CN114230600A - Side chain type fluorescent liquid crystal polymer based on alpha-cyanobenzene stilbene AIE property and preparation method and application thereof - Google Patents
Side chain type fluorescent liquid crystal polymer based on alpha-cyanobenzene stilbene AIE property and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
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- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 title description 3
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- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 15
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 claims abstract description 12
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 claims abstract description 10
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- 238000000034 method Methods 0.000 claims abstract 7
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- 238000003756 stirring Methods 0.000 claims description 20
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
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- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
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- 238000001914 filtration Methods 0.000 claims description 8
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 claims description 7
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- 238000001035 drying Methods 0.000 claims description 7
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- 238000004519 manufacturing process Methods 0.000 claims 1
- VFOKYTYWXOYPOX-PTNGSMBKSA-N (e)-2,3-diphenylprop-2-enenitrile Chemical compound C=1C=CC=CC=1C(/C#N)=C\C1=CC=CC=C1 VFOKYTYWXOYPOX-PTNGSMBKSA-N 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
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- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
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- USLPZCOPYRKTGY-UHFFFAOYSA-N 2-(2-phenylethenyl)benzonitrile Chemical compound N#CC1=CC=CC=C1C=CC1=CC=CC=C1 USLPZCOPYRKTGY-UHFFFAOYSA-N 0.000 description 1
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 1
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
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- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/36—Steroidal liquid crystal compounds
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Abstract
The invention relates to a side chain type fluorescent liquid crystal polymer based on alpha-cyano stilbene AIE properties, and a preparation method and application thereof. The side chain type fluorescent liquid crystal polymer with 1,3,5, 7-tetramethylcyclotetrasiloxane (CMHS) as a main chain is obtained by taking p-hydroxyphenylacetonitrile, 3-bromo-1-propylene, p-hydroxybenzaldehyde, cholesterol formyl chloride and 1,3,5, 7-tetramethylcyclotetrasiloxane (CMHS) as main raw materials and adopting a chemical synthesis method. The invention successfully transfers the AIE property of the alpha-cyano stilbene and the chiral property of the cholesterol to the side chain liquid crystal polymer through reasonable molecular design, and provides a new way for the development of high-efficiency fluorescent liquid crystal materials.
Description
Technical Field
The invention relates to the field of side chain liquid crystal polymers, in particular to a side chain fluorescent liquid crystal polymer containing alpha-cyano stilbene and a preparation method thereof.
Background
Liquid Crystals (LCs) have anisotropic optical properties and are often used as functional materials in the technology of displays and information storage devices. The liquid crystal phase is generally classified into a lyotropic liquid crystal phase formed according to the change in the concentration of a solution and a thermotropic liquid crystal phase in which anisotropy formed when a liquid crystal substance is heated exists only in a certain temperature range. Nowadays, Liquid Crystal Polymers (LCPs) are taking an important position in the intelligent field due to their wide range of applications, such as medical treatment, photovoltaics, display technology, and intelligent soft robots.
Cholesteric liquid crystals (ChLCs) can selectively reflect circularly polarized light. By adding optical rotators with different rotating pitches, colors such as red, green and blue can be prepared, and the requirement of color display is met. Siloxanes are commonly used as the backbone for the side chains. The low surface energy, high bond energy, mechanical energy and thermal stability of the siloxane-liquid crystal polymer greatly improve the thermal property of the siloxane-liquid crystal polymer, and show good thermal stability fluorescent molecules, and the alpha-cyano stilbene derivative is often used as a candidate material for constructing a chain response material.
Aggregation-induced emission (AIE) effects, in which some twisted organic dyes show significantly enhanced fluorescence emission in the aggregated or solid state, although their molecular dissolved state emits little, in sharp contrast to the usual aggregation-induced quenching (ACQ).
The fluorescent liquid crystal material combines the fluorescence property of the fluorescent material and the liquid crystallinity of the liquid crystal material, has important application value in the fields of fluorescent liquid crystal displays, optical information storage, organic light emitting diodes and the like, and is widely concerned.
Disclosure of Invention
In order to solve the problems, the invention provides a side chain type liquid crystal polymer with fluorescence performance, which realizes the combination of alpha-cyano stilbene AIE performance and liquid crystal performance of a liquid crystal polymer material. Provides theoretical and practical materials for preparing novel fluorescent liquid crystal materials.
The technical scheme adopted by the invention is as follows: a side chain fluorescent liquid crystal polymer based on alpha-cyanobenzene ethylene AIE properties has a structural formula shown as (I):
a preparation method of a side chain type fluorescent liquid crystal polymer based on alpha-cyanobenzene ethylene AIE properties comprises the following steps: respectively dissolving the intermediate 3 and 1,3,5, 7-tetramethylcyclotetrasiloxane (CMHS) in toluene, then sequentially pouring the mixture into a reaction vessel, fully stirring, raising the temperature to 50 ℃ when the solution is clear, adding hexachloroplatinic acid dissolved in THF into the system as a catalyst, continuously raising the temperature to 80 ℃ for reacting for 23-25 hours to a reaction end point, wherein the reaction end point is that infrared spectroscopy is used for detecting the reaction process in the reaction process, and when the wave number of 1,3,5, 7-tetramethylcyclotetrasiloxane (CMHS) is 2169cm-1When the stretching vibration peak of the Si-H bond disappears completely, the reaction is complete. After the obtained reaction product is subjected to rotary evaporation of a solvent, pouring the obtained product into methanol, standing overnight, filtering, washing a filter cake with hot ethanol, and performing vacuum drying to obtain a side-chain fluorescent liquid crystal polymer based on the AIE property of the alpha-cyanobenzene; the intermediate 3 has a structural formula shown as (II):
preferably, the intermediate 3:1,3,5, 7-tetramethylcyclotetrasiloxane is 5-6: 1; the concentration of hexachloroplatinic acid dissolved in THF is 1-2%.
Preferably, the preparation method of the intermediate 3 comprises the following steps: taking the intermediate 2 and 4-Dimethylaminopyridine (DMAP), adding THF and pyridine, fully stirring and dissolving, dropwise adding a THF solution dissolved with cholesterol formyl chloride, heating to 60 ℃ to react for 6-7 hours after dropwise adding, rotationally evaporating a solvent from a reaction product, and recrystallizing with absolute ethyl alcohol to obtain an intermediate 3; the intermediate 2 has a structural formula shown as (III):
preferably, the intermediate 2: 4-dimethylaminopyridine is 35-40:1 by mass ratio.
The preparation method of the intermediate 2 comprises the following steps: adding NaOH and absolute methanol into a reaction container, stirring until the NaOH and the absolute methanol are dissolved, adding the intermediate 1 and p-hydroxybenzaldehyde, heating to 50 ℃, reacting for 12-13 hours in a dark place, adjusting the pH of a system to be neutral after the reaction is finished, extracting with water and ethyl acetate, drying organic phase, and removing the solvent to obtain an intermediate 2; the intermediate 1 has a structural formula shown as (IV):
preferably, the mass ratio of the intermediate 1 to the parahydroxybenzaldehyde is 1.3-1.5: 1.
Preferably, the preparation method of the intermediate 1 comprises the following steps: adding p-hydroxyphenylacetonitrile and absolute ethyl alcohol into a reaction container, stirring until the p-hydroxyphenylacetonitrile and the absolute ethyl alcohol are dissolved, then slowly dropwise adding a solution prepared from KOH, KI and deionized water, stirring at normal temperature for 50-60 minutes, slowly dropwise adding 3-bromo-1-propene when the solution is a transparent solution, continuously stirring at normal temperature for 2-2.5 hours, then heating to 82 ℃, reacting for 16-17 hours, after the reaction is finished, pouring the reaction solution into dilute hydrochloric acid, adjusting the pH value to 4, filtering under reduced pressure to obtain a crude product, and recrystallizing the crude product with the absolute ethyl alcohol to obtain an intermediate 1.
Preferably, the solid-to-liquid ratio of the p-hydroxyphenylacetonitrile to the 3-bromopropylene is 11-12g to 10 mL; the solid-to-liquid ratio of the solution prepared from KOH, KI and deionized water is 10-12g of KOH and 10-12g of deionized water, and 14-15mL of the solution.
The invention provides an application of a side chain type fluorescent liquid crystal polymer based on alpha-cyano stilbene AIE property in preparation of a fluorescent liquid crystal material.
Compared with the prior art, the invention has the following remarkable advantages:
most of the fluorescent liquid crystal materials reported at present are small-molecule fluorescent liquid crystals, and the fluorescent liquid crystal materials have the defects of poor thermal stability, poor film-forming performance and the like. The fluorescent liquid crystal polymer material has good processability, thermal stability and film-forming property, and can effectively regulate and control the performance by adjusting the molecular structure, so that the fluorescent liquid crystal polymer material becomes a research hotspot in recent years. The invention synthesizes the cyano-stilbene-based side chain type fluorescent liquid crystal polymer which has good liquid crystal property and fluorescence property. The polymer provided by the invention has strong AIE characteristics, and provides a simple way and a feasible strategy for remarkably improving the luminous efficiency of a well-prepared AIE polymer material.
Drawings
FIG. 1 is a nuclear magnetic map of intermediate 1 prepared in example 1.
Figure 2 is a nuclear magnetic map of intermediate 2 prepared in example 1.
FIG. 3 is a nuclear magnetic map of intermediate 3 prepared in example 1.
FIG. 4 is a nuclear magnetic diagram of the objective liquid crystalline polymer prepared in example 1.
FIG. 5 is an infrared image of intermediates 1, 2, 3, the target liquid crystalline polymer, and the starting material prepared in example 1.
FIG. 6 is a thermogravimetric curve of the objective liquid crystalline polymer prepared in example 1.
FIG. 7 is a DSC of the objective liquid crystalline polymer prepared in example 1.
FIG. 8 shows the THF/H ratio of the target liquid crystalline polymer prepared in example 12Fluorescence spectrum in O mixed solution.
FIG. 9 is photographs of the target liquid crystalline polymer under a UV lamp prepared in example 1 in different states.
Detailed Description
A preparation method of a side chain type fluorescent liquid crystal polymer based on alpha-cyanobenzene ethylene AIE properties comprises the following steps:
preparation of intermediate 1
Adding p-hydroxyphenylacetonitrile and absolute ethyl alcohol into a reaction container, stirring until the p-hydroxyphenylacetonitrile and the absolute ethyl alcohol are dissolved, then slowly dropwise adding a solution prepared from KOH, KI and deionized water, stirring at normal temperature for 50-60 minutes, slowly dropwise adding 3-bromo-1-propene when the solution is a transparent solution, continuously stirring at normal temperature for 2-2.5 hours, then heating to 82 ℃, reacting for 16-17 hours, after the reaction is finished, pouring the reaction solution into dilute hydrochloric acid, adjusting the pH value to 4, filtering under reduced pressure to obtain a crude product, and recrystallizing the crude product with the absolute ethyl alcohol to obtain an intermediate 1. Preferably, the solid-to-liquid ratio of the p-hydroxyphenylacetonitrile to the 3-bromopropylene is 11-12g to 10 mL; the solid-to-liquid ratio of the solution prepared from KOH, KI and deionized water is 10-12g of KOH, KI and deionized water, 0.08-0.09g of the solution, and 14-15mL of the solution.
Preparation of (di) intermediate 2
Adding NaOH and absolute methanol into a reaction container, stirring until the NaOH and the absolute methanol are dissolved, adding the intermediate 1 and p-hydroxybenzaldehyde, heating to 50 ℃, reacting for 12-13 hours in a dark place, adjusting the pH of the system to be neutral after the reaction is finished, extracting with water and ethyl acetate, drying the organic phase, and removing the solvent to obtain an intermediate 2. Preferably, the mass ratio of the intermediate 1 to the parahydroxybenzaldehyde is 1.3-1.5: 1.
Preparation of (tri) intermediate 3
Taking the intermediate 2 and 4-Dimethylaminopyridine (DMAP), adding THF and pyridine, fully stirring and dissolving, dropwise adding a THF solution dissolved with cholesterol formyl chloride, heating to 60 ℃ to react for 6-7 hours after dropwise adding, rotationally evaporating the solvent of a reaction product, and recrystallizing with absolute ethyl alcohol to obtain an intermediate 3. Preferably, the intermediate 2: 4-dimethylaminopyridine is 35-40:1 by mass ratio.
Preparation of (tetra) side-chain fluorescent liquid crystal polymer based on alpha-cyanobenzene stilbene AIE property
Respectively dissolving the intermediate 3 and 1,3,5, 7-tetramethylcyclotetrasiloxane (CMHS) in toluene, then sequentially pouring the mixture into a reaction container, fully stirring, raising the temperature to 50 ℃ when the solution is clear, adding hexachloroplatinic acid dissolved in THF into the system as a catalyst, continuously raising the temperature to 80 ℃ for reacting for 23-25 hours until the reaction end point, pouring the obtained product into methanol after the solvent is rotationally evaporated from the reaction product, standing overnight, filtering, washing a filter cake with hot ethanol, and drying in vacuum to obtain the side-chain fluorescent liquid crystal polymer based on the alpha-cyanobenzene AIE property. Preferably, the intermediate 3:1,3,5, 7-tetramethylcyclotetrasiloxane is 5-6: 1; the concentration of hexachloroplatinic acid dissolved in THF is 1-2%.
The synthetic route is as follows:
in order that the invention may be better understood, the invention is further illustrated by the following examples, which are to be construed as being better understood and not as imposing any limitation on the scope thereof.
Example 1 side-chain fluorescent liquid crystalline Polymer based on alpha-Cyanostilbene AIE Properties
The preparation method comprises the following steps:
1) preparation of intermediate 1
In a 100mL three-necked flask equipped with a bulb condenser, a magnetic stirrer, and an alcohol thermometer, 11.57g of p-hydroxyphenylacetonitrile and 43mL of absolute ethanol were added and stirred until dissolved. A solution of 11.43g KOH, 0.09gKI and 14.3mL deionized water was slowly added dropwise via a constant pressure funnel, and the mixture was stirred at room temperature for 50 minutes. When the solution is light orange transparent, 10mL of 3-bromo-1-propene is slowly dropped into the solution by a constant pressure funnel, and after stirring the solution for 2 hours at normal temperature, the temperature is raised to 82 ℃ to react for 16 hours. After the reaction, the obtained reaction solution was poured into a dilute hydrochloric acid solution having a concentration of 4mol/L, and the pH was adjusted to 4 to produce a white precipitate. A white solid was obtained as crude product by filtration under reduced pressure. And (3) recrystallizing the crude product by using absolute ethyl alcohol to finally obtain a needle crystal, namely the intermediate 1.
2) Preparation of intermediate 2
In a 100mL three-necked flask equipped with a bulb condenser, a magnetic stirrer, and an alcohol thermometer, 0.6g of NaOH and 30mL of anhydrous methanol were added and stirred until dissolved. Then, 0.425g of intermediate 1 and 0.3g of p-hydroxybenzaldehyde were added, the temperature was raised to 50 ℃ and the reaction was carried out for 12 hours in the absence of light. After the reaction is finished, the pH value of the system is adjusted to be neutral by using a dilute hydrochloric acid solution with the concentration of 4 mol/L. Extracting with 20mL of water and 20mL of ethyl acetate for three times alternately, taking the organic phase, drying with anhydrous magnesium sulfate, and removing the solvent to obtain a light yellow product, namely the intermediate 2.
3) Preparation of intermediate 3
1.5g of intermediate 2 and 40mg of 4-Dimethylaminopyridine (DMAP) are dissolved in 200mL of THF and 8mL of pyridine, stirred for half an hour for thorough dissolution, and then 20mL of a THF solution containing 2.4g of cholesteryl formyl chloride are added dropwise. The temperature is raised to 60 ℃ for reaction for 6 hours. Removing the solvent by rotary evaporation, and recrystallizing with anhydrous ethanol to obtain the intermediate 3.
4) Side chain type fluorescent liquid crystal polymer
4.6g of intermediate 3 and 0.816g of 1,3,5, 7-tetramethylcyclotetrasiloxane (CMHS) were dissolved in 20mL of fresh distilled toluene, and then poured into a 50mL three-necked flask equipped with a spherical condenser, a magnetic stirrer, and an alcohol thermometer, in this order. Stirring was sufficient and when the solution became clear, the temperature was raised to 50 ℃. 0.5mL of hexachloroplatinic acid dissolved in THF was further added to the system as a catalyst (concentration of hexachloroplatinic acid was 1%). The temperature is continuously increased to 80 ℃ for reaction for 24-25 hours. Detecting the reaction process by infrared spectroscopy in the reaction process, when the wave number of 1,3,5, 7-tetramethylcyclotetrasiloxane (CMHS) is 2169cm-1When the stretching vibration peak of the Si-H bond disappears completely, the reaction is complete. And then evaporating most of the solvent of the reaction product by a rotary evaporator, pouring the evaporated solvent into 50mL of methanol, standing overnight, filtering to remove the methanol, washing a filter cake by hot ethanol, removing unreacted monomers to obtain a target product, namely the side chain type fluorescent liquid crystal polymer, and drying the target product in a vacuum drying oven for later use. Example 2 detection and Performance testing of side-chain fluorescent liquid Crystal polymers based on the AIE Properties of alpha-Cyanostilbene
The chemical structure of the side chain type fluorescent liquid crystal polymer is monitored by infrared spectroscopy and nuclear magnetic resonance spectroscopy.
FIG. 1 is a drawing of intermediate 1 prepared in example 11H NMR spectrum, as can be seen from FIG. 1, each peak position can correspond to hydrogen at each position in the compound one by one, which shows that the intermediate 1 conforms to the molecular design.
FIG. 2 is a drawing of intermediate 2 prepared in example 11H NMR spectrum, it can be seen from FIG. 2 that each peak position can correspond to hydrogen at each position in the compound,indicating that intermediate 2 is in accordance with the molecular design.
FIG. 3 is a drawing of intermediate 3 prepared in example 11H NMR spectrum, it can be seen from FIG. 3 that each peak position can correspond to hydrogen at each position in the compound one by one, indicating that the intermediate 3 conforms to the molecular design.
FIG. 4 is a drawing showing the preparation of the objective liquid-crystalline polymer of example 11H NMR spectrum, as can be seen from FIG. 4, each peak position can correspond to hydrogen at each position in the compound one by one, which shows that the target liquid crystal polymer conforms to the molecular design.
FIG. 5 is an infrared image of intermediate 1, intermediate 2, intermediate 3, the target liquid crystalline polymer and the starting material prepared in example 1. As can be seen from FIG. 5, the infrared curve of intermediate 1 was 3176cm-1And 1640cm-1The characteristic peak of the carbon-carbon double bond appears at 1025cm-1The characteristic peak of C-O-C appears, and the successful synthesis of the intermediate 1 is further illustrated by combining the nuclear magnetic hydrogen spectrum diagram of the intermediate 1. Comparing the infrared curve of p-hydroxybenzaldehyde with that of intermediate 3, the raw material p-hydroxybenzaldehyde is 1685cm-1The disappearance of characteristic peak of aldehyde group is converted into the intermediate 2 at 1640cm-1The successful synthesis of the intermediate 2 is further illustrated by combining the characteristic peak of the carbon-carbon double bond with the nuclear magnetic hydrogen spectrum of the intermediate 2. The infrared curve of the intermediate 3 is 1735cm-1，1245cm-1And 1115cm-1The characteristic peak of ester group appears, and the successful synthesis of the intermediate 3 is further illustrated by combining the nuclear magnetic hydrogen spectrum diagram of the intermediate 3. As can be seen from FIG. 5, 1,3,5, 7-tetramethylcyclotetrasiloxane (CMHS) has a wave number of 2169cm-1The Si-H bond stretching vibration peak completely disappears, which indicates that the reaction is completely finished. And further combining the nuclear magnetic hydrogen spectrum diagram of the target liquid crystal polymer to further illustrate the successful synthesis of the target product.
FIG. 6 is a thermogravimetric curve of a target liquid crystalline polymer measured at a temperature increase rate of 10 deg.C/min under a nitrogen atmosphere. From FIG. 6, it can be seen that the temperature at which the liquid crystalline polymer loses 5% weight is 170 ℃, indicating that the liquid crystalline polymer has a certain thermal stability.
FIG. 7 is a graph showing the results of secondary temperature increase at a temperature increase rate of 10 ℃/min under a nitrogen atmosphereDSC curve of the target liquid crystal polymer of (1). From FIG. 7, T of the target liquid crystalline polymer can be seengAt 21.34 ℃ and TiThe temperature was 174.22 ℃. Indicating that the target liquid crystalline polymer has a broad liquid crystalline interval.
FIG. 8 shows the target liquid crystalline polymer in THF/H2Fluorescence spectrum in O mixed solution. As can be seen from fig. 8, as the content of the poor solvent water increases, molecular aggregation is caused, resulting in an increase in the fluorescence intensity of the liquid crystal polymer.
FIG. 9 is a photograph of the target liquid crystalline polymer in a solid state with a water content of 0% and a water content of 90% under a 365nm ultraviolet lamp. The AIE properties of the target liquid crystalline polymer were further confirmed.
Claims (10)
1. A fluorescent liquid crystal polymer of side chain type based on the AIE property of alpha-cyanobenzene ethylene, which is characterized in that the fluorescent liquid crystal polymer of side chain type based on the AIE property of alpha-cyanobenzene ethylene has the structural formula as shown in (I):
2. a preparation method of a side chain type fluorescent liquid crystal polymer based on alpha-cyanobenzene ethylene AIE properties is characterized by comprising the following steps: respectively dissolving the intermediate 3 and 1,3,5, 7-tetramethylcyclotetrasiloxane in toluene, then sequentially pouring the mixture into a reaction container, fully stirring, raising the temperature to 50 ℃ when the solution is clear, adding hexachloroplatinic acid dissolved in THF into the system as a catalyst, continuously raising the temperature to 80 ℃ for reaction for 23-25 hours to a reaction end point, rotationally evaporating the solvent from the reaction product, pouring the obtained product into methanol, standing overnight, filtering, washing a filter cake with hot ethanol, and drying in vacuum to obtain the side-chain fluorescent liquid crystal polymer based on the AIE property of alpha-cyanobenzene ethylene; the intermediate 3 has a structural formula shown as (II):
3. the production method according to claim 2, wherein the intermediate 3:1,3,5, 7-tetramethylcyclotetrasiloxane is 5-6: 1; the concentration of hexachloroplatinic acid dissolved in THF is 1-2%.
4. The process according to claim 2, wherein the process for the preparation of intermediate 3 comprises the following steps: taking the intermediate 2 and 4-dimethylaminopyridine, adding THF and pyridine, fully stirring and dissolving, dropwise adding a THF solution dissolved with cholesterol formyl chloride, heating to 60 ℃ to react for 6-7 hours after dropwise adding, rotationally evaporating a solvent from a reaction product, and recrystallizing with absolute ethyl alcohol to obtain an intermediate 3; the intermediate 2 has a structural formula shown as (III):
5. the preparation method according to claim 4, wherein the intermediate 2: 4-dimethylaminopyridine is 35-40:1 by mass.
6. The process according to claim 4, wherein the process for the preparation of intermediate 2 comprises the following steps: adding NaOH and absolute methanol into a reaction container, stirring until the NaOH and the absolute methanol are dissolved, adding the intermediate 1 and p-hydroxybenzaldehyde, heating to 50 ℃, reacting for 12-13 hours in a dark place, adjusting the pH value of a system to be neutral after the reaction is finished, extracting with water and ethyl acetate, drying organic phase, and removing the solvent to obtain an intermediate 2; the intermediate 1 has a structural formula shown as (IV):
7. the preparation method according to claim 6, wherein the intermediate 1: p-hydroxybenzaldehyde is 1.3-1.5:1 by mass ratio.
8. The process according to claim 6, wherein the process for the preparation of intermediate 1 comprises the following steps: adding p-hydroxyphenylacetonitrile and absolute ethyl alcohol into a reaction container, stirring until the p-hydroxyphenylacetonitrile and the absolute ethyl alcohol are dissolved, then slowly dropwise adding a solution prepared from KOH, KI and deionized water, stirring at normal temperature for 50-60 minutes, slowly dropwise adding 3-bromo-1-propene when the solution is a transparent solution, continuously stirring at normal temperature for 2-2.5 hours, then heating to 82 ℃, reacting for 16-17 hours, after the reaction is finished, pouring the reaction solution into dilute hydrochloric acid, adjusting the pH value to 4, filtering under reduced pressure to obtain a crude product, and recrystallizing the crude product with the absolute ethyl alcohol to obtain an intermediate 1.
9. The preparation method according to claim 8, wherein the solid-to-liquid ratio of p-hydroxyphenylacetonitrile to 3-bromopropylene to 11-12g to 10 mL; the solid-to-liquid ratio of the solution prepared from KOH, KI and deionized water is 10-12g of KOH and 10-12g of deionized water, and 14-15mL of the solution.
10. The use of the side-chain fluorescent liquid crystal polymer based on the AIE properties of alpha-cyanobenzene as claimed in claim 1 in the preparation of fluorescent liquid crystal material.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643432A (en) * | 2012-04-01 | 2012-08-22 | 北京科技大学 | Preparation method for cholesteric siloxane side-chain liquid crystal polymer |
| CN109180865A (en) * | 2018-08-02 | 2019-01-11 | 大连理工大学 | A kind of side chain liquid crystalline polymer and preparation method thereof based on polystyrene alternate sequence containing cholesteryl |
| CN111154499A (en) * | 2020-01-12 | 2020-05-15 | 湘潭大学 | Chiral luminescent liquid crystal polymer with circular polarization luminescent property and preparation method thereof |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643432A (en) * | 2012-04-01 | 2012-08-22 | 北京科技大学 | Preparation method for cholesteric siloxane side-chain liquid crystal polymer |
| CN109180865A (en) * | 2018-08-02 | 2019-01-11 | 大连理工大学 | A kind of side chain liquid crystalline polymer and preparation method thereof based on polystyrene alternate sequence containing cholesteryl |
| CN111154499A (en) * | 2020-01-12 | 2020-05-15 | 湘潭大学 | Chiral luminescent liquid crystal polymer with circular polarization luminescent property and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| YOUDE CHEN等: "Side-chain chiral fluorescent liquid crystal polymers with highly efficient circularly polarized luminescence emission in a glassy-state SmC film" * |
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