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CN-121135943-B - Polymer cross-linking agent, preparation method thereof and application thereof in organic photoelectric material

CN121135943BCN 121135943 BCN121135943 BCN 121135943BCN-121135943-B

Abstract

The invention belongs to the technical field of optical functional materials, and particularly relates to a polymer cross-linking agent, a preparation method thereof and application thereof in an electromechanical light material. The invention provides a polymer cross-linking agent, which has a structure shown in a formula I. According to the invention, the crosslinking groups are introduced into the polymer crosslinking agent, and under the condition of illumination (350-450 nm ultraviolet irradiation) or heating, nitrogen is released to generate the reactive carbene, and the carbene is subjected to crosslinking reaction with the polymer frame and chromophore through C-H bond insertion reaction to form a stable three-dimensional network structure, so that the polymer crosslinking agent is suitable for improving the glass transition temperature and thermal stability of various structural materials, and has universality and wide applicability. The technology provides a new way for developing flexible photoelectronic devices, and the crosslinking characteristic of low energy consumption and high precision of the technology shows wide prospects in the fields of wearable equipment and integrated photon chips.

Inventors

  • BO SHUHUI
  • LI PENGWEI
  • LI RUONAN

Assignees

  • 中央民族大学

Dates

Publication Date
20260508
Application Date
20251017

Claims (7)

  1. 1. The organic photoelectric polymer is characterized by being obtained by crosslinking a polymer crosslinking agent and a chromophore, wherein the polymer crosslinking agent has a structure shown in a formula I: A formula I; in formula I, x+y+z=1; R 1 and R 2 are independently one or more of ester group, substituted ester group, amide group and substituted amide group; R 3 has any one of the structures of formula 1 to formula 20: ; r 4 is NO 2 , H or halo.
  2. 2. The organic photopolymer according to claim 1, wherein the method of preparing the polymeric crosslinker comprises the steps of: dissolving a monomer 1, a monomer 2, a monomer 3, an alkaline substance and an initiator into an organic solvent, and carrying out polymerization under the heating condition to obtain the polymer cross-linking agent; the structural formula of the monomer 1 is as follows: The structural formula of the monomer 2 is as follows: ; The structural formula of the monomer 3 is as follows: 。
  3. 3. The organic electro-optic polymer of claim 2, wherein the basic substance comprises one or more of triethylamine, tributylamine, pyridine, 4-dimethylaminopyridine, N-diisopropylethylamine, N-dimethylaniline, 1, 8-diazabicyclo [5.4.0] undec-7-ene, and 1, 5-diazabicyclo [4.3.0] non-5-ene.
  4. 4. The electro-mechanical photopolymer according to claim 2 wherein the initiator comprises a mixture of N, N-dimethyl-p-toluidine and benzoyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile or azobisisoheptonitrile; The organic solvent comprises one or more of anhydrous toluene, anhydrous N, N-dimethylformamide and anhydrous dimethyl sulfoxide.
  5. 5. The organic photopolymers according to claim 2, wherein the monomer 3 is prepared by the following method: And carrying out esterification reaction on R 3 OH and methacryloyl chloride or acryloyl chloride under alkaline conditions to obtain a monomer 3.
  6. 6. A method of preparing the organic photopolymer of claim 1 comprising the steps of: Mixing the solution of the polymer cross-linking agent with the chromophore and drying to obtain the electro-optic material; and sputtering the electro-optic material to an electrode, and then sequentially carrying out electric field polarization and photo-crosslinking to obtain the electro-optic polymer.
  7. 7. An organic light-emitting polymer film, which is made of the organic light-emitting polymer according to claim 1 or the organic light-emitting polymer prepared by the preparation method according to claim 6.

Description

Polymer cross-linking agent, preparation method thereof and application thereof in organic photoelectric material Technical Field The invention belongs to the technical field of optical functional materials, and particularly relates to a polymer cross-linking agent, a preparation method thereof and application thereof in an electromechanical light material. Background The electro-optic material is used as a core functional material in the fields of high-speed optical communication, photon calculation and sensing, and the electro-optic activity is derived from the non-central symmetrical arrangement of chromophores induced by an external electric field, but the arrangement can relax when the ambient temperature is close to or exceeds the glass transition temperature (Tg) of the material, so that the electro-optic activity is rapidly attenuated, and the long-term reliability and the service life of the device are severely restricted. Therefore, how to effectively improve the Tg of the organic photoelectric material and further ensure the long-term thermal stability of the organic photoelectric material is a core technical problem to be solved in the current organic photoelectric material field. In order to solve the problems, the common solution is that firstly, a high Tg polymer is taken as a host, chromophore molecules are taken as objects, the chromophore molecules are doped into the high Tg polymer, or branched chain substituent groups are introduced into the structure of the chromophore molecules, the dendritic substituent groups increase Tg, so that the thermal relaxation behavior of the chromophore is inhibited to a certain extent, and the attenuation of the electro-optic activity is relieved, but the strategy usually involves a complex molecular synthesis process, the preparation cost is higher, the improvement effect on the thermal stability is limited, and the application requirements of high-performance devices are difficult to meet. Secondly, crosslinking is widely recognized as an effective method of enhancing the long term thermal stability of electro-optic polymers, e.g., diels-Alder thermal crosslinking has been demonstrated to significantly improve thermal stability while maintaining high electro-optic activity (ADVANCED SCIENCE 2023, 10 (31), 2304229.) however such thermal crosslinking typically requires high temperatures above 130 ℃ to overcome the activation energy barrier, not only limiting compatibility with semiconductor lithography processes, but also risking mismatch of the polarization and crosslinking windows, resulting in incomplete chromophore alignment or low crosslinking efficiency, affecting final device performance. In recent years, carbene-mediated crosslinking strategies have been of great interest due to their high efficiency and versatility. However, although the prior art has reported that bisaziridine small molecule crosslinking agents can be used to prepare high density elastic circuits and multifunctional semiconductor patterns, how to extend small molecule crosslinking agents to high molecular weight polymer crosslinking systems and use them in electro-optical materials has been studied very little. Disclosure of Invention The invention aims to provide a polymer cross-linking agent, a preparation method thereof and application thereof in an organic photoelectric material. In order to achieve the above object, the present invention provides the following technical solutions: The invention provides a polymer cross-linking agent, which has a structure shown in a formula I: A formula I; In formula I, x+y+z=1; R 1 and R 2 are independently one or more of ester group, substituted ester group, amide group and substituted amide group; R 3 contains one or more substituents from the group consisting of bisaziridine, diazo and azide. Preferably, R 3 has any one of the structures of formula 1 to formula 20: r 4 is NO 2, H or halo. The invention also provides a preparation method of the polymer cross-linking agent, which comprises the following steps: dissolving a monomer 1, a monomer 2, a monomer 3, an alkaline substance and an initiator into an organic solvent, and carrying out polymerization under the heating condition to obtain the polymer cross-linking agent; the structural formula of the monomer 1 is as follows: the structural formula of the monomer 2 is as follows: ; The structural formula of the monomer 3 is as follows: 。 Preferably, the basic substance comprises one or more of triethylamine, tributylamine, pyridine, 4-dimethylaminopyridine, N-diisopropylethylamine, N-dimethylaniline, 1, 8-diazabicyclo [5.4.0] undec-7-ene and 1, 5-diazabicyclo [4.3.0] non-5-ene. Preferably, the initiator comprises a mixture of N, N-dimethyl-p-toluidine and benzoyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile or azobisisoheptonitrile; The organic solvent comprises one or more of anhydrous toluene, anhydrous N, N-dimethylformamide and anhydrous dimethyl sulfoxide. Preferably, the