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CN-116769157-B - Poly alpha-oximido amide compound and preparation method and application thereof

CN116769157BCN 116769157 BCN116769157 BCN 116769157BCN-116769157-B

Abstract

The invention belongs to the technical field of polymer chemistry and materialogy, and discloses a poly alpha-oximido amide compound and a preparation method and application thereof. The invention obtains a crude product by carrying out polymerization reaction on a binary isonitrile compound and a binary chloroxime compound in a mixed solvent of an organic solvent and water, and obtains the poly alpha-oximido amide compound by carrying out subsequent treatment on the crude product. The method disclosed by the invention is mild in condition, can realize efficient polymerization at room temperature without inert gas protection, and the polymerization process shows the characteristic of polymerization-induced luminescence. The poly alpha-oximido amide compound has good film forming property, solubility and thermal stability, and the film of the poly alpha-oximido amide compound shows high refractive index. In addition, the poly alpha-oximido amide compound has the characteristic of non-traditional luminescence, and can be applied to detection of transition metal ions.

Inventors

  • TANG BENZHONG
  • QIN ANJUN
  • LI MINGZHAO

Assignees

  • 华南理工大学

Dates

Publication Date
20260508
Application Date
20230707

Claims (7)

  1. 1. The preparation method of the poly alpha-oximido amide compound is characterized by comprising the following steps of: (1) Carrying out polymerization reaction on the binary isocyanide compound and the binary chlorooxime compound in a mixed solvent of an organic solvent and water to obtain a crude product; (2) Carrying out subsequent treatment on the crude product to obtain a poly alpha-oximido amide compound; The structural general formula of the binary isonitrile compound is shown as formula (II): (II); The structural general formula of the binary chlorine oxime compound is shown as formula (III): (III); The structural general formula of the poly alpha-oximido amide compound is shown as a formula (I): (I); In the formulas (I) - (III), n is an integer more than or equal to 2, R 1 ,R 2 is the same or different organic groups, R 1 is selected from any one of the structural formulas 1-28, R 2 is selected from any one of the structural formulas 1-28; Wherein m is an integer of 1 to 20, X=NH, O, S or SiH 2 , and represents a substitution position.
  2. 2. The preparation method of the poly alpha-oximido amide compound is characterized in that the organic solvent in the step (1) is more than one of tetrahydrofuran, dichloromethane, chloroform, toluene, 1, 4-dioxane, dimethyl sulfoxide and N, N-dimethylformamide, the volume ratio of the organic solvent in the step (1) to water is 4:1-1:4, the mole ratio of the binary isocyanide compound in the step (1) to the binary chloroxime compound is 1 (0.6-1.5), and the concentration of the binary isocyanide compound in the step (1) is 0.01-5 mol/L.
  3. 3. The preparation method of the poly alpha-oximido amide compound according to claim 1 is characterized in that the polymerization reaction temperature in the step (1) is 0-200 o ℃, the polymerization reaction time in the step (1) is 5-1000 minutes, and the polymerization reaction in the step (1) is carried out under normal pressure.
  4. 4. The preparation method of the poly alpha-oximido amide compound according to claim 1 is characterized in that the polymerization reaction in the step (1) is performed under the action of phosphate catalysts, wherein the concentration of the phosphate catalysts is 0-5 mol/L, and the number of the phosphate catalysts is more than one of Na 2 HPO 4 、K 2 HPO 4 、KH 2 PO 4 、NaH 2 PO 4 、K 3 PO 4 、Na 3 PO 4 .
  5. 5. The poly-alpha-oximido amide compound prepared by the preparation method of any one of claims 1-4.
  6. 6. Use of the poly-alpha-oximido amides according to claim 5 for the preparation of optical devices.
  7. 7. The application of the poly alpha-oximido amide compound in the detection of transition metal ions is characterized by comprising the following steps of dissolving the poly alpha-oximido amide compound in a good solvent, adding a sample to be detected, observing the change of fluorescence intensity of the mixed solution, and judging whether the sample to be detected contains transition metal ions, wherein the concentration of the poly alpha-oximido amide compound is 1-100 mu M, the good solvent is more than one of tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide and dimethyl sulfoxide, and the transition metal ions are Cu 2+ .

Description

Poly alpha-oximido amide compound and preparation method and application thereof Technical Field The invention belongs to the technical field of polymer chemistry and materialogy, and particularly relates to a poly alpha-oximido amide compound and a preparation method and application thereof. Background Water is a rich, natural, sustainable resource, however in most cases, water is detrimental to the equilibrium positive movement of the chemical reaction and the catalytic system, so the use of water as a monomer or solvent for the polymerization reaction is extremely challenging. Isonitriles are an important class of reactive synthons, commonly used as reactive monomers in multicomponent polymerizations. In recent years, the gradual polymerization based on isonitrile monomers has been rapidly developed and can be mainly classified into seven types of Passerini polymerization, ugi polymerization, multicomponent polymerization based on isonitrile compound and butynedioic acid diester compound, multicomponent polymerization based on isonitrile compound and green monomer, multicomponent polymerization based on isonitrile compound and industrial waste, and polymerization .（M. Li, X. Fu, J. Wang, A. Qin, and B. Z. Tang, Progress in Isocyanide-Based Step-Growth Polymerization,Macromol. Chem. Phys.,2022, 2200352.） based on isonitrile acetate, wherein multicomponent polymerization based on isonitrile compound and green monomer has attracted a wide attention. The isonitrile has a special electronic chemical structure, so that the isonitrile can capture carbon dioxide, water, amino acid and other green raw materials, takes sustainable resources as a polymerization monomer to construct a functional polymer material, and accords with the concept of sustainable development. However, these reactions are relatively harsh conditions, such as metal catalysis, high temperatures, and acidic or basic environments. Therefore, the development of novel, efficient and mild polymerization of isonitrile-based monomers with green color is of great significance. Disclosure of Invention Aiming at the defects existing in the prior art, the invention aims to provide a poly alpha-oximido amide compound and a preparation method and application thereof. In the invention, the binary isocyanide compound and the binary chlorooxime compound are polymerized in a mixed solvent of an organic solvent and water under the environment of normal temperature and normal pressure, wherein the water is taken as a green monomer to participate in the polymerization, so as to obtain a series of poly alpha-oximido amide compounds. Through systematic condition screening, we obtained optimal conditions for polymerization, resulting in polymers in high yields and high molecular weights. The preparation method can be carried out in an environment of normal temperature and normal pressure, and has the advantages of green reaction, high efficiency, high atom economy and easy operation. The prepared poly alpha-oximido amide compound has good processability, film forming property and non-traditional luminescence property. It is a further object of the present invention to provide a novel polymerization-induced luminescence system, a process for converting non-luminescent small molecules (i.e. monomers) into luminescent polymers. Still another object of the present invention is to provide an application of the poly α -oximido amides described above in the detection of transition metal ions. The aim of the invention is achieved by the following technical scheme: a preparation method of poly alpha-oximido amide compounds comprises the following steps: (1) Carrying out polymerization reaction on the binary isocyanide compound and the binary chlorooxime compound in a mixed solvent of an organic solvent and water to obtain a crude product; (2) Carrying out subsequent treatment on the crude product to obtain a poly alpha-oximido amide compound; The structural general formula of the binary isonitrile compound is shown as formula (II): (II); The structural general formula of the binary chlorine oxime compound is shown as formula (III): (III); The structural general formula of the poly alpha-oximido amide compound is shown as a formula (I): (I); In the formulas (I) - (III), n is an integer more than or equal to 2, and R 1,R2 is the same or different organic groups. Preferably, n is an integer of 2 to 400. Preferably, in the formulas (I) - (III), R 1 is selected from any one of the structural formulas 1-28, and R 2 is selected from any one of the structural formulas 1-28; Wherein m is an integer of 1 to 20, X=NH, O, S or SiH 2, and represents a substitution position. Preferably, the organic solvent in the step (1) is at least one selected from tetrahydrofuran, dichloromethane, chloroform, toluene, 1, 4-dioxane, dimethyl sulfoxide and N, N-dimethylformamide, and further preferably, the organic solvent is tetrahydrofuran, and the obtained poly alpha-oximido amide compound has highe