CN-117003688-B - Fluorescent monomer based on tetraphenyl ethylene and preparation method and application thereof

Abstract

The invention discloses a fluorescent monomer based on tetraphenyl ethylene, a preparation method and application thereof, and belongs to the technical field of polymer luminescent materials. The invention prepares a fluorescent monomer by connecting the active group tetra-styryl group containing aggregation-induced emission with a specific high molecular framework, and the fluorescent polymer prepared by the fluorescent monomer and the specific polymerization monomer can be used for detecting copper ions, and has high sensitivity and good repeatability in detection, thereby realizing visual observation.

Inventors

• GUO HONGLEI
• YUAN ZIHAO
• ZHU CANJIE
• ZHOU YIFEI
• Liang Huansen

Assignees

• 中山大学

Dates

Publication Date

20260505

Application Date

20230721

Claims (6)

1. 1. The fluorescent monomer based on the tetraphenyl ethylene is characterized in that the structural formula of the fluorescent monomer is shown as the following formula (I): Formula (I); r has the structure of formula (V): Formula (V); Wherein n has a value of 1 to 20.
2. 2. The tetraphenyl ethylene-based fluorescent monomer of claim 1, wherein n has a value of 10.
3. 3. The method for preparing a tetraphenyl ethylene-based fluorescent monomer according to claim 1 or 2, wherein the method comprises the steps of: s1, reacting a 4-hydroxybenzophenone solution, a4, 4' -dibromobenzophenone solution and a catalyst in nitrogen, and purifying by a silica gel chromatographic column to obtain a product 1; S2, reacting the product 1 obtained in the step S1 with 3-vinyl pyridine and a catalyst in nitrogen, and purifying by a silica gel chromatographic column to obtain a product 2; S3, reacting the product 2 obtained in the step S2 with a brominated raw material and a catalyst in nitrogen, and purifying by a silica gel chromatographic column to obtain the fluorescent monomer based on the tetraphenyl ethylene, wherein the brominated raw material is represented by a formula (XII): Formula (XII); Wherein n has a value of 1 to 20.
4. 4. The method for producing a tetraphenyl ethylene-based fluorescent monomer according to claim 3, wherein the brominated raw material is 11-bromoundec-1-ene.
5. 5. A fluorescent polymer prepared by using the fluorescent monomer according to claim 1 or 2, the preparation method of the fluorescent polymer comprises the following steps: a1, mixing the fluorescent monomer according to claim 1 or 2 with a polymerization reaction monomer, an initiator and a crosslinking agent in an organic solvent, and carrying out free radical copolymerization reaction to obtain a polymer solution; A2, transferring the polymer solution obtained in the step A1 into a solvent exchange liquid for soaking, and obtaining a fluorescent polymer after the solvent exchange is completed; the polymerization monomer is a combination of formula (XV) and formula (XVI): Formula (XV); formula (XVI).
6. 6. The use of the fluorescent polymer according to claim 5 in localized corrosion detection and warning of printed circuit boards.

Description

Fluorescent monomer based on tetraphenyl ethylene and preparation method and application thereof Technical Field The invention belongs to the technical field of polymer luminescent materials, and particularly relates to a fluorescent monomer based on tetraphenyl ethylene, and a preparation method and application thereof. Background In recent years, with the great development of science and technology, the fluorescence sensing technology has been widely studied due to high sensitivity, good selectivity, simple operation, low cost, high resolution, capability of realizing in-vivo rapid in-situ on-line detection, and the like. The fluorescent monomer can show obvious fluorescence emission or quenching when exposed to ultraviolet lamp, so the method is relatively simple and quick, and the fluorescent sensing technology is also widely applied to important fields such as environment monitoring, ion and small molecule detection, biological imaging, medical diagnosis and treatment and the like. Copper is widely used in various aspects of life and generally undergoes uniform corrosion during use. However, even if the copper is uniformly corroded in the printed wiring board having copper as a base, the entire circuit board is significantly affected. To address this problem, M.Schwind, W.Cheng, K.Habib et al have monitored early stages of copper corrosion of printed circuit boards by conventional techniques such as nanoplasma sensing (Journal of the Electrochemical Society,160 (2013) C487-C492), electrochemical characterization (International Journal of Electrochemical Science,14 (2019) 4254-4263), and holographic interferometry (Corrosion Science,40 (1998) 1435-1440), most of which have limitations, although they provide accurate results, such as complex and cumbersome electrochemical characterization and holographic interferometry, requiring long detection cycle times. Therefore, these conventional methods do not allow for a quick and easy inspection of localized copper substrate corrosion areas in a printed circuit board. The scholars Guo H (ACS APPLIED MATERIALS & Interfaces, 2023) proposed that by combining fluorescent monomers with hydrogel, a reusable metal surface corrosion detection sensor was developed, which can detect trace corrosion by the iron ions released from the outside, and the detection limit is as low as 10 -5 M, but the sensor still requires an ultraviolet lamp for auxiliary detection, and cannot realize direct visual detection. Aiming at the defects existing in the detection method of the copper ions, the search for the copper ion response fluorescent polymer which has high sensitivity and good repeatability and can realize visual observation is the key point of the research in the field of the current polymer luminescent materials. Disclosure of Invention The invention aims to overcome the defects of the prior art and provide a fluorescent monomer based on tetraphenyl ethylene, a preparation method and application thereof, wherein the fluorescent polymer prepared from the fluorescent monomer can be used for detecting copper ions, and has high sensitivity and good repeatability in detection, so that visual observation can be realized. In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: In a first aspect, the present invention provides a fluorescent monomer based on tetraphenyl ethylene, wherein the structural formula of the fluorescent monomer is shown as the following formula (I): The structure of R is selected from the following formula (II), formula (III), formula (IV), formula (V), formula (VI) or formula (VII): wherein n has a value of 0 to 20. The fluorescent monomer contains an aggregation-induced-luminescence active group tetrastyryl group, and is grafted onto a high molecular framework of the formula (II), the formula (III), the formula (IV), the formula (V), the formula (VI) or the formula (VII), and the fluorescent polymer prepared by the fluorescent monomer under the conditions can be used for detecting copper ions, has high sensitivity and good repeatability during detection, and can realize visual observation. As a preferred embodiment of the tetraphenyl ethylene-based fluorescent monomer according to the present invention, R is formula (V) and n has a value of 10. In a second aspect, the present invention provides a method for preparing a tetraphenyl ethylene-based fluorescent monomer according to the first aspect, the method comprising the steps of: s1, reacting a 4-hydroxybenzophenone solution, a4, 4' -dibromobenzophenone solution and a catalyst in nitrogen, and purifying by a silica gel chromatographic column to obtain a product 1; S2, reacting the product 1 obtained in the step S1 with 3-vinyl pyridine and a catalyst in nitrogen, and purifying by a silica gel chromatographic column to obtain a product 2; S3, reacting the product 2 of the step S2 with brominated raw materials and a catalyst in nitrogen, and purifying by a silica g