5-6 h, carrying out reduced pressure distillation after the reaction is finished, and removing excessive thionyl chloride to obtain a light yellow transparent liquid, namely 4-butenyl benzoyl chloride; the molar ratio of the 4-butenylbenzoic acid to the thionyl chloride is 1: (4-6).
Preferably, in the step (1), the acid scavenger is pyridine, and the heating reflux reaction time is 8 to 10 hours.
Preferably, in the step (2), the reaction time is 48 to 72 hours under normal temperature stirring.
Preferably, in the step (3), the reaction time is 60 to 72 hours under normal temperature stirring.
Preferably, in the step (3), the recrystallization purification step is to recrystallize with ethanol and then with ethyl acetate.
The synthetic reaction steps of the invention are as follows:
in the above reaction formula, n is selected from: 4,6,8, 10.
The invention takes butenylbenzoic acid, 4,4-dihydroxybiphenyl, dibasic acid (adipic acid, suberic acid, sebacic acid and dodecanedioic acid) and pyrene methanol as raw materials to prepare the fluorescent liquid crystal micromolecule with the temperature control optical texture and photoluminescence double anti-counterfeiting mechanism. Compared with fluorescent liquid crystal ionomers, the fluorescent liquid crystal micromolecules have good liquid crystal performance, clear and definite liquid crystal texture and high identification degree, also have good fluorescence characteristics, and have high fluorescence intensity and high color purity under the excitation of ultraviolet light with specific wavelength. The fluorescent liquid crystal micromolecules with the temperature-control optical texture and photoluminescence double anti-counterfeiting mechanism have potential application prospects in the aspects of anti-counterfeiting, optics, display and the like. The preparation method is simple, easy to operate, high in yield and easy for industrial production.
Drawings
FIG. 1 is an infrared spectrum of a butenylbenzoic acid feedstock;
FIG. 2 is an infrared spectrum of a liquid crystalline core 4-butenyl benzoyloxy diphenol monoester;
FIG. 3 is an infrared spectrum of the liquid crystal intermediate A1;
FIG. 4 is an infrared spectrum of fluorescent liquid crystal small molecule M1;
FIG. 5 is a nuclear magnetic spectrum of fluorescent liquid crystal small molecule M1;
FIG. 6 is a DSC graph of fluorescent liquid crystal small molecule M1;
FIG. 7 is a temperature-controlled optical texture of a fluorescent liquid crystal small molecule M1;
FIG. 8 is the appearance of fluorescent liquid crystal small molecule M1 and its fluorescence properties;
FIG. 9 is an infrared spectrum of fluorescent liquid crystal small molecule M2;
FIG. 10 is a nuclear magnetic spectrum of fluorescent liquid crystal small molecule M2;
FIG. 11 is a DSC graph of fluorescent liquid crystal small molecule M2;
FIG. 12 is an infrared spectrum of fluorescent liquid crystal small molecule M3;
FIG. 13 is a nuclear magnetic spectrum of fluorescent liquid crystal small molecule M3;
FIG. 14 is a DSC graph of fluorescent liquid crystal small molecule M3;
FIG. 15 is a nuclear magnetic spectrum of fluorescent liquid crystal small molecule M4;
fig. 16 is a DSC graph of fluorescent liquid crystal small molecule M4.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
Example 1
A fluorescent liquid crystal micromolecule M1 with temperature control optical texture and photoluminescence double anti-counterfeiting mechanisms: the structural formula of the fluorescent liquid crystal micromolecule is as follows:
the synthetic route of the compound is as follows:
the preparation method of the compound comprises the following steps:
(1) Liquid crystal nucleus: preparation of 4-butenyl benzoyloxy diphenol monoesters
Synthesis of (1-1) 4-butenyl benzoyl chloride
Adding 17.6g (0.1 mol) of 4-butenylbenzoic acid and 40mL of thionyl chloride into a reaction vessel in sequence to obtain a reaction solution I, stirring and reacting for 2-3 h at normal temperature, heating the reaction solution I to 50-60 ℃, then continuously stirring and reacting for 5-6 h, carrying out reduced pressure distillation after the reaction is finished, and removing excessive thionyl chloride to obtain 17.6g of light yellow transparent liquid 4-butenyl benzoyl chloride with the yield of 90%.
Synthesis of (1-2) 4-butenyl benzoyloxy diphenol monoester
Adding 33.48g (0.18 mol) 4,4-dihydroxybiphenyl and 400mL tetrahydrofuran into a reaction vessel to obtain a reaction solution II, stirring until 4,4-dihydroxybiphenyl is completely dissolved, adding 10.7g
(0.135 mol) of pyridine, slowly dropwise adding 17.6g (0.09 mol) of 4-butenyl benzoyl chloride into the reaction liquid II, stirring and reacting for 2-3 h at normal temperature, mounting a condenser pipe on a reaction container, heating and refluxing for reaction for 9h, stopping the reaction, cooling the reaction liquid to room temperature, performing suction filtration to remove insoluble substances, performing rotary evaporation on the filtrate to remove the solvent to obtain a crude product, and recrystallizing the crude product with hot ethanol for 3-6 times to obtain 27.6g (0.08 mol) of 4-butenyl benzoyloxy diphenol monoester, wherein the yield is 89%.
(2) Liquid crystal intermediate A1: synthesis of 4-butenyl benzoyloxy biphenyloxoacyl valeric acid.
46.7g (0.32 mol) of adipic acid was weighed out and placed in a reaction vessel, 3.78g (0.09 mol) of EDCI and 1.08g (0.009 mol) of DMAP were added to the reaction vessel, and 300mL of tetrahydrofuran was added thereto and stirred at room temperature for 2 hours to obtain a reaction solution III. 27.6g (0.08 mol) of 4-butenyl benzoyloxybiphenol monoester was dissolved in 100mL of tetrahydrofuran, and slowly dropped into the above reaction solution III using a dropping funnel, and the reaction was stirred at room temperature for 48 hours. Dropwise adding 1mL of distilled water into the reaction system, after reacting for 1h, carrying out suction filtration to remove insoluble substances, carrying out rotary evaporation on the filtrate to remove tetrahydrofuran to obtain a crude product, and carrying out recrystallization by using ethanol to obtain 28.4g (0.06 mol) of a liquid crystal intermediate 4-butenyl benzoyloxy diphenoxyacyl valeric acid with the yield of 75%.
(3) Fluorescent liquid crystal small molecule M1: synthesis of 4-butenyl benzoyloxy biphenoxyacyl butylpyrene methanol ester
14.2g (0.03 mol) of liquid crystal intermediate A1 was weighed and placed in a 250mL three-necked flask, 1.38g (0.033 mol) of EDCI and 0.37g (0.003 mol) of DMAP were added thereto, 100mL of tetrahydrofuran was added thereto, and the mixture was stirred at room temperature for 2 hours to obtain reaction solution IV. 7.66g (0.033 mol) of 1-pyrenemethanol was weighed and dissolved in tetrahydrofuran, and was slowly dropped into the above-mentioned reaction liquid IV using a dropping funnel, and stirred at room temperature for reaction for 60 hours. 0.5mL of distilled water was added dropwise to the reaction system, and the reaction was carried out for 2 hours. And (4) filtering to remove insoluble substances, and performing rotary evaporation on the filtrate to remove tetrahydrofuran to obtain a crude product. Recrystallizing with ethanol, and recrystallizing with ethyl acetate to obtain fluorescent liquid crystal micromolecule M1.
For the above prepared: performing infrared analysis on a liquid crystal nucleus (4-butenyl benzoyloxy diphenol monoester), a liquid crystal intermediate A1 (4-butenyl benzoyloxy diphenoxy valeric acid) and a fluorescent liquid crystal small molecule M1 (4-butenyl benzoyloxy diphenoxy acyl butylpyrene methanol); the fluorescent liquid crystal small molecule M1 is subjected to nuclear magnetic resonance, liquid crystal interval, liquid crystal texture, and fluorescence property analysis, as shown in fig. 1 to 8.
(1) Infrared analysis of Butylbenzoic acid feedstock
FIG. 1 shows the IR spectrum of a butenylbenzoic acid starting material, which is 2500-3200cm -1 The absorption peak at (A) is a stretching vibration absorption peak associated with-COOH of 2536cm -1 ，2959cm -1 The absorption peak at (A) is assigned to-CH 2 Absorption peak of (1), 1690cm -1 The absorption peak of carbonyl C = O in carboxyl, and the raw material accords with molecular design.
(2) Liquid crystal nucleus: infrared analysis of 4-butenyl benzoyloxy biphenol monoesters
FIG. 2 is an infrared spectrum of a liquid crystalline core 4-butenyl benzoyloxy biphenol monoester. 2500-3200cm -1 The absorption peak of the contraction vibration associated with-COOH disappeared at 1690cm -1 Absorption peak at carboxyl group of C = O disappeared at 1734cm -1 A characteristic absorption peak of C = O in the ester group of 3382cm was observed -1 A characteristic absorption peak of-OH, 1606cm -1 And 1500cm -1 The absorption peak is the absorption peak of the benzene ring skeleton, which shows that esterification reaction occurs between raw materials and liquid crystal nucleus is in accordance with molecular design.
(3) Liquid crystal intermediate A1: infrared analysis of 4-butenyl benzoyloxy biphenyloxy pentanoic acid
FIG. 3 is an infrared spectrum of the liquid crystal intermediate A1. 2500-3200cm -1 2930cm, a stretching vibration absorption peak associated with-OH in the carboxylic acid group -1 Is a methylene groupAbsorption peak of contraction vibration, 1732cm -1 C = O absorption peak at ester group, 1490cm -1 The absorption peak is generated by the vibration of the skeleton of the benzene ring, and the liquid crystal core structure is positioned at 3382cm -1 The disappearance of the characteristic absorption peak at-OH indicates that the liquid crystal nucleus and adipic acid have undergone a chemical reaction to form the liquid crystal intermediate A1.
(4) Fluorescent liquid crystal small molecule M1: infrared analysis of 4-butenyl benzoyloxy biphenoxyacyl butylpyrene methanol ester
FIG. 4 is an infrared spectrum of fluorescent liquid crystal small molecule M1. Belongs to a liquid crystal intermediate A1 in the range of 2500-3200cm -1 the-OH association vibration absorption peak in carboxylic acid group disappears, 2920cm -1 Is of the formula-CH 2 Expansion peak, 1732cm -1 Is C = O stretching vibration absorption peak in ester group at 1495cm -1 The position is an absorption peak generated by stretching vibration of a benzene ring framework. The fluorescent liquid crystal small molecule M1 can be preliminarily judged to accord with the molecular design.
(5) Fluorescent liquid crystal small molecule M1: nuclear magnetic analysis of 4-butenyl benzoyloxy biphenoxyacyl butylpyrene methanol ester
The nuclear magnetic data analysis of the fluorescent liquid crystal micromolecule M1 is as follows: 1 HNMR(500MHz,CDCl 3 ,δ):8.31(m,1H),8.10(m,2H),8.08-8.04(m,4H),7.92-7.81(m,5H),7.74-7.70(t,3H),7.23-6.97(d,6H),5.82(m,1H),5.49(s,2H),5.13-4.88(m,2H),2.56-2.29(m,8H),1.64(t,4H)。
(6) Fluorescent liquid crystal small molecule M1: liquid crystal interval analysis of 4-butenyl benzoyloxy biphenoxyacyl butylpyrene methanol ester
And (3) characterizing the liquid crystal interval of the fluorescent liquid crystal small molecule M1 by adopting a differential scanning calorimetry. FIG. 6 is a DSC chart of fluorescent liquid crystal small molecule M1. As clearly shown in the figure, the melting point of the liquid crystal monomer is 142 ℃, the clearing point is 154.1 ℃, the liquid crystal interval is 12.1 ℃, and the liquid crystal monomer belongs to thermotropic liquid crystal.
(7) Fluorescent liquid crystal small molecule M1: temperature-controlled optical texture analysis of 4-butenyl benzoyloxy biphenoxyacyl butylpyrene methanol ester
The optical texture of the fluorescent liquid crystal micromolecule M1 is shot by adopting a polarizing microscope, the liquid crystal optical texture is clear in the temperature rising process and the temperature reducing process within the liquid crystal temperature range of 142-154.1 ℃, as shown in figures 7 (a) and 7 (b), the optical texture presented within the liquid crystal temperature range has high reversibility, is clear and easy to identify, and the optical texture for temperature rising and temperature reducing is different, so that the optical texture can be applied to temperature control optical texture anti-counterfeiting.
(8) Fluorescent liquid crystal small molecule M1: fluorescence performance analysis of 4-butenyl benzoyloxy bisphenoxyacyl butylpyrene methanol ester
When the fluorescent liquid crystal small molecule M1 is not excited by ultraviolet light, the fluorescent liquid crystal small molecule M1 is light yellow powder as shown in FIG. 8 (a); under the excitation of excitation light at 340nm, the fluorescent liquid crystal small molecule M1 emits blue fluorescence, as shown in FIG. 8 (b); the fluorescence emission spectrum thereof was at 390nm, as shown in FIG. 8 (c). When no ultraviolet light is excited, the blue fluorescence disappears, and the fluorescence property, i.e. photoluminescence property of the fluorescent liquid crystal small molecule M1 has high reversibility.
Example 2
A fluorescent liquid crystal micromolecule M2 with temperature control optical texture and photoluminescence double anti-counterfeiting mechanisms: the structural formula of the fluorescent liquid crystal micromolecule is as follows:
the synthetic route of the compound is as follows:
the preparation of this compound is similar to example 1.
(1) Fluorescent liquid crystal small molecule M2: infrared analysis of 4-butenyl benzoyloxy biphenoxyacylhexylpyrene methanol ester
FIG. 9 is an infrared spectrum of fluorescent liquid crystal small molecule M2. 2500-3200cm -1 the-OH association vibration absorption peak in carboxylic acid group disappears, 2920cm -1 Is of the formula-CH 2 Peak of stretching vibration, 1732cm -1 Is C = O stretching vibration absorption peak in ester group, 1495cm -1 The position is an absorption peak generated by stretching vibration of a benzene ring framework. The fluorescent liquid crystal small molecule M2 can be preliminarily judged to accord with the molecular design.
(2) Fluorescent liquid crystal small molecule M2: nuclear magnetic analysis of 4-butenyl benzoyloxy biphenoxyacylhexylpyrenemethyl alcohol ester
The nuclear magnetic data analysis of the fluorescent liquid crystal micromolecule M2 is as follows: 1 HNMR(500MHz,CDCl 3 δ.8.31 (m, 1H), 8.10 (m, 2H), 8.08-8.04 (m, 4H), 7.92-7.81 (m, 5H), 7.74-7.70 (t, 3H), 7.23-6.97 (d, 6H), 5.82 (m, 1H), 5.49 (s, 2H), 5.13-4.88 (m, 2H), 2.56-2.29 (m, 8H), 1.66-1.33 (t, 8H). As shown in fig. 10.
(3) Fluorescent liquid crystal small molecule M2: liquid crystal interval analysis of 4-butenyl benzoyloxy biphenoxyacylhexylpyrene methanol ester
And (3) characterizing the liquid crystal interval of the fluorescent liquid crystal micromolecule M2 by adopting a differential scanning calorimetry. FIG. 11 is a DSC chart of fluorescent liquid crystal small molecule M2. As clearly shown in the figure, the melting point of the liquid crystal monomer is 130.75 ℃, the clearing point is 152.3 ℃, the liquid crystal interval is 21.55 ℃, and the liquid crystal monomer belongs to thermotropic liquid crystal.
Example 3
A fluorescent liquid crystal micromolecule M3 with temperature control optical texture and photoluminescence double anti-counterfeiting mechanisms: the structural formula of the fluorescent liquid crystal micromolecule is as follows:
the synthetic route of the compound is as follows:
the preparation of this compound is similar to example 1.
(1) Fluorescent liquid crystal small molecule M3: infrared analysis of 4-butenyl benzoyloxy biphenoxyacyloctylpyrene methanol ester
FIG. 12 is an infrared spectrum of fluorescent liquid crystal small molecule M3. In the range of 2500-3200cm -1 the-OH association vibration absorption peak in carboxylic acid group disappears, 2920cm -1 、2845cm -1 Is of the formula-CH 2 Expansion peak, 1732cm -1 Is C = O stretching vibration absorption peak in ester group, 1495cm -1 The position is an absorption peak generated by stretching vibration of a benzene ring framework. The fluorescent liquid crystal small molecule M3 can be preliminarily judged to accord with the molecular design.
(2) Fluorescent liquid crystal small molecule M3: nuclear magnetic analysis of 4-butenyl benzoyloxy biphenoxyacyloctapyrene methanol ester
The nuclear magnetic data analysis of the fluorescent liquid crystal micromolecule M3 is as follows: 1 HNMR(500MHz,CDCl 3 δ.8.31 (m, 1H), 8.10 (m, 2H), 8.08-8.04 (m, 4H), 7.92-7.81 (m, 5H), 7.74-7.70 (t, 3H), 7.23-6.97 (d, 6H), 5.82 (m, 1H), 5.49 (s, 2H), 5.13-4.88 (m, 2H), 2.56-2.29 (m, 8H), 1.66-1.30 (t, 12H). As shown in fig. 13.
(3) Fluorescent liquid crystal small molecule M3: liquid crystal interval analysis of 4-butenyl benzoyloxy biphenoxyacyloctapyrene methanol ester
And (3) characterizing the liquid crystal interval of the fluorescent liquid crystal small molecule M3 by adopting a differential scanning calorimetry. FIG. 14 is a DSC chart of fluorescent liquid crystal small molecule M3. As clearly shown in the figure, the melting point of the liquid crystal monomer is 125 ℃, the clearing point is 148 ℃, the liquid crystal interval is 23 ℃, and the liquid crystal monomer belongs to thermotropic liquid crystal.
Example 4
A fluorescent liquid crystal micromolecule M4 with a temperature control optical texture and photoluminescence double anti-counterfeiting mechanism is disclosed: the structural formula of the fluorescent liquid crystal micromolecule is as follows:
the synthetic route of the compound is as follows:
the preparation of this compound is similar to example 1.
(1) Fluorescent liquid crystal small molecule M4: nuclear magnetic analysis of 4-butenyl benzoyloxy bisphenoxyacyl decylpyrene methanol ester
The nuclear magnetic data analysis of the fluorescent liquid crystal micromolecule M4 is as follows: 1 HNMR(500MHz,CDCl 3 δ.8.31 (m, 1H), 8.10 (m, 2H), 8.08-8.04 (m, 4H), 7.92-7.81 (m, 5H), 7.74-7.70 (t, 3H), 7.23-6.97 (d, 6H), 5.82 (m, 1H), 5.49 (s, 2H), 5.13-4.88 (m, 2H), 2.56-2.29 (m, 8H), 1.66-1.26 (t, 16H). As shown in fig. 15.
(2) Fluorescent liquid crystal small molecule M4: liquid crystal interval analysis of 4-butenyl benzoyloxy biphenoxyacyl decyl pyrene methyl alcohol ester
And (3) characterizing the liquid crystal interval of the fluorescent liquid crystal micromolecule M4 by adopting a differential scanning calorimetry method. FIG. 16 is a DSC chart of fluorescent liquid crystal small molecule M4. As clearly shown in the figure, the melting point of the liquid crystal monomer is 129 ℃, the clearing point is 145 ℃, the liquid crystal interval is 16 ℃, and the liquid crystal monomer belongs to thermotropic liquid crystal.
The above description is only for the purpose of illustrating the embodiments of the present invention, and the scope of the present invention should not be limited thereto, and any modifications, equivalents and improvements made by those skilled in the art within the technical scope of the present invention as disclosed in the present invention should be covered by the scope of the present invention.
Claims (7)
1. A fluorescent liquid crystal micromolecule with temperature control optical texture and photoluminescence double anti-counterfeiting mechanisms is characterized in that the chemical structure of the fluorescent liquid crystal micromolecule is as shown in a formula I:
the value of n in formula I is as follows: 4,6,8, 10.
2. The preparation method of the fluorescent liquid crystal micromolecule with the temperature-controlled optical texture and photoluminescence double anti-counterfeiting mechanism as claimed in claim 1 is characterized by comprising the following steps of:
(1) Synthesis of liquid Crystal nuclei
Sequentially adding 4,4-dihydroxybiphenyl and tetrahydrofuran into a reaction container to obtain a reaction solution II, stirring until 4,4-dihydroxybiphenyl is completely dissolved, adding an acid scavenger, slowly dropwise adding 4-butenyl benzoyl chloride into the reaction solution II, stirring and reacting for 2-3 hours at normal temperature, and heating for reflux reaction; after the reaction is finished, cooling the reaction liquid to room temperature, carrying out suction filtration, removing insoluble substances, carrying out rotary evaporation on the filtrate to remove the solvent to obtain a crude product, and recrystallizing the crude product with hot ethanol for 3-6 times to obtain a white powdery solid, namely the liquid crystal nucleus 4-butenyl benzoyloxy diphenol monoester; the molar ratio of the 4-butenyl benzoyl chloride to the 4,4-dihydroxybiphenyl to the acid scavenger is 1: (1.5-2): (1.1-1.5);
(2) Synthesis of liquid crystal intermediates
Weighing dibasic acid, placing the dibasic acid in a reaction container, adding EDCI and DMAP, taking tetrahydrofuran as a solvent, and stirring for 2 hours at normal temperature to obtain a reaction solution III; weighing the 4-butenyl benzoyloxy diphenol monoester prepared in the step (1), dissolving the 4-butenyl benzoyloxy diphenol monoester in tetrahydrofuran, slowly dripping the solution into the reaction solution III, and stirring at normal temperature for reaction; dropwise adding 1mL of distilled water into the reaction system, after reacting for 1h, carrying out suction filtration to remove insoluble substances, carrying out rotary evaporation on the filtrate to remove tetrahydrofuran to obtain a crude product, and carrying out recrystallization purification to obtain a liquid crystal intermediate; the dibasic acid is one of adipic acid, suberic acid, sebacic acid and dodecanedioic acid, and the molar ratio of the dibasic acid to EDCI to DMAP to the 4-butenyl benzoyloxy diphenol monoester is 72: (20-25): (1.5-2.5): 18;
(3) Synthesis of fluorescent liquid crystal small molecules
Weighing the liquid crystal intermediate prepared in the step (2), placing the liquid crystal intermediate into a reaction container, adding EDCI and DMAP, taking tetrahydrofuran as a solvent, and stirring at normal temperature for 2 hours to obtain a reaction liquid IV; weighing 1-pyrene methanol, dissolving in tetrahydrofuran, slowly dropping into the reaction liquid IV, and stirring at normal temperature for reaction; dropwise adding 0.5mL of distilled water into the reaction system, reacting for 2h, performing suction filtration to remove insoluble substances, performing rotary evaporation on filtrate to remove tetrahydrofuran to obtain a crude product, and performing recrystallization purification to obtain fluorescent liquid crystal micromolecules; the molar ratio of the liquid crystal intermediate to EDCI to DMAP to pyrene methanol is 10: (10-11): (0.9-1): (10 to 11).
3. The method for preparing fluorescent liquid crystal micromolecules with temperature-controlled optical texture and photoluminescence double anti-counterfeiting mechanisms according to claim 2, wherein in the step (1), the synthesis process of the 4-butenyl benzoyl chloride is as follows: sequentially adding 4-butenylbenzoic acid and thionyl chloride into a reaction vessel to obtain a reaction solution I, stirring and reacting for 2-3 h at normal temperature, heating the reaction solution I to 50-60 ℃, then continuously stirring and reacting for 5-6 h, carrying out reduced pressure distillation after the reaction is finished, and removing excessive thionyl chloride to obtain a light yellow transparent liquid, namely 4-butenyl benzoyl chloride; the molar ratio of the 4-butenylbenzoic acid to the thionyl chloride is 1: (4-6).
4. The method for preparing fluorescent liquid crystal micromolecules with temperature-controlled optical texture and photoluminescence double anti-counterfeiting mechanism according to claim 2, characterized in that in the step (1), the acid scavenger is pyridine, and the heating reflux reaction time is 8-10 h.
5. The method for preparing fluorescent liquid crystal micromolecules with temperature-controlled optical texture and photoluminescence dual anti-counterfeiting mechanism according to claim 2, wherein in the step (2), the normal-temperature stirring reaction time is 48-72 h.
6. The method for preparing fluorescent liquid crystal micromolecules with temperature-controlled optical texture and photoluminescence double anti-counterfeiting mechanism according to claim 2, wherein in the step (3), the normal-temperature stirring reaction time is 60-72 h.
7. The method for preparing fluorescent liquid crystal micromolecules with temperature-controlled optical texture and photoluminescence double anti-counterfeiting mechanism according to claim 2, wherein in the step (3), the step of recrystallization purification is to use ethanol for recrystallization, and then use ethyl acetate for recrystallization.
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| US20100207078A1 (en) * | 2006-07-12 | 2010-08-19 | Seth Marder | Deprotection of functional groups by multi-photon induced electron transfer |
| CN111285970A (en) * | 2019-10-14 | 2020-06-16 | 浙江工业大学 | Pyrene fluorescent group and epoxy group grafted hyperbranched polyethylene, preparation method thereof and application thereof in preparation of fluorescent epoxy resin |
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| CN113150056A (en) * | 2021-03-30 | 2021-07-23 | 徐州工程学院 | Double anti-counterfeiting mechanism chiral fluorescent liquid crystal with three primary colors at room temperature and preparation method thereof |
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| CN112142770A (en) * | 2020-09-03 | 2020-12-29 | 徐州工程学院 | Janus oligomer with full-spectrum selective reflection and photoluminescence and preparation method thereof |
| CN113150056A (en) * | 2021-03-30 | 2021-07-23 | 徐州工程学院 | Double anti-counterfeiting mechanism chiral fluorescent liquid crystal with three primary colors at room temperature and preparation method thereof |
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