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CN-122011033-A - Reactive aggregation luminescent flame-retardant organic functional material and preparation method thereof

CN122011033ACN 122011033 ACN122011033 ACN 122011033ACN-122011033-A

Abstract

The invention belongs to the field of organic functional molecules and organic polymer functional materials, and particularly relates to a reactive aggregation luminescent flame-retardant organic functional material and a preparation method thereof. According to the invention, the flame-retardant group DOPO is introduced into the molecule containing the aggregation luminescent TPE group, so that the flame-retardant group DOPO which simultaneously contains the aggregation-induced luminescent performance TPE group and the flame-retardant function in the structure is designed and synthesized, and the aggregation luminescent function is ensured, and meanwhile, the flame-retardant performance is better.

Inventors

  • ZHONG LIU
  • LIU MENGJIA
  • ZHONG SHILONG
  • WANG CHENG
  • RAO JINGYI
  • CHEN XUDONG
  • LIU ZHIGUO

Assignees

  • 西华大学

Dates

Publication Date
20260512
Application Date
20260410

Claims (10)

  1. 1. A reactive aggregation luminescent flame-retardant organic functional material shown in a general formula (I): ; I is a kind of Wherein G is selected from any one of the following structural formulas: ; I-1 I-2 I-3 I-4 I-5 O in G forms an ether linkage with each of the carbons attached in formula I.
  2. 2. The preparation method of the reactive aggregation luminescent flame-retardant organic functional material as claimed in claim 1, which is characterized by comprising the following steps: step (1) DOPO-HQ (formula II) reacts with 4-formylbenzoyl chloride (formula III) to synthesize DOPO-HQ monoester (formula IV); ; formula II formula III formula IV Step (2) of reacting DOPO-HQ monoester (formula IV) with tetra (4-aminophenyl) ethylene (formula V) to synthesize an imine compound (formula VI); ; V (V) ; VI (VI) And (3) reacting the imine compound (formula VI) with bisphenol A diglycidyl ether (formula VII) to synthesize the reactive aggregation luminescent flame-retardant organic functional material (formula I): ; VII (VII) G is selected from any one of the following structural formulas: ; I-1 I-2 I-3 I-4 I-5 wherein O in G forms an ether linkage with each of the carbons attached in formula VII.
  3. 3. The method for preparing a reactive aggregation luminescent flame-retardant organic functional material according to claim 2, wherein in the step (1), the equivalent ratio of DOPO-HQ (formula II) to 4-formylbenzoyl chloride (formula III) is 1.0-1.1:1.0.
  4. 4. The method for preparing the reactive aggregation luminescent flame-retardant organic functional material according to claim 2, wherein in the step (1), the reaction is performed in the presence of a base selected from one or more of triethylamine, diisopropylethylamine, 1, 8-diazabicyclo [5.4.0] undec-7-ene, pyridine and 4- (dimethylamino) pyridine.
  5. 5. The method for preparing the reactive aggregation luminescent flame-retardant organic functional material according to claim 2, wherein in the step (1), the reaction temperature is-20 ℃ to 30 ℃.
  6. 6. The method for preparing a reactive aggregation luminescent flame-retardant organic functional material according to claim 2, wherein in the step (2), the equivalent ratio of DOPO-HQ monoester (formula IV) to tetra (4-aminophenyl) ethylene (formula V) is 2.0-2.2:1.
  7. 7. The method for preparing the reactive aggregation luminescent flame-retardant organic functional material according to claim 2, wherein in the step (2), the reaction temperature is 60-160 ℃.
  8. 8. The method for preparing a reactive aggregation luminescent flame-retardant organic functional material according to claim 2, wherein in the step (3), the equivalent ratio of the imine compound (formula VI) to bisphenol A diglycidyl ether (formula VII) is 1:2.0-2.4.
  9. 9. The method for preparing the reactive aggregation luminescent flame-retardant organic functional material according to claim 2, wherein in the step (3), the reaction temperature is 80-180 ℃.
  10. 10. The method for preparing the reactive aggregation luminescent flame-retardant organic functional material according to any one of claims 2 to 9, wherein at least any one of the following is satisfied: in the step (1), the solvent adopted in the reaction is selected from one or more of dichloromethane, tetrahydrofuran, dioxane, toluene, acetonitrile, ethylene glycol dimethyl ether, 2-methyl furan and DMF; In the step (2), the solvent adopted in the reaction is one or more selected from dioxane, toluene, xylene, ethylene glycol diethyl ether, N-dimethylformamide and N, N-dimethylacetamide; In the step (3), the solvent adopted in the reaction is one or more selected from dioxane, toluene, ethylene glycol diethyl ether, 2-methyl furan, diisopropyl ether, methyl tertiary butyl ether, 1, 2-dichloroethane, xylene, DMF and DMAc.

Description

Reactive aggregation luminescent flame-retardant organic functional material and preparation method thereof Technical Field The invention belongs to the field of organic functional molecules and organic polymer functional materials, and particularly relates to a reactive aggregation luminescent flame-retardant organic functional material and a preparation method thereof. Background The Tang Benzhong institution team first proposed the concept of aggregation-induced emission (AIE), explaining the phenomenon that certain molecules or fragments in an aggregated state are enhanced by intramolecular rotation, vibration or limited movement. Common organic molecules with AIE function include imides, triphenylamines, phenothiazines, carbazoles, tetraphenylstyrenes and the like, and based on the modules, a plurality of solid-state luminescent materials are synthesized, and the following structural formulas are shown: 。 For example, patent [ CN114163379 ] reports that carbazole derivatives containing fluorine and biphenyl groups have a function of emitting blue light, patent [ CN120554345 ] reports that phenothiazine derivatives containing aromatic rings and the like have a function of electroluminescence, patent [ CN120904080 ] reports that organic light-emitting materials are prepared by bonding two modules of tetraphenyl ethylene and triarylamine into the same molecule through chemical bonds, patent [ CN120574162 ] reports that isoindoline imide-containing compounds can be applied to OLED materials, patent [ WO2024202086 ] reports that triarylamine is modified into naphthol derivatives to have a function of photochromism, and the like. Tetraphenyl ethylene (TPE) is an organic light emitting molecule having a simple molecular structure, having been industrially produced, and exhibiting excellent aggregation-induced emission. TPE is taken as a basic building block, TPE organic luminophores containing different groups or functional groups are extended, and the TPE organic luminophore has wide application prospect. For example, patent WO2025184691 reports organic probes of cyano-containing tetraphenyl ethylene, patent CN120398922 reports tetraphenyl ethylene aggregate luminescent materials containing benzodithiophene derivatives, patent CN118994189 reports tetraphenyl ethylene luminescent materials containing crown ethers, patent CN120887872 reports tetraphenyl ethylene photosensitizers containing piperazine, and patent CN120904080 reports tetraphenyl ethylene luminescent materials containing benzyl cyanide groups. In order to expand the application range of TPE, derivatives containing chemically reactive functional groups are often obtained by chemical modification. For example, patent CN116903504 reports that carboxyl groups (TPE-COOH) are introduced into TPE to enhance water solubility, patent US20250170265 reports that amino groups (TPE-NH 2) are introduced into TPE as further modified active sites, patent WO2010027108 reports that graft polyethylene glycol (TPE-PEG) is introduced into TPE to reduce biotoxicity, and patent US12391800 reports that aldehyde groups (TPE-CHO) are introduced into TPE to prepare conjugated polymer luminescent materials. The structural formula is as follows: 。 Based on TPE, organic light emitting molecules of many TPE modules have been developed and are developed toward high performance, low cost, and multi-function. However, there is no organic aggregated luminescent molecule which integrates multiple reactive functional groups and has aggregated luminescence, flame retardance and so on. Disclosure of Invention The invention aims to solve the problem of simultaneous aggregation luminescence, flame retardance and reactivity, and selects specific raw materials, and introduces flame retardant group DOPO (abbreviation of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) into molecules containing aggregation luminescence TPE groups, namely, the TPE-containing tetra (4-aminophenyl) ethylene (abbreviation ATPE) is used as aggregation induced luminescence molecules, so that the TPE groups with aggregation induced luminescence performance and flame retardant groups DOPO with flame retardant function are designed and synthesized, and the TPE groups with aggregation luminescence performance is ensured, and meanwhile, the TPE has better flame retardant performance. In order to ensure that the polymer has wider application range, reactive functional groups such as alcoholic hydroxyl groups, phenolic hydroxyl groups, secondary amino groups, epoxy groups and the like are designed in the reactive aggregation luminescent flame-retardant organic functional molecules. Therefore, the invention firstly synthesizes DOPO-HQ monoester (IV) by using DOPO-HQ [10- (2, 5-dihydroxyphenyl) -10-hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide abbreviation ] and 4-formyl benzoyl chloride raw materials through esterification reaction, synthesizes intermediate imine (VI) by utilizing aldehyde group in the DOPO-HQ monoe