CN112250842A - Polymer material containing aggregation-induced emission groups and preparation method and application thereof - Google Patents

Polymer material containing aggregation-induced emission groups and preparation method and application thereof Download PDF

Info

Publication number
CN112250842A
CN112250842A CN202011007471.7A CN202011007471A CN112250842A CN 112250842 A CN112250842 A CN 112250842A CN 202011007471 A CN202011007471 A CN 202011007471A CN 112250842 A CN112250842 A CN 112250842A
Authority
CN
China
Prior art keywords
aggregation
group
polymer material
material containing
induced emission
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202011007471.7A
Other languages
Chinese (zh)
Other versions
CN112250842B (en
Inventor
唐本忠
秦安军
路琳
胡蓉蓉
赵祖金
王志明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to CN202011007471.7A priority Critical patent/CN112250842B/en
Publication of CN112250842A publication Critical patent/CN112250842A/en
Application granted granted Critical
Publication of CN112250842B publication Critical patent/CN112250842B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • C08G2261/124—Copolymers alternating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/312—Non-condensed aromatic systems, e.g. benzene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/316—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain bridged by heteroatoms, e.g. N, P, Si or B
    • C08G2261/3162—Arylamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/411—Suzuki reactions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/52—Luminescence
    • C08G2261/522—Luminescence fluorescent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/52—Luminescence
    • C08G2261/522—Luminescence fluorescent
    • C08G2261/5222—Luminescence fluorescent electrofluorescent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1408—Carbocyclic compounds
    • C09K2211/1425—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1408—Carbocyclic compounds
    • C09K2211/1433—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/1458—Heterocyclic containing sulfur as the only heteroatom

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

The invention belongs to the field of organic electrochromic and electroluminescent photochromic materials, and discloses a polymer material containing a gathering induced luminescent group, and a preparation method and application thereof. The preparation method of the polymer material containing the aggregation-induced emission groups comprises the following steps: the polymer material containing the aggregation-induced emission group is obtained by taking a monomer containing the aggregation-induced emission group and an aromatic ring derivative as raw materials, performing Suzuki-Miyaura coupling reaction and carrying out end capping by using phenylboronic acid and bromobenzene. The polymer has good solubility and high luminous performance, so that a device for information display, information high-density storage and multilevel security anti-counterfeiting can be prepared in a solution spraying mode, and the polymer has wide application prospect in the field of intelligent organic photoelectricity.
Figure DDA0002696434410000011

Description

Polymer material containing aggregation-induced emission groups and preparation method and application thereof
Technical Field
The invention belongs to the field of organic electrochromic and electroluminescent photochromic materials, and particularly relates to a polymer material containing a gathering induced luminescent group, and a preparation method and application thereof.
Background
The stimulus response material is widely applied to the fields of safety anti-counterfeiting, information encryption, data storage and the like, wherein the electrochromic material and the electroluminescent photochromic material generate reversible oxidation-reduction reaction under the electrical stimulus, and reversible change of appearance color and fluorescence emission can be realized. The electrochromic material is developed rapidly and is widely applied to the fields of intelligent windows, electronic paper, display and the like. However, the conventional luminescent materials cause the problem of luminescence quenching in the aggregation state (ACS appl. mater. interfaces 2016,8,18301-18308), which results in the low contrast ratio of the fluorescence switch of the materials and limits the practical application thereof, so that it is necessary to develop the electroluminescent photochromic material with high solid-state luminescence. On the other hand, electrochromic and electrochromism materials are generally applied to the display field (ACS appl. mater. interfaces2019,11, 11684-.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a polymer material containing a gathering induced luminescent group, and a preparation method and application thereof.
In view of the above disadvantages and shortcomings of the prior art, the present invention is primarily directed to a polymer material containing aggregation-induced emission groups. The material has excellent solubility and thermal stability, better luminous performance, electrochromic and electroluminescent photochromic characteristics, improved fluorescence switch contrast, and wide application prospect in the field of intelligent organic photoelectric devices, and can be prepared into devices for information display, information high-density storage and dynamic anti-counterfeiting in a solution spraying manner.
Another object of the present invention is to provide a method for preparing the above polymer material containing aggregation-inducing luminescent groups.
The invention also aims to provide the application of the polymer material containing the aggregation-induced emission group in information display, information high-density storage and dynamic anti-counterfeiting.
The purpose of the invention is realized by at least one of the following technical solutions.
The polymer material containing aggregation-induced emission groups has a structural formula
Figure BDA0002696434390000021
Wherein R is the same or different aromatic ring derivative groups, and n is an integer of 2-200.
Further, R is one of the following 1-9 substituents:
Figure BDA0002696434390000031
wherein R' is hydrogen atom, tert-butyl, methoxyl, cyano, fluorine atom or alkyl chain, m is a natural number of 0-10, and is a substitution position.
Further, the alkyl chain is a straight chain with 1-20 carbon atoms, a branched chain with 1-20 carbon atoms, a cyclic alkyl chain with 1-20 carbon atoms, an alkyl chain with carbon atoms substituted by oxygen atoms, alkenyl groups, alkynyl groups, aryl groups, carbonyl groups, hydroxyl groups, amino groups, carboxyl groups, cyano groups, nitro groups or ester groups, and one of the alkyl chains with hydrogen atoms substituted by fluorine atoms, chlorine atoms, bromine atoms and iodine atoms.
The polymer material containing the aggregation-induced emission group provided by the invention has the characteristics of electrochromism and electrochromism.
The invention provides a method for preparing the polymer material containing the aggregation-induced emission groups, which comprises the following steps:
the polymer material containing the aggregation-induced emission group is obtained by taking a monomer containing the aggregation-induced emission group and an aromatic ring derivative as raw materials, performing Suzuki-Miyaura coupling reaction, and then performing end capping by using phenylboronic acid and bromobenzene.
Further, the monomer containing the aggregation-induced emission group has a structural formula
Figure BDA0002696434390000041
Further, the aromatic ring derivative is one or more of carbazole derivatives, fluorene derivatives, triphenylamine derivatives, phenothiazine derivatives and phenoxazine derivatives. The group of the aromatic ring derivative is R.
Further, the molar ratio of the aggregation-inducing luminescent group-containing monomer to the aromatic ring derivative is 1: 1.
Further, the molar ratio of the phenylboronic acid to the bromobenzene is 1:1-3: 1; the molar ratio of the aromatic ring derivative to the phenylboronic acid is 1:10-1: 30.
Preferably, the molar ratio of the phenylboronic acid to the bromobenzene is 2: 1; the molar ratio of the aromatic ring derivative to the phenylboronic acid is 1: 20.
The polymer material containing the aggregation-induced emission group has the characteristics of electrochromism and electrochromism, so that the polymer material can be applied to the preparation of information display devices, information high-density storage devices and multiple anti-counterfeiting devices.
According to the preparation method provided by the invention, the polymer material is prepared by connecting different aromatic ring derivatives with the aggregation-induced luminescent group, the material has strong fluorescence luminescence characteristics in a solid state, and meanwhile, the appearance color and fluorescence luminescence of the polymer can be obviously changed under the stimulation of voltage, so that the double-function characteristics of electrochromism and electrochromism are shown. Therefore, the polymer material obtained by the invention can be used for preparing electrochromic and electrochromism dual-function devices, and the devices can present patterns and data with different colors by controlling the change of voltage, so that the functions of information display, information high-density storage and multiple anti-counterfeiting can be realized, and the polymer material is expected to be widely applied in the fields of intelligent display, advanced information encryption and the like.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the polymer material containing the poly-induced-luminescent-group has the characteristics of high-efficiency solid-state luminescence and obvious change of appearance color and fluorescence color under electric stimulation, and can be used for preparing devices for information display, information high-density storage and multilevel security and anti-counterfeiting;
(2) the polymer material containing the poly-aggregation induced emission group has the advantages of simple synthesis method, easily obtained raw materials and higher yield;
(3) the polymer material containing the poly-aggregation induced emission groups has obvious changes of appearance color and fluorescence emission color under electric stimulation, and can be applied to the fields of information display, information high-density storage, dynamic anti-counterfeiting and the like.
Drawings
FIG. 1 is a fluorescence spectrum obtained by testing the polymer having aggregation-inducing luminescent groups of example 1 in a mixed solvent of water and tetrahydrofuran.
FIG. 2 is a graph showing the change in absorption spectra of polymers containing aggregation-inducing luminescent groups under different voltage stimuli using example 1.
FIG. 3 is a graph showing the change of fluorescence spectra of the polymer material containing the aggregation-inducing luminescent group according to example 1 under different voltage stimuli.
FIG. 4 is a fluorescence spectrum obtained by testing the polymer material containing aggregation-inducing luminescent groups of example 2 in a mixed solvent of water and tetrahydrofuran.
FIG. 5 is a graph showing the change of absorption spectra of polymer materials containing aggregation-inducing luminescent groups under different voltage stimuli using example 2.
FIG. 6 is a graph showing the change of fluorescence spectra of polymers containing aggregation-inducing luminescent groups under different voltage stimuli using example 2.
FIG. 7 is a schematic view of the preparation of an information high density storage and anti-counterfeiting device using the polymer containing the aggregation-induced emission group of example 1 or 2.
Detailed Description
The following description of the embodiments of the present invention is provided in connection with the accompanying drawings and examples, but the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
Preparation of the polymeric Material P containing aggregation-inducing luminescent groups (TPE-TPAM):
Figure BDA0002696434390000061
the synthetic route is as follows:
Figure BDA0002696434390000062
into a 20mL polymerization tube were added 105.4mg (0.2mmol) of monomer M1, 97.5mg (0.2mmol) of monomer M2 and 8mg (0.007mmol) of catalyst Pd (PPh)3)4One drop of phase transfer catalyst methyl trioctyl ammonium chloride was added. Under nitrogen, 4mL of toluene solvent and 0.8mL of aqueous potassium carbonate solution (2M) were injected by syringe, and after 48 hours at 85 ℃, 0.1mL (1mmol) of phenylboronic acid was added, and after 12 hours at 85 ℃, 242mg (2mmol) of bromobenzene was added, and the reaction was continued at 85 ℃ for 12 hours. After the reaction is finished, adding 5mL of tetrahydrofuran for dissolving, dropwise adding the obtained polymer into a methanol solvent stirred at 1000 r/min, standing for 5min, filtering to obtain filter residue, performing Soxhlet extraction and purification, dissolving with 5mL of tetrahydrofuran, dropwise adding into the methanol solvent stirred at 1000 r/min, standing for 5min, filtering to obtain filter residue, and drying to obtain a yellow-green final product P (TPE-TPAM). The yield of the final product P (TPE-TPAM) was determined to be 60%, the weight average molecular weight was 12500 and the molecular weight distribution was 1.48. The polymer is easy to dissolve in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, toluene and the like at room temperature, and shows that the polymer has excellent solubility. The product identification data is as follows:1H NMR(500MHz,CD2Cl2),δ(TMS,ppm):7.59-7.51,7.46-7.18,7.17-6.91,6.89-6.71,3.84-3.61.
FIG. 1 is a fluorescence spectrum obtained by testing the polymer P containing aggregation-inducing luminescent groups of example 1 (TPE-TPAM) in a mixed solvent of water and tetrahydrofuran, and it can be seen from FIG. 1 that the fluorescence intensity gradually increases with the increase of water content, and an obvious aggregation-inducing luminescent phenomenon is shown.
FIG. 2 is a graph showing the change of absorption spectra of the polymer containing the aggregation-induced emission groups in example 1 under different voltage stimuli, and it can be seen from FIG. 2 that the absorption spectra show significant changes and the absorption values of short-wave portions decrease with increasing voltage; and the absorption value of the long wave part is continuously increased, and the typical electrochromic characteristic is shown.
FIG. 3 is a graph showing the change of fluorescence spectra of the polymer containing the aggregation-induced emission groups in example 1 under different voltage stimuli, and it can be seen from FIG. 3 that the fluorescence intensity in the fluorescence emission spectra is continuously reduced with the continuous increase of the voltage, thus showing the obvious characteristic of electrochromism.
Example 2
Preparation of the polymeric Material P containing aggregation-inducing luminescent groups (DPDPDPE-TPAM):
Figure BDA0002696434390000071
the synthetic route is as follows:
Figure BDA0002696434390000072
into a 20mL polymerization tube was charged 105.4mg (0.2mmol) of monomer M1,99.9mg (0.2mmol) of monomer M3 and 8mg (0.007mmol) of catalyst Pd (PPh)3)4One drop of phase transfer catalyst methyl trioctyl ammonium chloride was added. Under nitrogen, 4mL of toluene solvent and 0.8mL of aqueous potassium carbonate solution (2M) were injected by syringe, and after 48 hours at 85 ℃, 0.1mL (1mmol) of phenylboronic acid was added, and after 12 hours at 85 ℃, 242mg (2mmol) of bromobenzene was added, and the reaction was continued at 85 ℃ for 12 hours. And after the reaction is finished, adding 5mL of tetrahydrofuran for dissolving, dropwise adding the obtained polymer into a methanol solvent stirred at 1000 r/min, standing for 5min, filtering to obtain filter residue, performing Soxhlet extraction and purification, dissolving with 5mL of tetrahydrofuran, dropwise adding into the methanol solvent stirred at 1000 r/min, standing for 5min, filtering to obtain filter residue, and drying to obtain a yellow-green final product P (DPDPDPPE-TPAM). The yield of the final product P (DPDPDPPE-TPAM) was determined to be 65%, the weight average molecular weight was 15400 and the molecular weight distribution was 1.56. The polymer is easy to dissolve in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, toluene and the like at room temperature, and shows that the polymer has excellent solubility. The product identification data is as follows:1H NMR(500MHz,CDCl3),δ(TMS,ppm):7.63-7.14,7.12-6.64,6.25-6.21,3.77-3.68.
FIG. 4 is a fluorescence spectrum obtained by testing the polymer P containing aggregation-inducing luminescent group of example 2 (DPDPDPE-TPAM) in a mixed solvent of water and tetrahydrofuran, and it can be seen from FIG. 4 that the fluorescence intensity gradually increases with the increase of water content, showing a significant aggregation-inducing luminescent phenomenon.
FIG. 5 is a graph showing the change of absorption spectra of polymers containing aggregation-induced emission groups under different voltage stimuli in example 2, and it can be seen from FIG. 5 that the absorption values of the short-wave part are reduced with the increase of the voltage; and the absorption value of the long wave part is continuously increased, and the obvious electrochromic characteristic is shown.
FIG. 6 is a graph showing the change of fluorescence spectra of the polymer containing the aggregation-induced emission groups in example 2 under different voltage stimuli, and it can be seen from FIG. 6 that the fluorescence intensity in the fluorescence emission spectra is continuously reduced with the continuous increase of the voltage, thus showing the obvious characteristic of electrochromism.
Example 3
Preparation of the polymeric Material P containing aggregation-inducing luminescent groups (DPDPDPE-TPA) of this example:
Figure BDA0002696434390000081
the synthetic route is as follows:
Figure BDA0002696434390000091
99.45mg (0.2mmol) of monomer M4, 99.9mg (0.2mmol) of monomer M3 and 8mg (0.007mmol) of catalyst Pd (PPh) were charged in a 20mL polymerization tube3)4One drop of phase transfer catalyst methyl trioctyl ammonium chloride was added. Under nitrogen, 4mL of toluene solvent and 0.8mL of aqueous potassium carbonate solution (2M) were injected by syringe, and after 48 hours at 85 ℃, 0.1mL (1mmol) of phenylboronic acid was added, and after 12 hours at 85 ℃, 242mg (2mmol) of bromobenzene was added, and the reaction was continued at 85 ℃ for 12 hours. And after the reaction is finished, adding 5mL of tetrahydrofuran for dissolving, dropwise adding the obtained polymer into a methanol solvent stirred at 1000 r/min, standing for 5min, filtering to obtain filter residue, performing Soxhlet extraction and purification, dissolving with 5mL of tetrahydrofuran, dropwise adding into the methanol solvent stirred at 1000 r/min, standing for 5min, filtering to obtain filter residue, and drying to obtain a yellow-green final product P (DPDPDPPE-TPA). The final product P (DPDPDPDPE-TPA) was analyzed by assay in 68% yield, with a weight average molecular weight of 12400 and a molecular weight distribution of 1.53. The polymer is easy to dissolve in common organic solvents such as dichloromethane, chloroform, tetrahydrofuran, toluene and the like at room temperature, and shows that the polymer has excellent solubility. In a system of tetrahydrofuran and water, the fluorescence intensity is continuously increased, an obvious aggregation-induced luminescence phenomenon is shown, the fluorescence quantum efficiency is higher in a solid state, and stronger green luminescence is shown. Under the stimulation of voltage, the color and fluorescence of the polymer film can be reversibly adjusted, and obvious electrochromic and electroluminescent photochromic characteristics are represented.
Example 4
An information display device based on electrochromic and electroluminescent photochromic materials, as shown in fig. 7, comprises a glass substrate 1, a first transparent conducting layer 2, a polymer material layer 3, an electrolyte layer 4, a second transparent conducting layer 5 and a glass substrate 6 from top to bottom in sequence; according to the content of the displayed information, moulds with different shapes are arranged, the polymer material layer obtains the information of the X shape by using the moulds in a spraying mode, and the polymer in the embodiment 1 is selected as the material. The transparent conducting layer is AZO, FTO or ITO; the electrolyte layer is a gel system of acetonitrile, propylene carbonate, tetrabutyl ammonium hexafluorophosphate and polymethyl methacrylate; the device obtained by packaging can be observed under a fluorescent lamp and an ultraviolet lamp respectively to obtain information for display expression, when the voltage is 0V, the appearance color of the X is light green, the fluorescence color is stronger green, when the voltage is 1.8V, the appearance color of the X is dark brown, and the fluorescence color is in a quenching state. Under different voltages, the device can present different appearance colors and fluorescent signals, so that the effect of information display can be realized.
Example 5
A digital anti-counterfeiting device based on electrochromic and electroluminescent photochromic materials comprises a glass substrate 1, a first transparent conducting layer 2, a polymer material layer 3, an electrolyte layer 4, a second transparent conducting layer 5 and a glass substrate 6 in sequence from top to bottom as shown in figure 7; according to the content of the information, moulds with different digital shapes are arranged, the polymer material is sprayed by the moulds to obtain the information with the shape of the number 8, and the polymer in the embodiment 2 is selected as the material. The transparent conducting layer is AZO, FTO or ITO; the electrolyte layer is a gel system of acetonitrile, propylene carbonate, tetrabutylammonium perchlorate and polymethyl methacrylate; the device obtained by packaging can be respectively observed under a fluorescent lamp and an ultraviolet lamp to obtain specific digital contents, when the voltage is 0V, the appearance color of the 8 is orange, the fluorescence color is strong orange yellow, when the voltage is 1.2V, the appearance color of the 8 is dark brown, and the fluorescence color is a quenching state. Under different voltages, the device presents different appearance colors and fluorescence signals, and the digital color changes to a certain extent. Therefore, only when the accurate voltage is known, the number with specific color can be obtained, and the effect of digital multi-stage anti-counterfeiting is realized.
Example 6
An information high-density memory device based on electrochromic and electroluminescent photochromic materials, as shown in fig. 7, comprises a glass substrate 1, a first transparent conducting layer 2, a polymer material layer 3, an electrolyte layer 4, a second transparent conducting layer 5 and a glass substrate 6 from top to bottom in sequence; and arranging a mould with a plurality of square grids, and respectively coating different polymer materials by using the mould in a spraying manner, wherein the polymer materials are the polymers in the embodiments 1 and 2. The transparent conducting layer is AZO, FTO or ITO; the electrolyte layer is a gel system of acetonitrile, propylene carbonate, tetrabutyl ammonium hexafluorophosphate and polymethyl methacrylate; the device obtained by packaging is called a color code device, and under different voltages, the device can present different appearance colors and fluorescent signals, so that different color codes can be obtained. When the voltage is 0V, the appearance color of the color code is light green and orange, and the fluorescence color is stronger green and orange yellow; when the voltage is 1.2V, the appearance color of the orange grid area is dark brown, and the appearance color of the green grid area is dark green; the fluorescence color of the orange grid area is in a quenching state, and the fluorescence intensity of the green grid area is reduced to be in a dark green state. When the voltage is 1.8V, the appearance color of the orange grid area is black, and the appearance color of the green grid area is dark brown; the fluorescence color of the orange grid area is in a quenching state, and the fluorescence of the green grid area is in a quenching state. Under different voltages, the device can present different appearance colors and fluorescent signals, so that the effect of displaying various color codes can be realized. In addition, each color code can be designed through a later computer program, and specific information content can be obtained through scanning by utilizing mobile phone software. The device increases the multidimensional space of color change on the basis of a two-dimensional physical space, breaks the limitation of the physical space and realizes high-density storage of information.
The data show that the polymer is obtained by taking the monomer containing the aggregation-induced emission group and the aromatic ring derivative as raw materials, and the polymer has obvious aggregation-induced emission characteristics and electrochromic and electroluminescent photochromic performances. The device for information display, information high-density storage and safety anti-counterfeiting is prepared by solution spraying processing, and has wide application prospect in the field of intelligent organic photoelectricity.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.

Claims (10)

1. A polymer material containing aggregation-induced emission groups is characterized in that the structural formula is
Figure FDA0002696434380000011
Wherein R is an aromatic ring derivative group, and n is an integer of 2 to 200.
2. The polymer material containing a poly-aggregation-inducing luminescent group according to claim 1, wherein R is one of the following substituents 1 to 9:
Figure FDA0002696434380000012
wherein R' is hydrogen atom, tert-butyl, methoxyl, cyano, fluorine atom or alkyl chain, m is a natural number of 0-10, and is a substitution position.
3. The polymeric material containing a aggregation-inducing luminescent group according to claim 2, wherein the alkyl chain is a straight chain having 1 to 20 carbon atoms, a branched chain having 1 to 20 carbon atoms, a cyclic alkyl chain having 1 to 20 carbon atoms, an alkyl chain in which a carbon atom is substituted with an oxygen atom, an alkenyl group, an alkynyl group, an aryl group, a carbonyl group, a hydroxyl group, an amino group, a carboxyl group, a cyano group, a nitro group, or an ester group, and an alkyl chain in which a hydrogen atom is substituted with one of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
4. The polymer material containing aggregation-induced emission groups according to claim 1, wherein the material has electrochromic and electroluminescent properties.
5. A method for preparing the polymer material containing aggregation-inducing luminescent groups according to any one of claims 1 to 4, comprising the steps of:
the polymer material containing the aggregation-induced emission group is obtained by taking a monomer containing the aggregation-induced emission group and an aromatic ring derivative as raw materials, performing Suzuki-Miyaura coupling reaction, and then performing end capping by using phenylboronic acid and bromobenzene.
6. The method according to claim 5, wherein the monomer having aggregation-inducing emission group has a formula
Figure FDA0002696434380000021
7. The method according to claim 5, wherein the aromatic ring derivative is at least one of carbazole derivatives, fluorene derivatives, triphenylamine derivatives, phenothiazine derivatives and phenoxazine derivatives.
8. The method according to claim 5, wherein the molar ratio of the monomer containing an aggregation-inducing luminescent group to the aromatic ring derivative is 1: 1.
9. The method for preparing polymer material containing aggregation-inducing luminescent group according to claim 5, wherein the molar ratio of phenylboronic acid to bromobenzene is 1:1-3: 1; the molar ratio of the aromatic ring derivative to the phenylboronic acid is 1:10-1: 30.
10. Use of the polymer material containing aggregation-induced emission groups according to any one of claims 1 to 4 for the preparation of information display devices, information high-density storage devices and multiple anti-counterfeiting devices.
CN202011007471.7A 2020-09-23 2020-09-23 Polymer material containing aggregation-induced emission groups and preparation method and application thereof Active CN112250842B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011007471.7A CN112250842B (en) 2020-09-23 2020-09-23 Polymer material containing aggregation-induced emission groups and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011007471.7A CN112250842B (en) 2020-09-23 2020-09-23 Polymer material containing aggregation-induced emission groups and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN112250842A true CN112250842A (en) 2021-01-22
CN112250842B CN112250842B (en) 2021-12-21

Family

ID=74231856

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011007471.7A Active CN112250842B (en) 2020-09-23 2020-09-23 Polymer material containing aggregation-induced emission groups and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN112250842B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113683766A (en) * 2021-07-06 2021-11-23 华南理工大学 Polymer material with shape and color memory function and preparation method and application thereof
US20220334443A1 (en) * 2021-04-15 2022-10-20 Ambilight Inc. Light-emitting electrochromic device

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104031077A (en) * 2014-05-23 2014-09-10 华南理工大学 Tetraphenylethylene-containing organic semiconductor material, and preparation method and application thereof
CN109880084A (en) * 2019-02-25 2019-06-14 黑龙江大学 Conjugated polymer containing fluorine-triphenylamine structure and tetraphenyl ethylene unit and preparation method thereof and the application in electrochromism

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104031077A (en) * 2014-05-23 2014-09-10 华南理工大学 Tetraphenylethylene-containing organic semiconductor material, and preparation method and application thereof
CN109880084A (en) * 2019-02-25 2019-06-14 黑龙江大学 Conjugated polymer containing fluorine-triphenylamine structure and tetraphenyl ethylene unit and preparation method thereof and the application in electrochromism

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHU ZHIWEI ET AL.: "A comparison of ACQ, AIE and AEE-based polymers loaded on polyurethane foams as sensors for explosives detection", 《SENSORS》 *
ZIYU WANG ET AL.: "Donor-Acceptor-Type Conjugated Polymer-Based Multicolored Drug Carriers with Tunable Aggregation-Induced Emission Behavior for Self-Illuminating Cancer Therapy", 《ACS APPLIED MATERIALS & INTERFACES》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220334443A1 (en) * 2021-04-15 2022-10-20 Ambilight Inc. Light-emitting electrochromic device
US11868016B2 (en) * 2021-04-15 2024-01-09 Ambilight Inc. Light-emitting electrochromic device
CN113683766A (en) * 2021-07-06 2021-11-23 华南理工大学 Polymer material with shape and color memory function and preparation method and application thereof
CN113683766B (en) * 2021-07-06 2022-05-24 华南理工大学 Polymer material with shape and color memory function and preparation method and application thereof

Also Published As

Publication number Publication date
CN112250842B (en) 2021-12-21

Similar Documents

Publication Publication Date Title
CN112250842B (en) Polymer material containing aggregation-induced emission groups and preparation method and application thereof
Tu et al. Highly Efficient Pure‐White‐Light‐Emitting Diodes from a Single Polymer: Polyfluorene with Naphthalimide Moieties
Donuru et al. Near-infrared emissive BODIPY polymeric and copolymeric dyes
Koyuncu et al. Electrochromic and electroluminescent devices based on a novel branched quasi-dendric fluorene-carbazole-2, 5-bis (2-thienyl)-1H-pyrrole system
JP2011503260A (en) Green to transparent soluble electrochromic polymer
CN1322019C (en) Light-emitting polymer and organoelectroluminescent display using the same
Reeves et al. Dual cathodically and anodically coloring electrochromic polymer based on a spiro bipropylenedioxythiophene [(poly (spiroBiProDOT)]
Coya et al. Synthesis and tunable emission of novel polyfluorene co-polymers with 1, 8-naphthalimide pendant groups and application in a single layer–single component white emitting device
Huang et al. Corannulene-based donor–acceptor-type conjugated polymers with electrochromic properties
İçli-Özkut et al. A neutral state yellow to navy polymer electrochrome with pyrene scaffold
Cansu-Ergun et al. Carbazole based electrochromic polymers bearing ethylenedioxy and propylenedioxy scaffolds
Carbas et al. SYNTHESıS OF A NEW ELECTROCHROMıC POLYMER BASED ON TETRAPHENYLETHYLENE CORED TETRAKıS CARBAZOLE COMPLEX AND ıTS ELECTROCHROMıC DEVıCE APPLıCATıON
Asawapirom et al. Dialkylfluorene-oligothiophene and dialkylfluorene-dithienylvinylene alternating copolymers
Wen et al. Hyperbranched triazine-containing polyfluorenes: Efficient blue emitters for polymer light-emitting diodes (PLEDs)
Cai et al. Synthesis and optoelectronic properties of new polyarylates with 2-naphthyldiphenylamine units
Donuru et al. Deep‐red emissive conjugated poly (2, 6‐BODIPY‐ethynylene) s bearing alkyl side chains
Xu et al. Novel unsymmetrically hyperbranched polythiophenes with conjugation gradient
CN112430314B (en) Electrochromic polymer containing indacenodithiophene structure, preparation method, polymer film and application
Charas et al. Tuning the optoelectronic properties of polyfluorenes by copolymerisation with thiophene moieties
Qu et al. Synthesis and properties of carbazole-based hyperbranched conjugated polymers
He et al. Aggregation-enhanced emission and efficient electroluminescence of conjugated polymers containing tetraphenylethene units
KR20040036539A (en) Ladder-type and blue light emitting polymer with excellent heat stability
Bolognesi et al. From block copolymers to end-capped polymers: A suitable method to control the electro-optical properties of polymeric materials
CN1151187C (en) Copolymer type conjugated polymer whose main chain contains double bond, its preparation method and application
Yassar et al. Synthesis and photovoltaic properties of mono-substituted quaterthiophenes bearing strong electron-withdrawing group

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant