阅读说明：本技术 一种聚1,4,5-取代***及其制备方法和应用 (Poly-1, 4, 5-substituted triazole and preparation method and application thereof ) 是由 唐本忠 李白雪 秦安军 于 2019-11-07 设计创作，主要内容包括：本发明属于聚合物合成技术领域,公开了一种聚1,4,5-取代三唑及其制备方法和应用。所述聚1,4,5-取代三唑具有式(I)所示的结构通式,其中,n为2～200的整数,R<Sup>1</Sup>,R<Sup>2</Sup>为相同或不同的有机基团。其制备方法为：在惰性或空气氛围下,将二元炔醛化合物和二元叠氮化合物在有机溶剂中进行环加成聚合反应,得到聚1,4,5-取代三唑。本发明从单体结构出发,调整羰基与炔基的位置,设计合成的炔醛单体,能够保证炔类单体的高反应活性,使其能在无催化条件下与叠氮化合物进行聚合。该方法简单高效,能够合成具有较高分子量的聚合物。<Image he="255" wi="700" file="DDA0002263898840000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention belongs to the technical field of polymer synthesis, and discloses poly-1, 4, 5-substituted triazole and a preparation method and application thereof. The poly-1, 4, 5-substituted triazole has a structural general formula shown in formula (I), wherein n is an integer of 2-200, and R is 1 ，R 2 Are identical or different organic radicals. The preparation method comprises the following steps: under the inert or air atmosphere, carrying out cycloaddition polymerization reaction on a binary alkyne-aldehyde compound and a binary azide compound in an organic solvent to obtain the poly-1, 4, 5-substituted triazole. The method starts from a monomer structure, adjusts the positions of carbonyl and alkynyl, designs the synthesized alkyne-aldehyde monomer, can ensure the high reaction activity of the alkyne monomer, and can polymerize with azide under the condition of no catalysis. The method is simple and efficient, and can synthesize polymers with higher molecular weight.)

1. A poly-1, 4, 5-substituted triazole characterized by: the poly 1,4, 5-substituted triazole has a general structural formula shown in formula (I):

wherein n is an integer of 2-200, R¹，R²Are identical or different organic radicals.

2. A poly-1, 4, 5-substituted triazole as claimed in claim 1 wherein: the R is¹Is any one of the following chemical structural formulas 1-12:

the R is²Is any one of the following chemical structural formulas (1) to (12):

wherein m and h are integers of 1-15; x is C, O or S element, and represents a substitution position.

3. The process for producing a poly-1, 4, 5-substituted triazole according to claim 1 or 2, which comprises the following production steps:

under the inert or air atmosphere, carrying out cycloaddition polymerization reaction on a binary alkyne-aldehyde compound with a structure shown in a formula (II) and a binary azide compound with a structure shown in a formula (III) in an organic solvent, and separating a product to obtain poly (1, 4, 5-substituted triazole);

4. The process according to claim 3 for the preparation of a poly-1, 4, 5-substituted triazole, wherein: the organic solvent is one or the mixture of more than two of toluene, 1, 4-dioxane, dimethyl sulfoxide, N-dimethylformamide, dimethylacetamide and N-methylpyrrolidone.

5. The process according to claim 3 for the preparation of a poly-1, 4, 5-substituted triazole, wherein: the temperature of the cycloaddition polymerization reaction is 80-160 ℃, and the reaction time is 1-5 h.

6. The process according to claim 3 for the preparation of a poly-1, 4, 5-substituted triazole, wherein: the molar ratio of the binary alkynal compound to the binary azide compound is 1 (1-1.1); the concentration of the binary alkynal compound in the organic solvent is 0.2-0.8 mol/L.

7. The process according to claim 3 for the preparation of poly-1, 4, 5-substituted triazoles, wherein the isolation of the product is carried out by: after the reaction is finished, dissolving the product in a solvent, then adding the solvent into methanol for precipitation, collecting the precipitate, and drying the precipitate to constant weight to obtain the poly-1, 4, 5-substituted triazole.

8. Use of a poly-1, 4, 5-substituted triazole of claim 1 or 2 for detecting hydrazine.

9. Use of a poly-1, 4, 5-substituted triazole according to claim 1 or 2 for post-modification.

10. The post-modification use of a poly-1, 4, 5-substituted triazole as claimed in claim 9, wherein: the post-modification application refers to the preparation of functional polytriazoles with different thermal stabilities and optical properties by carrying out Schiff base or Knoevenagel reaction on poly-1, 4, 5-substituted triazole and amine or nitrile monomers.

Technical Field

The invention belongs to the technical field of polymer synthesis, and particularly relates to poly-1, 4, 5-substituted triazole and a preparation method and application thereof.

Background

The development and establishment of new polymerization methodology are of great significance for the construction of high molecular materials with unique structures and advanced functions. In the field of polymer synthesis, alkyne-azide click polymerization has become an important method for preparing nitrogen-containing functional materials. The polymerization reaction mainly obtains products mainly comprising poly-1, 4-and 1, 5-substituted triazole, and because hydrogen atoms on a triazole ring in the poly-1, 4, 5-substituted triazole can be replaced by other functional groups, the structure and function regulation and control of the products can be realized through the introduction of different functional groups. Therefore, the preparation of poly-1, 4, 5-substituted triazole and the research on the structural derivation thereof are particularly important for realizing the diversification of the structure and the function of the poly-triazole.

The research on preparation of poly-1, 4, 5-substituted triazole by alkyne-azide cycloaddition polymerization is still in the beginning at home and abroad. Furthermore, some polymerization reactions for the preparation of the above poly-1, 4, 5-substituted triazoles require metal catalysts; some are only suitable for aliphatic azides; and most of the substituents of the triazole ring in the obtained product are ketocarbonyl or phenyl, and the structural regulation and derivation degrees of freedom are lower. Based on the method, the poly-1, 4, 5-substituted triazole with high structural derivation degree is prepared by alkyne-azide cycloaddition polymerization under the condition of no metal catalysis, so that the polymer structure is enriched, and the development of a response type fluorescence sensor has important significance.

Disclosure of Invention

In view of the above disadvantages and shortcomings of the prior art, the present invention is primarily directed to a poly-1, 4, 5-substituted triazole.

Another object of the present invention is to provide a process for the preparation of the above poly-1, 4, 5-substituted triazoles.

It is still another object of the present invention to provide the use of the above poly-1, 4, 5-substituted triazole for the detection of hydrazine.

It is a further object of the present invention to provide post-modification applications of the above-described poly-1, 4, 5-substituted triazoles.

The purpose of the invention is realized by the following technical scheme:

a poly-1, 4, 5-substituted triazole having the general structural formula shown in formula (I):

wherein n is an integer of 2-200, R¹，R²Are identical or different organic radicals.

Further, said R¹Is any one of the following chemical structural formulas 1-12:

wherein m is an integer of 1-15; x is C, O or S element, indicating the substitution position. The R is²Is any one of the following chemical structural formulas (1) to (12):

wherein h is an integer of 1-15; x is C, O or S element, and represents a substitution position.

The preparation method of the poly-1, 4, 5-substituted triazole comprises the following preparation steps:

under the inert or air atmosphere, carrying out cycloaddition polymerization reaction on a binary alkyne-aldehyde compound with a structure shown in a formula (II) and a binary azide compound with a structure shown in a formula (III) in an organic solvent, and separating a product to obtain poly (1, 4, 5-substituted triazole);

further, the organic solvent is one or a mixture of more than two of toluene, 1, 4-dioxane, dimethyl sulfoxide, N-dimethylformamide, dimethylacetamide and N-methylpyrrolidone; dimethyl sulfoxide is preferred.

Further, the temperature of the cycloaddition polymerization reaction is 80-160 ℃, and the reaction time is 1-5 h.

Furthermore, the molar ratio of the binary alkynal compound to the binary azide compound is 1 (1-1.1).

Further, the concentration of the binary alkynal compound in the organic solvent is 0.2-0.8 mol/L, preferably 0.5-0.6 mol/L.

Further, the method for separating the product comprises the following steps: after the reaction is finished, dissolving the product in a solvent, then adding the solvent into methanol for precipitation, collecting the precipitate, and drying the precipitate to constant weight to obtain the poly-1, 4, 5-substituted triazole.

The application of the poly-1, 4, 5-substituted triazole in hydrazine detection.

Post-modification applications of the above poly-1, 4, 5-substituted triazoles.

Further, the post-modification application refers to that poly-1, 4, 5-substituted triazole and amine or nitrile monomer are subjected to Schiff base or Knoevenagel reaction to prepare functional polytriazole with different thermal stability and optical characteristics.

The preparation method and the obtained product have the following advantages and beneficial effects:

(1) the method starts from a monomer structure, adjusts the positions of carbonyl and alkynyl, designs the synthesized alkyne-aldehyde monomer, can ensure the high reaction activity of the alkyne monomer, and can polymerize with azide under the condition of no catalysis. The method is simple and efficient, and can synthesize polymers with higher molecular weight.

(2) The polymerization process of the invention has no byproduct and accords with atom economy.

(3) The poly-1, 4, 5-substituted triazole prepared by the polymerization method can realize the selective detection of hydrazine.

(4) The poly-1, 4, 5-substituted triazole obtained by the invention has better thermal stability and excellent processability, the substituent on the triazole ring is aldehyde group with good derivation, and a series of poly-triazole with precise structure and advanced function can be prepared by various polymer post-modification means.

Drawings

FIG. 1 is a CDCl solution of poly-1, 4, 5-substituted triazole P1 and its corresponding monomer₃Medium nuclear magnetic resonance hydrogen spectrum.

FIG. 2 is a schematic representation of poly-1, 4, 5-substituted triazole P1 and its corresponding monomer in CDCl₃Nuclear magnetic resonance carbon spectrum.

FIG. 3 is a graph of the UV-VIS absorption spectra of solutions of poly-1, 4, 5-substituted triazole P1 at various hydrazine contents.

FIG. 4 is a graph of the fluorescence spectra of solutions of poly-1, 4, 5-substituted triazole P1 at various hydrazine contents.

FIG. 5 is a graph showing the selectivity results of poly-1, 4, 5-substituted triazole P1 for amine compound detection.

FIG. 6 is a diagram showing UV-VIS absorption spectra of a solution of poly-1, 4, 5-substituted triazole P1 and the post-modification product PM2 tetrahydrofuran.

FIG. 7 is a fluorescence spectrum of a solution of poly-1, 4, 5-substituted triazole P1 and the post-modification product PM2 in tetrahydrofuran.

Detailed Description

The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.