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 PDFInfo
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 190
- 239000004814 polyurethane Substances 0.000 title claims abstract description 190
- 125000005259 triarylamine group Chemical group 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 title abstract description 126
- 239000000463 material Substances 0.000 claims abstract description 44
- 239000002360 explosive Substances 0.000 claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 150000004985 diamines Chemical class 0.000 claims abstract description 13
- ZYIGFXHZSKIVOO-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)-1,2-diphenylethenyl]phenol Chemical group C1=CC(O)=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC(O)=CC=1)C1=CC=CC=C1 ZYIGFXHZSKIVOO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001514 detection method Methods 0.000 claims abstract description 12
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- HZCHTHIZSZIGID-UHFFFAOYSA-N 4-n-[4-(4-amino-n-naphthalen-2-ylanilino)phenyl]-4-n-naphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=C2C=CC=CC2=CC=1)C1=CC=C(N(C=2C=CC(N)=CC=2)C=2C=C3C=CC=CC3=CC=2)C=C1 HZCHTHIZSZIGID-UHFFFAOYSA-N 0.000 claims description 53
- -1 N,N'-bis(4-aminophenyl)- N,N'-di-2-naphthyl-1,4-biphenylenediamine diamine Chemical class 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 34
- 239000003960 organic solvent Substances 0.000 claims description 20
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 5
- 239000007790 solid phase Substances 0.000 claims description 5
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 claims 3
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 claims 1
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- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 14
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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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
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:
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:
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:
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:
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:
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:
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
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.
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