Hydrogen bond type polyimine material

Abstract

The invention relates to a hydrogen bond type polyimine material, belonging to an organic photoelectric material. Polymers P1, P2 and P3 are obtained through Stille cross-coupling reaction, the transmittance, coloring efficiency, response time and other properties of the polymer are optimized, and the preparation method has important guiding significance on electrochromic application of the polymer. The invention discloses a preparation method of a hydrogen bond type polyimine material, the polymer material is prepared through Stille cross-coupling reaction, the structural formula of the polymer material is shown in the specification, and n is a natural number from 1 to 10000. The series of conjugated polymers can obviously influence the polymer structure and the photoelectron performance through the change of the acceptor unit, so that the optical contrast ratio and the coloring efficiency of electrochromism are improved, and the conjugated polymers are novel electrochromism functional layer materials.

Description

Technical Field

[0001] This invention relates to the field of organic optoelectronic materials, and in particular to the application of hydrogen-bonded polyimide materials in the field of electrochromism. Background Technology

[0002] Electrochromic (EC) materials can reversibly alter their optical properties (such as color or transparency) through electrochemically induced redox reactions. Changes in the material's transmittance and / or reflectance are persistent and can be triggered by applying energy. Depending on the electrochromic material used, different wavelengths of the spectrum can be selectively blocked, thereby independently modulating the transmission of ultraviolet, visible, and near-infrared light. These materials are used to manufacture dimming mirrors and smart windows for use in automobiles and aircraft under different lighting conditions. Controlling near-infrared light transmittance enables thermal management, reducing building air conditioning energy consumption and improving energy efficiency. In recent years, research on electrochromic devices as digital displays has increased, simultaneously meeting the requirements of visual comfort and energy efficiency.

[0003] Transition metal oxides, metal coordination compounds, organic dyes, and π-conjugated polymers all exhibit electrochromic properties. Polymer electrochromic materials possess advantages such as high coloring intensity, easy structural modification, and good film-forming properties. The imine group (–CH=N–) and vinylidene group (–CH=CH–) are isoelectronic and can be generated through a mild condensation reaction between an aldehyde and a primary amine, with water as a byproduct. This bond exhibits excellent thermal and photochemical stability. Due to the higher electronegativity of nitrogen than carbon, the imine group inherently possesses electron-deficient characteristics compared to its corresponding vinylidene group. Currently, the imine group is the only known chemical bond that can simultaneously provide π-conjugation and controllable degradation. Over the past 30 years, conjugated polyimides have attracted considerable attention in the optoelectronics field as semiconductor polymers. In recent years, with the development of transient electronics, research interest in degradable π-conjugated polyimides as semiconductor materials has been growing.

[0004] In the field of electrochromism, material properties are influenced by the synergistic effect of electron and ion transport, and balancing the relationship between the two is crucial. However, traditional imine-based materials suffer from poor hole / electron transport capabilities due to their short effective conjugation length, weak molecular aggregation, and poor hole / electron transport capacity, severely limiting their application in electrochromic devices. In our previous study on polyimides, we utilized intramolecular hydrogen bonding to lock repeating units into a coplanar structure, thereby extending the π delocalization effect within the polymer chain and enhancing interchain aggregation, ultimately improving the hole / electron transport capacity of the material. Summary of the Invention

[0005] This invention addresses the shortcomings of existing technologies by researching a method for preparing hydrogen-bonded polyimide materials and exploring their optical properties. This series of conjugated polymers, by altering the acceptor units, can significantly affect the polymer structure and its photoelectronic properties, thereby improving the optical contrast and coloring efficiency of electrochromic materials, representing a novel type of electrochromic functional layer material.

[0006] This invention is achieved through the following technical solution: A first aspect of the present invention provides a hydrogen-bonded polyimide material, characterized in that it has the following structure:

[0007] Where n is a natural number from 1 to 10000.

[0008] A second aspect of the present invention provides a method for preparing the above-mentioned hydrogen-bonded polyimide material, comprising the following steps: A conjugated polymer was obtained by polymerizing monomers M1, M2 and M3 in a certain molar ratio with 5,7-bis(trimethyltin)-2,3-dihydrothiopheno[3,4-b][1,4]dioxin, tris(dibenzylideneacetone)dipalladium-chloroform adduct, tris(o-methylphenyl)phosphine, and degassed anhydrous toluene.

[0009] Preferably, in the above steps, the molar ratio of monomers M1, M2, and M3 to 5,7-bis(trimethyltin)-2,3-dihydrothiopheno[3,4-b][1,4]dioxin is 1:1.

[0010] Preferably, in the above steps, the Stille cross-coupling reaction is as follows: monomers M1, M2 and M3 are dissolved in degassed anhydrous toluene along with 5,7-bis(trimethyltin)-2,3-dihydrothiopheno[3,4-b][1,4]dioxin, a certain proportion of tris(dibenzylideneacetone)dipalladium-chloroform adduct, and tris(o-methylphenyl)phosphine. The mixture is stirred at 65°C for 12 hours.

[0011] A third aspect of the present invention provides the application of the above-described conjugated polymer in the field of electrochromism. Attached Figure Description

[0012] Figure 1 The above are the proton NMR spectra of P1, P2, and P3.

[0013] Figure 2 The following are the spectroelectrochemical spectra of P1, P2, and P3.

[0014] Figure 3 The diagram shows the kinetic curves for P1, P2, and P3. Detailed Implementation

[0015] It should be noted that the following detailed descriptions are illustrative and intended to provide further explanation of this application. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains.

[0016] To enable those skilled in the art to better understand the technical solutions of this application, the technical solutions of this application will be described in detail below with reference to specific embodiments. Unless otherwise specified, experimental conditions not detailed in the embodiments are generally based on conventional conditions or conditions recommended by the reagent company; reagents, consumables, etc., used in the following embodiments can be obtained commercially unless otherwise specified. Example

[0017] Preparation of hydrogen-bonded polyimide material P1 The chemical reaction process is shown below, with specific reaction steps and conditions as follows:

[0018] Bis(2-octyldodecyl)(((1E,1'E)-hydrazine-1,2-diethylene)bis(methylene))bis(5-bromothiophene-2,3-diyl)) dicarboxylate (M1) (0.192 g, 0.18 mmol), 5,7-bis(trimethyltin)-2,3-dihydrothieno[3,4-b][1,4]dioxin (EDOT-Sn) (0.085 g, 0.18 mmol), tris(dibenzylideneacetone)dipalladium-chloroform adduct (0.003 g, 0.004 mmol), and tris(o-methylphenyl)phosphine (0.004 g, 0.014 mmol) were added to a Schrank tube with degassed anhydrous toluene (6.0 mL). The mixture was stirred at 65°C for 12 hours. After cooling to room temperature, the mixture was poured into methanol to precipitate and filtered. The residue was washed sequentially with methanol, n-hexane, and dichloromethane using a Soxhlet extractor under nitrogen protection. The polymer was dissolved in chloroform and concentrated, then precipitated in methanol and filtered to give P1 dark blue solid (0.173 g, 89% yield). Nuclear magnetic resonance spectroscopy was then performed. Figure 1 ). Example

[0019] Preparation of hydrogen-bonded polyimide material P2 Bis(2-octyldodecyl)(((1E,1'E)-(1,4-phenylenebis(aza-ylidene))bis(methylene))bis(5-bromothiophene-2,3-diyl)) dicarboxylate (M2) (0.189 g, 0.17 mmol), EDOT-Sn (0.078 g, 0.17 mmol), tris(dibenzylacetone)dipalladium-chloroform adduct (0.003 g, 0.003 mmol), and tris(o-methylphenyl)phosphine (0.004 g, 0.013 mmol) were added to a Schrank tube with degassed anhydrous toluene (6.0 mL). The mixture was stirred at 65°C for 12 hours. Subsequent processing was the same as for P1, yielding P2, a dark blue solid (0.169 g, 89% yield), and its nuclear magnetic resonance spectrum was measured. Figure 1 ). Example

[0020] Preparation of hydrogen-bonded polyimide material P3 Bis(2-octyldodecyl)(((1E,1'E)-(pyrazine-2,5-diylbis(aza-ylidene))bis(methylene))bis(5-bromothiophene-2,3-diyl)) dicarboxylate (M3) (0.190 g, 0.17 mmol), EDOT-Sn (0.078 g, 0.17 mmol), tris(dibenzylacetone)dipalladium-chloroform adduct (0.003 g, 0.003 mmol), and tris(o-methylphenyl)phosphine (0.004 g, 0.013 mmol) were added to a Schrank tube with degassed anhydrous toluene (6.0 mL). The mixture was stirred at 65°C for 8 hours. Subsequent processing was the same as for P1, yielding P3, a dark blue solid (0.173 g, 90% yield), and its nuclear magnetic resonance spectrum was measured. Figure 1 ). Example

[0021] Taking the polymer materials obtained in Examples 1, 2, and 3 as examples, their application in the field of electrochromic materials. The following examples will illustrate the polymer provided by the present invention and its application process in the field of electrochromic technology, but the present invention is not limited to the examples given.

[0022] (1) Spectroelectrochemistry The polymers obtained in Examples 1, 2, and 3 were sprayed onto ITO conductive glass to form a polymer film. The ITO conductive glass coated with the polymer film was placed in a three-electrode electrolytic cell containing an acetonitrile solution of tetrabutylammonium hexafluoride. The working electrode was the ITO conductive glass coated with the polymer film, the counter electrode was a platinum sheet, and the reference electrode was an Ag / AgCl electrode. Using a potentiostatic method, the voltage applied to the working electrode was adjusted by an electrochemical workstation, and the changes in the absorption spectrum of the polymer under different voltages were recorded using a UV-Vis spectrometer, thus obtaining the spectroelectrochemical spectrum of the polymer. Figure 2 ).

[0023] (2) Dynamics The transmittance of a polymer film in its oxidized and reduced states at a specific wavelength under a square wave potential was measured using a UV-Vis spectrophotometer, thereby calculating optical contrast, response time, etc. The UV-Vis spectrophotometer records a time-transmittance curve, while the electrochemical workstation records a time-current curve. The coloring efficiency can also be calculated from these two curves. Figure 3 .

[0024] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A hydrogen-bonded polyimide material, characterized in that, It has the following structure: ， Where n is a natural number from 1 to 10000.

2. The method for preparing the conjugated polymer according to claim 1, characterized in that, Includes the following steps: A conjugated polymer was obtained by polymerizing monomers M1, M2, and M3 in a certain molar ratio with 5,7-bis(trimethyltin)-2,3-dihydrothiopheno[3,4-b][1,4]dioxin, tris(dibenzylacetone)dipalladium-chloroform adduct, tris(o-methylphenyl)phosphine, and degassed anhydrous toluene. 。 3. The method for preparing monomers M1, M2, and M3 according to claim 2, characterized in that, Monomers M1, M2, and M3 were prepared by dehydration condensation reaction of urethane-functionalized thiophene aldehyde with hydrazine, p-phenylenediamine, and 2,5-diaminopyrazine under acetic acid catalysis.

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