CN109400836B - Preparation method and application of polyurethane derivative containing triarylamine structure and tetraphenylethylene group - Google Patents

Preparation method and application of polyurethane derivative containing triarylamine structure and tetraphenylethylene group Download PDF

Info

Publication number
CN109400836B
CN109400836B CN201811489724.1A CN201811489724A CN109400836B CN 109400836 B CN109400836 B CN 109400836B CN 201811489724 A CN201811489724 A CN 201811489724A CN 109400836 B CN109400836 B CN 109400836B
Authority
CN
China
Prior art keywords
tetraphenylethylene
polyurethane
bis
aminophenyl
polyurethane derivative
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.)
Active
Application number
CN201811489724.1A
Other languages
Chinese (zh)
Other versions
CN109400836A (en
Inventor
牛海军
张旭
路庆义
杨彩誉
张薇
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.)
Heilongjiang University
Original Assignee
Heilongjiang University
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 Heilongjiang University filed Critical Heilongjiang University
Priority to CN201811489724.1A priority Critical patent/CN109400836B/en
Publication of CN109400836A publication Critical patent/CN109400836A/en
Application granted granted Critical
Publication of CN109400836B publication Critical patent/CN109400836B/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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/675—Low-molecular-weight compounds
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3237—Polyamines aromatic
    • C08G18/3243—Polyamines aromatic containing two or more aromatic rings
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • 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

Abstract

The invention relates to a preparation method and application of a polyurethane derivative containing a triarylamine structure and a tetraphenylethylene group, and relates to a polyurethane derivative containing a triarylamine structure and a tetraphenylethylene group, and a preparation method and application thereof. The invention aims to solve the problem that the existing multifunctional material has few functional types. The invention firstly synthesizes diamine monomer and 1, 2-bis (4-hydroxyphenyl) -1, 2-diphenylethylene containing hydroxyl structure, and simultaneously introduces 4, 4' -diphenylmethane diisocyanate, and the diamine monomer is prepared by means of copolymerization. The material has electrochromic and fluorescence sensing hole transmission functions, and can be used as automobile rearview mirror materials and display materials; and can be used for preparing explosive detection and memory performance devices. The invention is applied to the field of multifunctional materials.

Description

Preparation method and application of polyurethane derivative containing triarylamine structure and tetraphenylethylene group
Technical Field
The invention relates to a polyurethane derivative containing a triarylamine structure and a tetraphenylethylene group, and a preparation method and application thereof.
Background
Polyurethanes (PU) have many desirable properties, such as better flexibility, greater tensile strength, greater hardness, greater resistance to chemical solvents and temperature conditions, greater abrasion resistance, greater oil resistance, and longer fatigue life. Polyurethanes are also potential candidates for film preparation due to good mechanical and chemical properties. Although the polyurethane has excellent comprehensive performance, the traditional PU has some defects, such as high processing difficulty, poor solubility and the like, which greatly limits the application of the polyurethane material in industry. Therefore, in recent years, more and more researchers are concerned about the research on the preparation and modification of polyurethane and the application of related materials.
Multifunctional materials are rapidly evolving by virtue of their excellent capabilities for use in sensors, actuators, memory devices and high contrast displays. External stimuli such as chemicals, acids and bases, temperature, light and electricity can change the chemical or physical properties of these materials. A common method for preparing multi-stimulus responsive materials is to introduce groups with special functions and sensitivity on the same molecular skeleton. In the last decade, despite great advances in this area, the simultaneous synthesis of polymers with more than three functions remains a challenge.
Disclosure of Invention
The invention provides a polyurethane derivative containing a triarylamine structure and a tetraphenylethylene group, a preparation method and application thereof, aiming at solving the problem that the existing multifunctional material has few functional types.
The invention relates to a polyurethane derivative containing a triarylamine structure and a tetraphenylethylene group, which is characterized in that the polyurethane derivative containing the triarylamine structure and the tetraphenylethylene group is a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and a tetraphenylethylene group or a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine group and a tetraphenylethylene group;
wherein the structural formula of the polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene groups is as follows:
Figure GDA0002740600470000011
wherein n is an integer of 3-10;
the structural formula of the polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine group and tetraphenylethylene group is as follows:
Figure GDA0002740600470000021
wherein n is an integer of 3 to 10.
The method for preparing the polyurethane derivative containing the triarylamine structure and the tetraphenylethylene group comprises the following steps: mixing 1, 2-bis (4-hydroxyphenyl) -1, 2-diphenylethylene, 4' -diphenylmethane diisocyanate and a solvent N, N-dimethylacetamide, and stirring and refluxing for 5-15h at the room temperature at the stirring speed of 800-900 r/min to obtain a precursor; adding diamine monomer containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine or N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine into the precursor prepared in the first step, heating to 70-120 ℃, stirring and refluxing for 5-15h, cooling, pouring into methanol, filtering, and drying the obtained solid phase in vacuum to obtain the polyurethane derivative containing the triarylamine structure and the tetraphenylethylene group;
wherein the molar ratio of diamine monomer containing N, N ' -bis (4-aminophenyl) -N, N ' -di-2-naphthyl-1, 4-phenylenediamine or N, N ' -bis (4-aminophenyl) -N, N ' -di-2-naphthyl-1, 4-biphenyldiamine, 1, 2-bis (4-hydroxyphenyl) -1, 2-diphenylethylene and 4,4 ' -diphenylmethane diisocyanate is (0.5-2.5) to 1: 2;
the volume mass ratio of the solvent N, N-dimethylacetamide to the diamine monomer containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine or N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine is (10-30) mL (0.5-2.5) g.
The invention relates to an application of a polyurethane derivative containing a triarylamine structure and a tetraphenylethylene group as an electrochromic material.
The invention relates to application of a polyurethane derivative containing a triarylamine structure and a tetraphenylethylene group as an electroluminescent material.
The invention relates to application of a polyurethane derivative containing a triarylamine structure and a tetraphenylethylene group as an explosive detection material.
The invention has the beneficial effects that:
the triarylamine groups with destroyed accumulation performance are introduced into the polyurethane structure, so that the high thermal stability of the original polyurethane can be maintained, the solubility of the triarylamine groups can be increased, the film forming capability is enhanced, the manufacturing of a large-area thin film electrochromic device is facilitated, and an electroactive center is provided to promote the treatment and application of the electrochromic device; tetraphenylethylenes (TPEs) containing four rotatable phenyl rings have been well developed for their Aggregation Induced Emission (AIE) activity. TPE derivatives can overcome the problem of quenching (ACQ) caused by aggregation of conventional organic luminophores, which greatly facilitates their various applications in bioprobes, chemical sensing and optoelectronic devices. The polyurethane derivative prepared by the invention takes the propeller type triarylamine as a monomer, can effectively reduce the strong acting force between polymer molecular chains, increases the solubility of the polymer, and simultaneously the triarylamine is easy to form the triarylamine with cationic free radicals which are different from a neutral state. The polyurethane derivative containing triarylamine structure and tetraphenylethylene group has high-temperature resistance, the decomposition temperature is above 350 ℃ in nitrogen atmosphere, and the polyurethane derivative is suitable for being used in devices. The polyurethane derivative material containing triarylamine structure and tetraphenylethylene group is prepared into a film, so that the film does not have large aggregation phenomenon and crushing phenomenon on an ITO substrate, and has good wetting capacity on the ITO substrate. This means that the prepared polyurethane derivative material containing triarylamine structure and tetraphenylethylene group has good film forming property, and can be used for preparing large-area thin films. After voltage is applied, the transmittance of the film can still reach 50%, the transparency is good, and the polymer film can keep good stability of the circulating ring in the voltage application process, can be circulated for more than 20 times and has unchanged transparency.
The polyurethane derivative containing triarylamine structure and tetraphenylethylene group has the following advantages in practical application that (1) the polyurethane derivative has good electrochemical redox reversibility, and can still keep reversibility after dozens of redox cycles; (2) the response time of color change is fast, and the color can be changed rapidly within 2 seconds after voltage is applied; (3) the change in color is reversible; (4) the color change sensitivity is high; (5) the cycle life is longer; (6) the color-changing material has a storage memory function, can be stably kept in an original state or a state after color changing before and after response, can be maintained for months to years after color changing, and can be kept unchanged for half a year after electrochromism in the experiment; (7) the material has the color change before and afterBetter chemical stability, and the product can exist stably in the air at normal temperature and normal pressure. (8) Has response to explosive TNT and picric acid, and has detectable concentration of 1 × 10 for both picric acid and TNT-12mol/L, good sensitivity. (9) The fluorescence switch has good electroluminescent property, the fluorescence intensity of the fluorescence switch can be quenched in the process of applying voltage, the contrast ratio of the fluorescence switch can reach more than 100, and the fluorescence switch has great application potential in the aspects of intelligent photoelectricity and sensors (10), has good photoelectric response capability and keeps stable in the cycle process of 500 s.
In conclusion, the polyurethane derivative containing triarylamine structure and tetraphenylethylene group has 10 functions.
Drawings
FIG. 1 is a hydrogen nuclear magnetic spectrum of a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene groups prepared in example one;
FIG. 2 is a cyclic voltammogram of a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene groups prepared in example one;
FIG. 3 is a graph of the stability and transmittance of polyurethane derivatives containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene groups prepared in example one after application of a voltage;
FIG. 4 is an electrochromic diagram of a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene groups prepared in example one;
FIG. 5 is an electroluminescence chart of a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene groups prepared in example one;
FIG. 6 is a graph showing the thermogravimetry of polyurethane derivatives containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene groups prepared in example one;
FIG. 7 is a graph showing the aggregation induction of the polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene group prepared in example one;
FIG. 8 is a graph showing the detection of picric acid, which is a p-explosive substance, of a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and a tetraphenylethylene group, prepared in example one;
FIG. 9 is a graph showing the detection of a p-explosive TNT of a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and a tetraphenylethylene group, prepared in example one;
FIG. 10 is a graph of the memory properties of polyurethane derivatives containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene groups prepared in example one.
FIG. 11 is a graph of the optoelectronic properties of the polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene groups prepared in example one;
FIG. 12 is a hydrogen nuclear magnetic spectrum of a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine groups and tetraphenylethylene groups prepared in example two;
FIG. 13 is a cyclic voltammogram of a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine group and a tetraphenylethylene group prepared in example two;
FIG. 14 is a graph of the stability and transmittance of polyurethane derivatives containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine groups and tetraphenylethylene groups prepared in example two after application of a voltage;
FIG. 15 is an electrochromic diagram of a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine groups and tetraphenylethylene groups prepared in example two;
FIG. 16 is an electroluminescent plot of a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine group and a tetraphenylethylene group prepared in example two;
FIG. 17 is a graph showing the thermogravimetric curves of the polyurethane derivatives containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine groups and tetraphenylethylene groups prepared in example II;
FIG. 18 is an aggregation induction map of a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine group and tetraphenylethylene group prepared in example two;
FIG. 19 is a graph showing the detection of picric acid, which is a p-explosive substance, of the polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine group and tetraphenylethylene group prepared in example II;
FIG. 20 is a graph showing the detection of p-explosive TNT of a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine group and tetraphenylethylene group prepared in example II;
FIG. 21 is a graph showing the memory properties of polyurethane derivatives containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine groups and tetraphenylethylene groups prepared in example II;
FIG. 22 is a graph showing the photoelectric properties of the polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine group and tetraphenylethylene group prepared in example II.
Detailed Description
The technical solution of the present invention is not limited to the specific embodiments listed below, and includes any combination of the specific embodiments.
The first embodiment is as follows: the polyurethane derivative containing a triarylamine structure and a tetraphenylethylene group in the present embodiment is characterized in that the polyurethane derivative containing a triarylamine structure and a tetraphenylethylene group is a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and a tetraphenylethylene group or a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine group and a tetraphenylethylene group;
wherein the structural formula of the polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene groups is as follows:
Figure GDA0002740600470000051
wherein n is an integer of 3-10;
the structural formula of the polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine group and tetraphenylethylene group is as follows:
Figure GDA0002740600470000052
wherein n is an integer of 3 to 10.
In the embodiment, the triarylamine groups with the destroyed accumulation performance are introduced into the polyurethane structure, so that the high thermal stability of the original polyurethane can be maintained, the solubility of the triarylamine groups can be increased, the film forming capability is enhanced, the manufacturing of a large-area thin film electrochromic device is facilitated, and an electroactive center is provided to promote the treatment and application of the electrochromic device; tetraphenylethylenes (TPEs) containing four rotatable phenyl rings have been well developed for their Aggregation Induced Emission (AIE) activity. TPE derivatives can overcome the problem of quenching (ACQ) caused by aggregation of conventional organic luminophores, which greatly facilitates their various applications in bioprobes, chemical sensing and optoelectronic devices. The polyurethane derivative prepared by the embodiment takes the propeller type triarylamine as a monomer, so that the strong acting force between polymer molecular chains can be effectively reduced, the solubility of the polymer is increased, and meanwhile, the triarylamine is easy to form the triarylamine with a cationic free radical which is different from a neutral state. The polyurethane derivative containing a triarylamine structure and a tetraphenylethylene group in this embodiment has high heat resistance, and is generally suitable for use in devices because the decomposition temperature is 350 ℃ or higher in a nitrogen atmosphere. The polyurethane derivative material containing triarylamine structure and tetraphenylethylene group in the embodiment is made into a film, so that the film has no large aggregation phenomenon and breakage phenomenon on an ITO substrate, and also has good wetting capacity on the ITO substrate. This means that the prepared polyurethane derivative material containing triarylamine structure and tetraphenylethylene group has good film forming property, and can be used for preparing large-area thin films. After voltage is applied, the transmittance of the film can still reach 50%, the transparency is good, and the polymer film can keep good stability of the circulating ring in the voltage application process, can be circulated for more than 20 times and has unchanged transparency.
The polyurethane derivative containing the triarylamine structure and the tetraphenylethylene group has the advantages that (1) the polyurethane derivative has good electrochemical redox reversibility and can still keep reversibility after dozens of redox cycles; (2) the response time of color change is fast, and the color can be changed rapidly within 2 seconds after voltage is applied; (3) the change in color is reversible; (4) the color change sensitivity is high; (5) the cycle life is longer; (6) the color-changing material has a storage memory function, can be stably kept in an original state or a state after color changing before and after response, can be maintained for months to years after color changing, and can be kept unchanged for half a year after electrochromism in the experiment; (7) the material has better chemical stability before and after color change, and can stably exist in the air at normal temperature and normal pressure. (8) Has response to explosive TNT and picric acid, and has detectable concentration of 1 × 10 for both picric acid and TNT-12mol/L, good sensitivity. (9) The fluorescence switch has good electroluminescent property, the fluorescence intensity of the fluorescence switch can be quenched in the process of applying voltage, the contrast ratio of the fluorescence switch can reach more than 100, and the fluorescence switch has great application potential in the aspects of intelligent photoelectricity and sensors (10), has good photoelectric response capability and keeps stable in the cycle process of 500 s.
The polyurethane derivative containing a triarylamine structure and a tetraphenylethylene group according to this embodiment has ten functions.
The second embodiment is as follows: the method for preparing the polyurethane derivative containing the triarylamine structure and the tetraphenylethylene group comprises the following steps: mixing 1, 2-bis (4-hydroxyphenyl) -1, 2-diphenylethylene, 4' -diphenylmethane diisocyanate and a solvent N, N-Dimethylacetamide (DMAC), stirring and refluxing for 5-15h at room temperature at the stirring speed of 800-900 r/min to obtain a precursor; adding diamine monomer containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine or N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine into the precursor prepared in the first step, heating to 70-120 ℃, stirring and refluxing for 5-15h, cooling, pouring into methanol, filtering, and drying the obtained solid phase in vacuum to obtain the polyurethane derivative containing the triarylamine structure and the tetraphenylethylene group;
wherein the molar ratio of diamine monomer containing N, N ' -bis (4-aminophenyl) -N, N ' -di-2-naphthyl-1, 4-phenylenediamine or N, N ' -bis (4-aminophenyl) -N, N ' -di-2-naphthyl-1, 4-biphenyldiamine, 1, 2-bis (4-hydroxyphenyl) -1, 2-diphenylethylene and 4,4 ' -diphenylmethane diisocyanate is (0.5-2.5) to 1: 2;
the volume mass ratio of the solvent N, N-Dimethylacetamide (DMAC) to the diamine monomer having N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine or N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine is (10-30) mL (0.5-2.5) g.
The third concrete implementation mode: the second embodiment is different from the first embodiment in that: diamine monomer containing N, N ' -bis (4-aminophenyl) -N, N ' -di-2-naphthyl-1, 4-phenylenediamine or N, N ' -bis (4-aminophenyl) -N, N ' -di-2-naphthyl-1, 4-biphenyldiamine, 1, 2-bis (4-hydroxyphenyl) -1, 2-diphenylethylene and 4,4 ' -diphenylmethane diisocyanate in a molar ratio of 2:1: 2. The rest is the same as the second embodiment.
The fourth concrete implementation mode: the second or third embodiment is different from the first or second embodiment in that: in the second step, the molar ratio of diamine monomer containing N, N ' -bis (4-aminophenyl) -N, N ' -di-2-naphthyl-1, 4-phenylenediamine or N, N ' -bis (4-aminophenyl) -N, N ' -di-2-naphthyl-1, 4-biphenyldiamine, 1, 2-bis (4-hydroxyphenyl) -1, 2-diphenylethylene, 4 ' -diphenylmethane diisocyanate, solvent N, N-Dimethylacetamide (DMAC) is 1: 1: 2: 20. the other embodiments are the same as the second or third embodiment.
The fifth concrete implementation mode: the embodiment mode provides application of the polyurethane derivative containing triarylamine structure and tetraphenylethylene group as an electrochromic material.
The sixth specific implementation mode: the fifth embodiment is different from the fifth embodiment in that: the application method of the polyurethane derivative containing triarylamine structure and tetraphenylethylene group as the electrochromic material comprises the following steps: dissolving a polyurethane derivative containing a triarylamine structure and a tetraphenylethylene group in an organic solvent to obtain a polyurethane derivative solution, and then coating the polyurethane derivative solution on conductive glass to obtain an electrochromic material; wherein the organic solvent is tetrahydrofuran, chloroform, N '-dimethylacetamide, N' -dimethylformamide or N-methylpyrrolidone. The rest is the same as the fifth embodiment.
The seventh embodiment: the embodiment mode provides application of the polyurethane derivative containing triarylamine structure and tetraphenylethylene group as an electroluminescent material.
The specific implementation mode is eight: the fifth embodiment is different from the fifth embodiment in that: the application method of the polyurethane derivative containing triarylamine structure and tetraphenylethylene group as the electroluminescent material is as follows: dissolving a polyurethane derivative containing a triarylamine structure and a tetraphenylethylene group in an organic solvent to obtain a polyurethane derivative solution, and then coating the polyurethane derivative solution on conductive glass to obtain an electroluminescent material; wherein the organic solvent is tetrahydrofuran, chloroform, N '-dimethylacetamide, N' -dimethylformamide or N-methylpyrrolidone. The rest is the same as the seventh embodiment.
The specific implementation method nine: the embodiment of the invention relates to application of a polyurethane derivative containing a triarylamine structure and a tetraphenylethylene group as an explosive detection material.
The detailed implementation mode is ten: the present embodiment differs from the ninth embodiment in that: the application method of the polyurethane derivative containing the triarylamine structure and the tetraphenylethylene group as the explosive detection comprises the following steps: dissolving a polyurethane derivative containing a triarylamine structure and a tetraphenylethylene group in an organic solvent to obtain a polyurethane derivative solution, then dropwise adding a solution containing explosives into the polyurethane derivative solution, and detecting whether the explosives exist in the solution by using the change of the fluorescence intensity of the solution. The rest is the same as in the ninth embodiment.
In the explosive of the embodiment, the detectable concentrations of picric acid and TNT are both 1 × 10-12mol/L, good sensitivity.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows: the preparation method of the polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene groups comprises the following steps: mixing 1, 2-bis (4-hydroxyphenyl) -1, 2-diphenylethylene (5mmol,0.2g) and 4, 4' -diphenylmethane diisocyanate (10mmol,0.25g) with 10mL of N, N-Dimethylacetamide (DMAC) solvent, and stirring and refluxing for 10h at room temperature at the stirring speed of 800r/min to obtain a precursor; then adding N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine (10mmol,0.6g) into the prepared precursor, heating to 80 ℃, stirring and refluxing for 10h, cooling, pouring into methanol, filtering, and drying the obtained solid phase in vacuum to obtain the polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene; the chemical structural formula is as follows:
Figure GDA0002740600470000081
wherein n is an integer of 3 to 10.
The application method of the polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene group as the electrochromic material is as follows: dissolving a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene groups in an organic solvent to obtain a polyurethane derivative solution, and then coating the polyurethane derivative solution on conductive glass to obtain an electrochromic material; wherein the organic solvent is tetrahydrofuran, chloroform, N '-dimethylacetamide, N' -dimethylformamide or N-methylpyrrolidone.
The application method of the polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene group as the electroluminescent material is as follows: dissolving a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene groups in an organic solvent to obtain a polyurethane derivative solution, and then coating the polyurethane derivative solution on conductive glass to obtain an electroluminescent material; wherein the organic solvent is tetrahydrofuran, chloroform, N '-dimethylacetamide, N' -dimethylformamide or N-methylpyrrolidone.
The application method of the polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene groups as the explosive detection comprises the following steps: dissolving a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene groups in an organic solvent to obtain a polyurethane derivative solution, then dropwise adding a solution containing explosives into the polyurethane derivative solution, and detecting whether the explosives exist in the solution by using the change of the fluorescence intensity of the solution. In this example, the detectable concentrations of picric acid and TNT in the explosive were 1X 10-12mol/L, good sensitivity.
The performance of a film coated with a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene groups was tested:
FIG. 1 is a hydrogen nuclear magnetic spectrum of a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene groups prepared in example one; as can be seen from the figure 1 of the drawings,1H-NMR (DMSO, TMS): the peak at δ ═ 9.33ppm is the chemical shift of H on CO — NH, and δ ═ 6.4 to 7.30ppm is the chemical shift of H on the benzene ring, and it is considered that in example one, a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and a tetraphenylethylene group was synthesized.
FIG. 2 is a cyclic voltammogram of a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene groups prepared in example one; as can be seen from FIG. 2, two oxidation peaks appear at 1.10V/1.50V and two reduction peaks appear at 0.90V/1.20V, respectively.
FIG. 3 is a graph of the stability and transmittance of polyurethane derivatives containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene groups prepared in example one after application of a voltage; as can be seen from fig. 3, after voltage application, the transmittance of the polyurethane derivative film containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene groups still reached 60%, indicating that the transparency was good, and the polymer film could maintain good stability of the cyclic ring during voltage application, and could be cycled for more than 20 cycles without change in transparency.
FIG. 4 is an electrochromic diagram of a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene groups prepared in example one; as can be seen from FIG. 4, the polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene group prepared in example one had an absorption peak at 360nm before no voltage was applied, and when the voltage was applied from 0.0V to 1.6V, the absorption peak at 360nm gradually increased, and a new absorption peak appeared at 465/645 and gradually increased; the electrochromic colors all range from light yellow to dark blue.
FIG. 5 is an electroluminescence chart of a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene groups prepared in example one; the fluorescence intensity reaches the highest level before no voltage is applied, and gradually decreases from 0.0V to 1.5V with the applied voltage, and finally approaches to zero.
FIG. 6 is a graph showing the thermogravimetry of polyurethane derivatives containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene groups prepared in example one; as can be seen from fig. 6, the polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene group prepared in example one starts to lose a large amount of weight at about 400 ℃, when the temperature is 410 ℃, the amount of weight loss is 5%, and when the temperature is 450 ℃, the amount of weight loss is 10%; when the temperature is 611 ℃, the weight loss is 20%, and when the temperature reaches 800 ℃, the carbon residual amount of the polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene groups prepared in the first example is 59%, so that the polyurethane derivative has better high-temperature resistance.
FIG. 7 is a graph showing the aggregation-induced emission effect of a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene groups prepared in example one; it can be seen from FIG. 7 that the fluorescence intensity of the polymer gradually increases as the mass fraction of water increases; wherein a is 80%, b is 60%, c is 40%, d is 20%, and e is 0%.
FIG. 8 is a fluorescence plot of the response of the polyurethane derivatives containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene groups prepared in example one to picric acid; it can be seen from FIG. 8 that the fluorescence intensity of the polymer solution gradually decreased with increasing picric acid concentration.
FIG. 9 is a fluorescence plot of the response of the polyurethane derivatives containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene groups prepared in example one to TNT; it can be seen from fig. 9 that the fluorescence intensity of the polymer solution gradually decreased as the concentration of TNT increased.
FIG. 10 is a graph of the memory properties of polyurethane derivatives containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene groups prepared in example one; it can be seen from fig. 10 that in the first voltage sweep, from 0 to-6V (sweep 1), a sharp increase in current is observed when the negative threshold voltage is-1.0V and the memory device switches from the low conductivity state (OFF) to the high conductivity state (ON). This conversion process can be used as a "write" process for ITO/PI/Al devices. During the next scan (scan 2), the current is still in the ON state and the device remains in the high ON state. In the third scan from 0 to +6V (scan 3), we observed a sudden drop in current at a threshold voltage of +3.9V, indicating that the memory device underwent a transition from the ON state to the original OFF state. This transition from ON to OFF may be as an "erase" process. As forward bias is applied, the current remains in the low on state in the subsequent voltage sweep (sweep 4). Thus, the memory devices manufactured with PU are binary flash data storage devices.
FIG. 11 is a graph of the optoelectronic properties of the polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine and tetraphenylethylene groups prepared in example one; it can be seen from fig. 11 that the photoelectric properties of the polymer are very stable under light and dark conditions.
Example two, a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine groups and tetraphenylethylene groups was prepared by the following method: mixing 1, 2-bis (4-hydroxyphenyl) -1, 2-diphenylethylene (5mmol,0.2g) and 4, 4' -diphenylmethane diisocyanate (10mmol,0.25g) with 10mL of N, N-Dimethylacetamide (DMAC) solvent, and stirring and refluxing for 10h at room temperature at the stirring speed of 800r/min to obtain a precursor; then adding diamine monomer (10mmol,0.68g) containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine into the precursor prepared previously, heating to 80 ℃, stirring and refluxing for 10h, cooling, pouring into methanol, filtering, and carrying out vacuum drying on the obtained solid phase to obtain the polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine group and tetraphenylethylene group; the chemical structural formula is as follows:
Figure GDA0002740600470000111
wherein n is an integer of 3 to 10.
The application method of the polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine group and tetraphenylethylene group as the electrochromic material is as follows: dissolving a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine group and tetraphenylethylene group in an organic solvent to obtain a polyurethane derivative solution, and then coating the polyurethane derivative solution on conductive glass to obtain an electrochromic material; wherein the organic solvent is tetrahydrofuran, chloroform, N '-dimethylacetamide, N' -dimethylformamide or N-methylpyrrolidone.
The application method of the polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine group and tetraphenylethylene group as the electroluminescent material is as follows: dissolving a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine group and tetraphenylethylene group in an organic solvent to obtain a polyurethane derivative solution, and then coating the polyurethane derivative solution on conductive glass to obtain an electroluminescent material; wherein the organic solvent is tetrahydrofuran, chloroform, N '-dimethylacetamide, N' -dimethylformamide or N-methylpyrrolidone.
The application method of the polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine group and tetraphenylethylene group as the explosive detection comprises the following steps: dissolving a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine group and tetraphenylethylene group in an organic solvent to obtain a polyurethane derivative solution, then dropwise adding a solution containing explosives into the polyurethane derivative solution, and detecting whether the explosives exist in the solution by using the change of the fluorescence intensity of the solution. In this example, the detectable concentrations of picric acid and TNT in the explosive were 1X 10- 12mol/L, good sensitivity.
The polyurethane derivatives containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine groups and tetraphenylethylene groups were coated to form films, and their properties were tested:
FIG. 12 is a hydrogen nuclear magnetic spectrum of a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine groups and tetraphenylethylene groups prepared in example two; as can be seen from the graph of figure 12,1H-NMR (DMSO, TMS): the peak at δ ═ 9.33ppm is the chemical shift of H on CO — NH, and δ ═ 6.4 to 7.30ppm is the chemical shift of H on the benzene ring, and it is considered that in example one, a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine group and tetraphenylethylene group was synthesized.
FIG. 13 is a cyclic voltammogram of a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine group and a tetraphenylethylene group prepared in example two; as can be seen from FIG. 13, two oxidation peaks appear at 1.27V/1.47V, and two reduction peaks appear at 0.60V/0.95V, respectively.
FIG. 14 is a graph of the stability and transmittance of polyurethane derivatives containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine groups and tetraphenylethylene groups prepared in example two after application of a voltage; as can be seen from fig. 14, after voltage is applied, the transmittance of the polyurethane derivative film containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine group and tetraphenylethylene group can still reach 35%, which indicates that the transparency is relatively good, and the polymer film can maintain good stability of the circulating ring during the voltage application process, can be circulated for more than 20 times and has no change in transparency.
FIG. 15 is an electrochromic diagram of a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine groups and tetraphenylethylene groups prepared in example two; as can be seen from FIG. 15, the polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine group and tetraphenylethylene group prepared in example II had an absorption peak at 347nm before no voltage was applied, and when the applied voltage was from 0.0V to 1.6V, the absorption peak at 347nm gradually rose, and a new absorption peak appeared at 485/650nm and gradually rose; the electrochromic colors all range from light yellow to dark blue.
FIG. 16 is an electroluminescent plot of a polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine group and a tetraphenylethylene group prepared in example two; the fluorescence intensity reaches the highest level before no voltage is applied, and gradually decreases from 0.0V to 1.5V with the applied voltage, and finally approaches to zero.
FIG. 17 is a graph showing the thermogravimetric curves of the polyurethane derivatives containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine groups and tetraphenylethylene groups prepared in example II; as can be seen from fig. 17, the polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine group and tetraphenylethylene group prepared in example one starts to lose a large amount of weight at about 400 ℃, when the temperature is 410 ℃, the amount of weight loss is 5%, and when the temperature is 450 ℃, the amount of weight loss is 10%; when the temperature is 611 ℃, the weight loss amount is 20%, and when the temperature reaches 800 ℃, the carbon residual amount of the polyurethane derivative containing the N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine group and the tetraphenylethylene group prepared in example two is 59%, so that the polyurethane derivative has better high temperature resistance.
FIG. 18 is a graph showing the aggregation-induced emission effect of the polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine group and tetraphenylethylene group prepared in example II; it can be seen from fig. 18 that the fluorescence intensity of the polymer gradually increased as the mass fraction of water increased.
FIG. 19 is a fluorescent plot of the response of the polyurethane derivatives containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine groups and tetraphenylethylene groups prepared in example two to picric acid; it can be seen from FIG. 19 that the fluorescence intensity of the polymer solution gradually decreased with increasing picric acid concentration.
FIG. 20 is a fluorescent plot of the response of the polyurethane derivatives containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine groups and tetraphenylethylene groups prepared in example two to TNT; it can be seen from fig. 20 that the fluorescence intensity of the polymer solution gradually decreased as the concentration of TNT increased.
FIG. 21 is a graph showing the memory properties of polyurethane derivatives containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine groups and tetraphenylethylene groups prepared in example II; it can be seen from fig. 21 that in the first voltage sweep, from 0 to-6V (sweep 1), a sharp increase in current is observed when the negative threshold voltage is-2.0V and the memory device switches from the low conductivity state (OFF) to the high conductivity state (ON). This conversion process can be used as a "write" process for ITO/PI/Al devices. During the next scan (scan 2), the current is still in the ON state and the device remains in the high ON state. In the third scan from 0 to +6V (scan 3), a sudden drop in current at a threshold voltage of +4.0V indicates that the memory device is undergoing a transition from the ON state to the original OFF state. This transition from ON to OFF may be as an "erase" process. As forward bias is applied, the current remains in the low on state in the subsequent voltage sweep (sweep 4). Thus, the memory devices manufactured with PU are binary flash data storage devices.
FIG. 22 is a graph showing the photoelectric properties of the polyurethane derivative containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine group and tetraphenylethylene group prepared in example II; it can be seen from fig. 22 that the photoelectric properties of the polymer are very stable under light and dark conditions.
As a result of testing the solubility of the polyurethane derivatives containing a triarylamine structure and a tetraphenylethylene group, as shown in table 1, it was found from table 1 that the polyurethane derivatives containing a triarylamine structure and a tetraphenylethylene group of the examples had good solubility.
TABLE 1
Figure GDA0002740600470000141
The experiments of the first and second examples show that the triarylamine groups with the stacking failure performance are introduced into the polyurethane structure, so that the high thermal stability of the original polyurethane can be maintained, the solubility of the polyurethane can be increased, the film forming capability is enhanced, the large-area thin-film electrochromic device can be manufactured, and an electroactive center is provided to promote the treatment and application of the electrochromic device; tetraphenylethylenes (TPEs) containing four rotatable phenyl rings have been well developed for their Aggregation Induced Emission (AIE) activity. TPE derivatives can overcome the problem of quenching (ACQ) caused by aggregation of conventional organic luminophores, which greatly facilitates their various applications in bioprobes, chemical sensing and optoelectronic devices. The polyurethane derivative prepared by the embodiment takes the propeller type triarylamine as a monomer, so that the strong acting force between polymer molecular chains can be effectively reduced, the solubility of the polymer is increased, and meanwhile, the triarylamine is easy to form the triarylamine with a cationic free radical which is different from a neutral state. The polyurethane derivative containing triarylamine structure and tetraphenylethylene group in this embodiment has high temperature resistance, generally has a decomposition temperature of 350 ℃ or higher in a nitrogen atmosphere, and is suitable for use in devices. The polyurethane derivative material containing triarylamine structure and tetraphenylethylene group in the embodiment is prepared into a film, so that the film does not have large aggregation phenomenon and crushing phenomenon on an ITO substrate, and also shows good wetting ability on the ITO substrate. This means that the polyurethane derivative material containing a triarylamine structure and a tetraphenylethylene group has good film-forming characteristics and can be used for producing a large-area thin film. After voltage is applied, the transmittance of the film can still reach 50%, the transparency is good, and the polymer film can keep good stability of the circulating ring in the voltage application process, can be circulated for more than 20 times and has unchanged transparency.
The polyurethane derivative containing the triarylamine structure and the tetraphenylethylene group has the following advantages in practical application, namely (1) the polyurethane derivative has good electrochemical redox reversibility, and can still keep reversibility after dozens of redox cycles; (2) the response time of color change is fast, and the color can be changed rapidly within 2 seconds after voltage is applied; (3) the change in color is reversible; (4) the color change sensitivity is high; (5) the cycle life is longer; (6) the color-changing material has a storage memory function, can be stably kept in an original state or a state after color changing before and after response, can be maintained for months to years after color changing, and can be kept unchanged for half a year after electrochromism in the experiment; (7) the material has better chemical stability before and after color change, and can stably exist in the air at normal temperature and normal pressure. (8) Picric acid responds to the explosive TNT. (9) The fluorescence switch has good electroluminescent property, the fluorescence intensity of the fluorescence switch can be quenched in the process of applying voltage, the contrast ratio of the fluorescence switch can reach more than 100, and the fluorescence switch has great application potential in the aspects of intelligent photoelectricity and sensors (10), has good photoelectric response capability and keeps stable in the cycle process of 500 s.
In summary, the polyurethane derivatives containing triarylamine structure and tetraphenylethylene group prepared in the first and second examples have ten functions, and multifunctional materials with more functional types are prepared.

Claims (8)

1. The preparation method of the polyurethane derivative containing triarylamine structure and tetraphenylethylene group is characterized by comprising the following steps: mixing 1, 2-bis (4-hydroxyphenyl) -1, 2-diphenylethylene, 4' -diphenylmethane diisocyanate and a solvent N, N-dimethylacetamide, and stirring and refluxing for 5-15h at the room temperature at the stirring speed of 800-900 r/min to obtain a precursor; adding diamine monomer containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine or N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine into the precursor prepared in the first step, heating to 70-120 ℃, stirring and refluxing for 5-15h, cooling, pouring into methanol, filtering, and drying the obtained solid phase in vacuum to obtain the polyurethane derivative containing the triarylamine structure and the tetraphenylethylene group;
wherein the molar ratio of diamine monomer containing N, N ' -bis (4-aminophenyl) -N, N ' -di-2-naphthyl-1, 4-phenylenediamine or N, N ' -bis (4-aminophenyl) -N, N ' -di-2-naphthyl-1, 4-biphenyldiamine, 1, 2-bis (4-hydroxyphenyl) -1, 2-diphenylethylene and 4,4 ' -diphenylmethane diisocyanate is (0.5-2.5) to 1: 2;
the volume mass ratio of the solvent N, N-dimethylacetamide to the diamine monomer containing N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-phenylenediamine or N, N '-bis (4-aminophenyl) -N, N' -di-2-naphthyl-1, 4-biphenyldiamine is (10-30) mL (0.5-2.5) g.
2. The method for preparing polyurethane derivatives containing triarylamine structure and tetraphenylethylene group as claimed in claim 1, wherein the molar ratio of diamine monomer containing N, N ' -bis (4-aminophenyl) -N, N ' -di-2-naphthyl-1, 4-phenylenediamine or N, N ' -bis (4-aminophenyl) -N, N ' -di-2-naphthyl-1, 4-biphenyldiamine, 1, 2-bis (4-hydroxyphenyl) -1, 2-diphenylethylene, and 4,4 ' -diphenylmethane diisocyanate is 2:1: 2.
3. Use of the polyurethane derivatives containing triarylamine structures and tetraphenylethylene groups, prepared according to claim 1, characterized by the use of the polyurethane derivatives containing triarylamine structures and tetraphenylethylene groups as electrochromic materials.
4. The use of the triarylamine structure-containing and tetraphenylethylene group-containing polyurethane derivative according to claim 3, wherein the use of the triarylamine structure-containing and tetraphenylethylene group-containing polyurethane derivative as an electrochromic material comprises: dissolving a polyurethane derivative containing a triarylamine structure and a tetraphenylethylene group in an organic solvent to obtain a polyurethane derivative solution, and then coating the polyurethane derivative solution on conductive glass to obtain an electrochromic material; wherein the organic solvent is tetrahydrofuran, chloroform, N-dimethylacetamide, N-dimethylformamide or N-methylpyrrolidone.
5. Use of the polyurethane derivatives containing triarylamine structures and tetraphenylethylene groups, prepared according to claim 1, characterized by the use of the polyurethane derivatives containing triarylamine structures and tetraphenylethylene groups as electroluminescent materials.
6. The use of the triarylamine structure-containing and tetraphenylethylene group-containing polyurethane derivative according to claim 5, wherein the use of the triarylamine structure-containing and tetraphenylethylene group-containing polyurethane derivative as an electroluminescent material comprises: dissolving a polyurethane derivative containing a triarylamine structure and a tetraphenylethylene group in an organic solvent to obtain a polyurethane derivative solution, and then coating the polyurethane derivative solution on conductive glass to obtain an electroluminescent material; wherein the organic solvent is tetrahydrofuran, chloroform, N-dimethylacetamide, N-dimethylformamide or N-methylpyrrolidone.
7. The use of the polyurethane derivatives containing triarylamine structures and tetraphenylethylene groups, prepared according to claim 1, characterized by the use of the polyurethane derivatives containing triarylamine structures and tetraphenylethylene groups as explosives detection materials.
8. The application of the polyurethane derivative containing the triarylamine structure and the tetraphenylethylene group as claimed in claim 7, wherein the application method of the polyurethane derivative containing the triarylamine structure and the tetraphenylethylene group as the explosive detection material comprises the following steps: dissolving a polyurethane derivative containing a triarylamine structure and a tetraphenylethylene group in an organic solvent to obtain a polyurethane derivative solution, then dropwise adding a solution containing explosives into the polyurethane derivative solution, and detecting whether the explosives exist in the solution by using the change of the fluorescence intensity of the solution.
CN201811489724.1A 2018-12-06 2018-12-06 Preparation method and application of polyurethane derivative containing triarylamine structure and tetraphenylethylene group Active CN109400836B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811489724.1A CN109400836B (en) 2018-12-06 2018-12-06 Preparation method and application of polyurethane derivative containing triarylamine structure and tetraphenylethylene group

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811489724.1A CN109400836B (en) 2018-12-06 2018-12-06 Preparation method and application of polyurethane derivative containing triarylamine structure and tetraphenylethylene group

Publications (2)

Publication Number Publication Date
CN109400836A CN109400836A (en) 2019-03-01
CN109400836B true CN109400836B (en) 2021-01-22

Family

ID=65457688

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811489724.1A Active CN109400836B (en) 2018-12-06 2018-12-06 Preparation method and application of polyurethane derivative containing triarylamine structure and tetraphenylethylene group

Country Status (1)

Country Link
CN (1) CN109400836B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110186882B (en) * 2019-05-21 2021-07-13 哈尔滨工程大学 Fluorescent test paper for detecting nitro compound and preparation method thereof
CN110527283B (en) * 2019-07-26 2021-05-11 河北大学 PES (polyether sulfone) based flexible white fluorescent polyester and preparation method thereof

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007180072A (en) * 2005-12-26 2007-07-12 Fuji Xerox Co Ltd Organic electroluminescence element
TWI388079B (en) * 2008-07-29 2013-03-01 Univ Nat Taiwan A electron hole transport material
CN105980156A (en) * 2014-02-10 2016-09-28 帝人株式会社 Multilayer body
WO2015137395A1 (en) * 2014-03-14 2015-09-17 日産化学工業株式会社 Aniline derivative and use thereof
CN104829817B (en) * 2015-05-27 2016-08-17 黑龙江大学 A kind of aromatic polyester containing triphenylamine and its preparation method and application
CN105693985B (en) * 2016-03-16 2019-01-18 江苏科技大学 A kind of preparation process of aqueous fluorescent polyurethane composition
CN106632977A (en) * 2016-12-13 2017-05-10 苏州吉人高新材料股份有限公司 Isocyanate curing agent with fluorescence characteristic and preparation method thereof
CN108865117B (en) * 2018-07-23 2021-03-16 吉林大学 Aggregation-induced emission organic fluorescent small molecular material and application thereof in DNT and TNT gas fluorescence detection

Also Published As

Publication number Publication date
CN109400836A (en) 2019-03-01

Similar Documents

Publication Publication Date Title
CN109336787B (en) Preparation method and application of multifunctional polyurethane derivative containing triarylamine structure and tetraphenylethylene group
Cheng et al. High-performance electrofluorochromic devices based on aromatic polyamides with AIE-active tetraphenylethene and electro-active triphenylamine moieties
Yen et al. Flexible multi‐colored electrochromic and volatile polymer memory devices derived from starburst triarylamine‐based electroactive polyimide
Sun et al. AIE-active polyamide containing diphenylamine-TPE moiety with superior electrofluorochromic performance
Yen et al. Novel starburst triarylamine-containing electroactive aramids with highly stable electrochromism in near-infrared and visible light regions
CN109575230B (en) Preparation method and application of multifunctional polyurethane derivative
Carbas et al. A new blue light emitting and electrochromic polyfluorene derivative for display applications
Qin et al. Synthesis and electrochromic properties of polyacrylate functionalized poly (3, 4-ethylenedioxythiophene) network films
CN108586741B (en) Fluorescent polyamic acid polymer, preparation method and application thereof in fluorescent multi-stimulus response
Sun et al. Electroactive (A3+ B2)-type hyperbranched polyimides with highly stable and multistage electrochromic behaviors
Kuo et al. Electrochemical fluorescence switching properties of conjugated polymers composed of triphenylamine, fluorene, and cyclic urea moieties
CN109400836B (en) Preparation method and application of polyurethane derivative containing triarylamine structure and tetraphenylethylene group
Hsiao et al. Redox-active and fluorescent pyrene-based triarylamine dyes and their derived electrochromic polymers
Zhang et al. Multi-stimuli responsive novel polyimide smart materials bearing triarylamine and naphthalimide groups
Hu et al. Synthesis, characterization and fluorescence performance of a waterborne polyurethane‐based fluorescent dye 4‐amino‐N‐cyclohexyl‐1, 8‐naphthalimide, WPU‐ACN
Su et al. High-performance blue fluorescent/electroactive polyamide bearing p-phenylenediamine and asymmetrical SBF/TPA-based units for electrochromic and electrofluorochromic multifunctional applications
Xu et al. Benzothiadiazole, hexylthiophen and alkoxy benzene based solution processable copolymer: Effect of the electron withdrawing substituents (fluorine atoms) on electrochemical, optical and electrochromic properties
İçli-Özkut et al. A neutral state yellow to navy polymer electrochrome with pyrene scaffold
Huang et al. Preparation and characterization of near-infrared and multi-colored electrochromic aramids based on aniline-derivatives
Sun et al. Highly stable and fast blue color/fluorescence dual-switching polymer realized through the introduction of ether linkage between tetraphenylethylene and triphenylamine units
Zheng et al. Preparation and multifunction of electrochromic polyamides containing flexible backbone chains with electrochemical, fluorescence and memory properties
Liu et al. Synthesis, electrochromic properties and flash memory behaviors of novel DAD polyazomethines containing EDOT and thiophene units
Wu et al. Polyurethanes prepared from isocyanates containing triphenylamine derivatives: synthesis and optical, electrochemical, electrochromic and memory properties
CN109593172B (en) Benzoxazine structure-containing triarylamine polymer and preparation method and application thereof
Yang et al. Integrated electrochromic and electrofluorochromic properties from polyaniline-like polymers with triphenylacrylonitrile as side groups

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