A poly-alpha-oximamide compound, a preparation method and application thereof
Poly-α-oxime amides were prepared by polymerizing diisocyanates and dichlorooximes at room temperature and pressure, solving the problem of harsh polymerization conditions for isonitriles and achieving efficient, green synthesis and polymerization-induced luminescence properties, which are suitable for the detection of transition metal ions.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- SOUTH CHINA UNIV OF TECH
- Filing Date
- 2023-07-07
- Publication Date
- 2026-05-08
AI Technical Summary
Existing isonitrile polymerization reactions require harsh conditions, making it difficult to carry out efficiently at room temperature and pressure. Furthermore, there is a lack of green and efficient polymerization methods to utilize natural monomers to construct functional polymer materials.
Polymerization of diisocyanates and dichlorooximes was carried out in a mixed solvent of organic solvent and water at ambient temperature and pressure using phosphate catalysts to obtain polyα-oxime amides.
It achieves the preparation of polymers with high yield and high molecular weight, with good processing performance and non-traditional luminescent properties, and is suitable for the detection of transition metal ions.
Smart Images
Figure CN116769157B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of polymer chemistry and materials science, specifically relating to a polyα-oxime amide compound, its preparation method, and its application. Background Technology
[0002] Water is an abundant, natural, and sustainable resource; however, in most cases, water is detrimental to the equilibrium motion of chemical reactions and catalytic systems. Therefore, using water as a monomer or solvent in polymerization reactions presents significant challenges. Isocyanides are an important class of reactive syntheticons, often used as monomers in multicomponent polymerization. In recent years, step-growth polymerization based on isocyanide monomers has developed rapidly, and can be mainly divided into the following seven categories: Passerini polymerization, Ugi polymerization, multicomponent polymerization based on isocyanide compounds and butynedioic acid diesters, multicomponent polymerization based on isocyanide compounds and green monomers, multicomponent polymerization based on isocyanide compounds and industrial waste, and polymerization based on isocyanide acetates. (M. Li, X. Fu, J. Wang, A. Qin, and BZ Tang, Progress in Isocyanide-Based Step-Growth Polymerization, Macromol. Chem. Phys. (2022, 2200352.) Multicomponent polymerization based on isonitriles and green monomers has attracted widespread attention. Due to the unique electronic chemical structure of isonitriles, they can capture green raw materials such as carbon dioxide, water, and amino acids, using sustainable resources as monomers to construct functional polymer materials, which aligns with the concept of sustainable development. However, these reactions require relatively harsh conditions, such as metal catalysis, high temperatures, and acidic or alkaline environments. Therefore, developing novel, efficient, and mild-condition polymerization based on isonitriles and green monomers is of great significance. Summary of the Invention
[0003] To address the shortcomings of existing technologies, the present invention aims to provide a polyα-oxime amide compound, its preparation method, and its applications. In this invention, a diisocyanate compound and a dichlorooxime compound are polymerized in a mixed solvent of organic solvent and water under ambient temperature and pressure. Water, as a green monomer, also participates in the polymerization reaction, yielding a series of polyα-oxime amide compounds. Through systematic condition screening, the optimal conditions for the polymerization reaction were obtained, resulting in polymers with high yields and high molecular weights. The preparation method of this invention can be carried out under ambient temperature and pressure, and the reaction is green, efficient, atom-economical, and easy to operate. The prepared polyα-oxime amide compounds exhibit good processability, film-forming properties, and non-traditional luminescence characteristics.
[0004] Another object of the present invention is to provide a novel polymerization-induced emission system for the process of converting non-luminescent small molecules (i.e. monomers) into luminescent polymers.
[0005] Another object of the present invention is to provide the application of the above-mentioned poly-α-oxime amide compounds in the detection of transition metal ions.
[0006] The objective of this invention is achieved through the following technical solution:
[0007] A method for preparing a polyα-oxime amide compound includes the following steps:
[0008] (1) A diisocyanate compound and a dichlorooxime compound were polymerized in a mixed solvent of organic solvent and water to obtain a crude product;
[0009] (2) The crude product was further processed to obtain poly-α-oxime amide compounds;
[0010] The general structural formula of the aforementioned binary isonitrile compounds is shown in formula (II):
[0011] (II);
[0012] The general structural formula of the aforementioned binary chlorooxime compounds is shown in formula (Ⅲ):
[0013] (III);
[0014] The general structural formula of the polyα-oxime amide compounds is shown in formula (Ⅰ):
[0015] (I);
[0016] In equations (I) to (III), n R is an integer greater than or equal to 2. 1 R 2 These are the same or different organic groups.
[0017] Preferred, n It is an integer between 2 and 400.
[0018] Preferably, in equations (I) to (III), R 1 Selected from any one of structural formulas 1 to 28; R 2 Selected from any one of structural formulas 1 to 28;
[0019]
[0020]
[0021]
[0022]
[0023] Where m is an integer from 1 to 20; X = NH, O, S or SiH2; * indicates the substitution position.
[0024] Preferably, the organic solvent in step (1) is selected from at least one of tetrahydrofuran, dichloromethane, chloroform, toluene, 1,4-dioxane, dimethyl sulfoxide, and N,N-dimethylformamide; as a further preferred option, the organic solvent is tetrahydrofuran, in which case the obtained polyα-oxime amide compound has a higher molecular weight and better solubility, which is convenient for the next step of application.
[0025] Preferably, the volume ratio of the organic solvent to water in step (1) is 4:1 to 1:4; more preferably, the volume ratio of the organic solvent to water is 1:3.
[0026] Preferably, the molar ratio of the diisocyanate compound to the dichlorooxime compound in step (1) is 1:(0.6~1.5), and the concentration of the diisocyanate compound is 0.01~5 mol / L; as a further preferred embodiment, the molar ratio of the diisocyanate compound to the dichlorooxime compound is 1:1.2, and the concentration of the diisocyanate compound is 0.017 mol / L.
[0027] Preferably, the polymerization reaction in step (1) is carried out at a temperature of 0~200°C. o C; as a further preferred option, the temperature is room temperature.
[0028] Preferably, the polymerization reaction time in step (1) is 5 to 1000 minutes; more preferably, the polymerization reaction time is 360 minutes.
[0029] Preferably, the polymerization reaction in step (1) is carried out under normal pressure.
[0030] Preferably, the polymerization reaction in step (1) is carried out under the action of a phosphate catalyst; more preferably, the catalyst is one or more of Na2HPO4, K2HPO4, KH2PO4, NaH2PO4, K3PO4, and Na3PO4; more preferably, it is a phosphate buffer solution (PBS). More preferably, the concentration of the phosphate catalyst is 0~5 mol / L. More preferably, the concentration is 0.01~0.1 mol / L.
[0031] Preferably, the subsequent processing described in step (2) refers to centrifuging the reaction stock solution to obtain the polymer, washing the precipitate multiple times with water and methanol, collecting the precipitate, and vacuum drying to constant weight.
[0032] The poly-α-oxime amide compounds prepared by the above method exhibit polymerization-induced emission characteristics during the polymerization process of this invention. The poly-α-oxime amide compounds possess good thermal stability and film-forming properties, and their films have a high refractive index. Furthermore, these poly-α-oxime amide compounds exhibit non-traditional luminescence characteristics and can be applied to the detection of transition metal ions.
[0033] The above-mentioned poly-α-oxime amide compounds are used as luminescent materials.
[0034] The above-mentioned poly-α-oxime amide compounds are used in the fabrication of optical devices.
[0035] The application of the above-mentioned poly-α-oxime amide compounds in the detection of transition metal ions includes the following steps: dissolving the poly-α-oxime amide compound in its good solvent, adding the sample to be tested to the solution, observing the change in fluorescence intensity of the mixed solution, and determining whether the sample to be tested contains transition metal ions.
[0036] Preferably, the concentration of the polyα-oxime amide compound is 1~100 μM; the good solvent is one or more of tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide; and the transition metal ion is Mn. 2+ Fe 3+ Fe 2+ Co 2+ Ni 2+ Cu 2+ Pd 2+ Au 3+ Rh 3+ Ru 3+ UO4 2+ One or more of them.
[0037] Compared with the prior art, the present invention has the following advantages:
[0038] (1) The polymerization reaction of this invention has not been reported before and is highly innovative and significant. This method not only enriches the library of multicomponent polymerization reactions based on isonitriles, but also provides a new method for synthesizing functional polymer materials using natural monomers.
[0039] (2) The preparation method of the present invention is simple to operate, the reaction raw materials and catalysts are readily available, and water can be used as monomer and solvent; the polymerization reaction conditions are mild and efficient, and high molecular weight polymers are obtained in high yield; the poly-α-oxime amide compounds obtained have good thermal stability and excellent processability, and their solid films have a high refractive index.
[0040] (3) The polymerization reaction process of the present invention exhibits polymerization-induced light emission characteristics, providing a novel system for polymerization-induced light emission.
[0041] (4) The poly-α-oxime amide compounds of the present invention exhibit non-traditional luminescence properties and can be applied to the detection of transition metal ions. Attached Figure Description
[0042] Figure 1 The poly-α-oxime amide compounds prepared in Example 1, along with their corresponding monomers and model compounds, were subjected to DMSO- d 6. 1H NMR spectra; where A is the spectrum of monomer M1, B is the spectrum of monomer M2, C is the spectrum of the model small molecule α-oxime amide, and D is the spectrum of the poly-α-oxime amide compound prepared in Example 1.
[0043] Figure 2 The poly-α-oxime amide compounds prepared in Example 1, along with their corresponding monomers and model compounds, were subjected to DMSO- d 6. Carbon NMR spectra; where A is the spectrum of monomer M1, B is the spectrum of monomer M2, C is the spectrum of the model small molecule α-oxime amide, and D is the spectrum of the poly-α-oxime amide compound prepared in Example 1.
[0044] Figure 3 The thermogravimetric curve of the polyα-oxime amide compound prepared in Example 1 is shown.
[0045] Figure 4 The refractive index curve of the polyα-oxime amide compound film prepared in Example 1 is shown.
[0046] Figure 5 The ultraviolet absorption spectrum (A), excitation spectrum, and photofluorescence spectrum (B) of the polyα-oxime acyl compound prepared in Example 1.
[0047] Figure 6 This is a comparison of the photofluorescence spectra of the polyα-oxime acyl compound prepared in Example 1 with monomer 1a, monomer 2a, and the model small molecule.
[0048] Figure 7 The photofluorescence spectrum of the poly-α-oxime acyl compound prepared in Example 3 after interaction with copper ions is shown. Detailed Implementation
[0049] The present invention will be further described in detail below with reference to specific embodiments and accompanying drawings. However, the implementation of the present invention is not limited thereto. For process parameters not specifically noted, conventional techniques can be referred to.
[0050] Example 1
[0051] The synthesis process of monomer M1 in this embodiment is as follows: 1,6-hexanediamine (40 mmol, 4.65 g), ethyl formate (400 mmol, 32.2 mL), and a stir bar were added to a 250 mL flask and stirred overnight at 60 °C. After the reaction was completed, the organic solvent in the reaction system was removed by rotary evaporator to obtain the intermediate N,N'-diformyl-1,6-diaminohexane. The intermediate N,N'-diformyl-1,6-diaminohexane (40 mmol, 6.89 g) and the stir bar were added to a 250 mL flask, and the system was evacuated and purged with nitrogen three times. Then, dichloromethane (60 mL) and triethylamine (60 mL) were added. The reaction apparatus was placed in a low-temperature reactor at -60 °C and cooled for 5 minutes. Phosphorus oxychloride (80 mmol, 7.3 mL) was dissolved in dichloromethane (40 mL) and added dropwise to the reaction system. After the addition was complete, the system was cooled at -60 °C. The reaction was carried out at ℃ for 1 hour, then allowed to proceed overnight at room temperature. After the reaction was complete, 100 mL of saturated sodium carbonate aqueous solution was added to quench the reaction. The mixture was extracted with dichloromethane, and the organic phases were combined. Dichloromethane was removed by rotary evaporation. Finally, the product was obtained by silica gel column chromatography using petroleum ether and dichloromethane as eluents, with a yield of 85%. The structure is as follows:
[0052]
[0053] M1
[0054] The synthesis process of monomer M2 in this embodiment is as follows: Terephthalaldehyde (20 mmol, 2.68 g), hydroxylamine hydrochloride (40 mmol, 2.78 g), and a stir bar were added to a 250 mL flask. Methanol solution (40 mL) was added and stirred to dissolve the soluble compounds. Immediately afterwards, sodium acetate aqueous solution (20 wt%, 10 mL) was added, and the mixture was stirred at room temperature for 1 hour. After the reaction was complete, the methanol solution in the reaction system was removed by rotary evaporation. Ethyl acetate (50 mL) was added, and the mixture was washed three times with saturated brine. The ethyl acetate was then removed by rotary evaporation to obtain the intermediate product, terephthalaldehyde oxime. Terephthalaldehyde oxime (20 mmol, 3.28 g), N-chlorosuccinimide (22 mmol, 2.94 g), and a stir bar were added to a 100 mL flask. N,N-dimethylformamide (20 mL) was then added, and the mixture was stirred at room temperature for 1 hour. After the reaction was complete, ethyl acetate (50 mL) was added... The product was washed 10 times with saturated brine, and ethyl acetate was removed by rotary evaporation. Finally, the product was separated by silica gel column chromatography using petroleum ether and ethyl acetate as eluents, with a yield of 75%. The structure is as follows:
[0055]
[0056] M2
[0057] A method for preparing a polyα-oxime amide compound (P1) includes the following steps:
[0058] (1) Add 27.2 mg (0.2 mmol) monomer M1 and 55.9 mg (0.24 mmol) monomer M2 to a 20 mL reaction flask, inject 4.0 mL of tetrahydrofuran with a syringe, and then immediately add 8.0 mL of 0.03 mol / L phosphate buffer solution (PBS). Stir the reaction at room temperature for 6 hours (400 rpm).
[0059] (2) After the reaction is completed, the polymer will precipitate out of the reaction system and the crude polymer product is obtained by centrifugation; the polymer product is washed multiple times with deionized water and methanol, and finally vacuum dried to constant weight (drying temperature is 50 °C) to obtain poly-α-oxime amide compound P1.
[0060] Analysis showed that the yield of poly-α-oxime amide compound P1 was 90%, the weight-average molecular weight was 53,600, and the molecular weight distribution was 3.34.
[0061] The synthesis of the model small molecule α-oxime amide was as follows: Isonitrile n-butane (5 mmol, 415.6 mg) and α-chlorobenzaldehyde oxime (5.5 mmol, 855.7 mg) were added to a 250 mL flask. 20 mL of tetrahydrofuran was injected using a syringe, followed immediately by 40 mL of 0.05 mol / L phosphate buffered saline (PBS). The mixture was stirred at room temperature for 6 hours (400 rpm). After the reaction was complete, the tetrahydrofuran was removed from the reaction system using a rotary evaporator. Ethyl acetate (30 mL) was added, and the mixture was washed three times with saturated brine. The ethyl acetate was then removed using a rotary evaporator. Finally, the product was obtained by silica gel column chromatography using petroleum ether and ethyl acetate as eluents, with a yield of 85%. The structure is as follows:
[0062]
[0063] The NMR spectra of this poly-α-oxime amide compound, its corresponding monomer, and the model small molecule α-oxime amide (* represents solvent peaks) are shown below. Figure 1 , Figure 2 The spectrum is shown below (where A is the spectrum of monomer M1, B is the spectrum of monomer M2, C is the spectrum of the model small molecule α-oxime amide, and D is the spectrum of poly-α-oxime amide compounds); Figure 1 For hydrogen spectrum, Figure 2 This is a carbon spectrum. From... Figure 1The data indicates that the polymer is a poly-α-oxime amide compound, with peaks at chemical shifts of 1.32, 1.47, and 3.19 ppm. Figure 1 The peak at position D corresponds to the characteristic peak of hydrogen atoms on three carbon atoms in an aliphatic chain; the peak at a chemical shift of 7.55 ppm ( Figure 1 The peak at position D corresponds to the characteristic peak of hydrogen atoms on the benzene ring; the peak at a chemical shift of 8.51 ppm ( Figure 1 The peak (D) in the figure corresponds to the characteristic peak of the hydrogen atom in the amide; the peak at a chemical shift of 11.56 ppm ( Figure 1 D) corresponds to the characteristic peak of the hydroxyl hydrogen atom on the oxime group. From Figure 2 We can see poly-α-oxime amide compounds ( Figure 2 The chemical shifts of the amide carbon and oxime carbon corresponding to D) are 163.57 and 152.84 ppm, respectively. All of these confirm the correctness of the polymer structure.
[0064] Figure 3 The thermogravimetric plot of poly-α-oxime amide compound P1 shows that the decomposition temperature (the temperature corresponding to a 5% weight loss) is 244 °C, indicating that the prepared poly-α-oxime amide compound has good thermal stability.
[0065] Figure 4 The refractive index curve of the polyα-oxime amide compound P1 film is shown. The refractive index at 589 nm is 1.6173, indicating that this polyα-oxime amide compound has a high refractive index. Furthermore, this polyα-oxime amide compound is readily soluble in common organic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide at room temperature, indicating excellent solubility and processability.
[0066] Figure 5 This is the photophysical spectrum of polyα-oxime acyl compound P1. Figure 5 In the image, A represents the ultraviolet absorption spectrum of P1, with a maximum absorption wavelength of 290 nm. Figure 5 In the figure, the dashed line B represents the excitation spectrum of P1, and the solid line represents the photofluorescence spectrum of P1. From the figure, we can see that the absorption and excitation spectra of P1 are mismatched; the excitation wavelength of 290 nm cannot excite the polymer to emit light. Therefore, the luminescence of this polymer is non-traditional.
[0067] Figure 6The image shows a comparison of the photofluorescence spectra of monomers 1a and 2a, the model compound, and poly-α-oxime acyl compound P1. Monomers 1a and 2a showed almost no emission under excitation light of 370 nm, the model compound showed weak emission at 430 nm, while P1 showed strong emission at 450 nm. Furthermore, the luminescence of the polymer gradually increased with increasing degree of polymerization, indicating that this polymerization process exhibits polymerization-induced luminescence characteristics.
[0068] The structural formula of the poly-α-oxime amide compound P1 is:
[0069]
[0070] P1
[0071] Example 2
[0072] In this embodiment, monomer M1 is the same as monomer M1 in Example 1;
[0073] The synthesis method of monomer M3 in this embodiment is consistent with the synthesis method of monomer M2 in Example 1. The specific process is as follows: 4,4'-oxydibenzaldehyde (4.52 g, 20 mmol), hydroxylamine hydrochloride (40 mmol, 2.78 g), and a stir bar were added to a 250 mL flask. Methanol solution (40 mL) was added and stirred to dissolve the hydroxylamine hydrochloride. Then, sodium acetate aqueous solution (20 wt%, 10 mL) was immediately added and stirred at room temperature for 1 hour. After the reaction was completed, the methanol solution in the reaction system was removed by rotary evaporator. Ethyl acetate (50 mL) was added and washed three times with saturated brine. Then, ethyl acetate was removed by rotary evaporator to obtain the intermediate product m-4,4'-oxydibenzaldehyde oxime. 4,4'-oxydibenzaldehyde oxime (20 mmol, 5.13 g), N-chlorosuccinimide (22 mmol, 2.94 g), and a stir bar were added to a 100 mL flask. Then, N,N-dimethylformamide (20 mmol, 5.13 g), hydroxylamine hydrochloride (22 mmol, 2.94 g), and a stir bar were added. The mixture was stirred at room temperature for 1 hour (mL); after the reaction was complete, ethyl acetate (50 mL) was added, and the mixture was washed 10 times with saturated brine. Ethyl acetate was removed by rotary evaporation. Finally, the product was separated by silica gel column chromatography using petroleum ether and ethyl acetate as eluents, with a yield of 73%. The structure is as follows:
[0074]
[0075] M3
[0076] A method for preparing a polyα-oxime amide compound (P2) includes the following steps:
[0077] (1) Add 27.2 mg (0.2 mmol) monomer M1 and 78.0 mg (0.24 mmol) monomer M3 to a 20 mL reaction flask, inject 4.0 mL of tetrahydrofuran with a syringe, and then immediately add 8.0 mL of 0.03 mol / L phosphate buffer solution (PBS). Stir the reaction at room temperature for 6 hours (400 rpm).
[0078] (2) After the reaction is completed, the polymer will precipitate out of the reaction system and the crude polymer product is obtained by centrifugation; the polymer product is washed multiple times with deionized water and methanol, and finally vacuum dried to constant weight (drying temperature is 50 °C) to obtain poly-α-oxime amide compound P2.
[0079] Analysis showed that the yield of poly-α-oxime amide compound P2 was 93%, the weight-average molecular weight was 43,400, and the molecular weight distribution was 2.91.
[0080]
[0081] P2
[0082] Example 3
[0083] The synthesis of monomer M4 in this embodiment is as follows: 1,4-phenylenediamine (20 mmol, 2.72 g), chloroform (50 mmol, 4.0 mL), benzyltriethylammonium chloride (0.44 mmol, 0.1 g), and a stir bar were added to a 100 mL round-bottom flask. 15 mL of dichloromethane was added and stirred to dissolve the mixture. Then, 20 mL of NaOH aqueous solution (50 wt%) was slowly added under vigorous stirring, and the mixture was stirred overnight at 40 ºC. After the reaction was complete, the reaction solution was cooled to room temperature, and 50 mL of deionized water was added to quench the reaction. The aqueous phase was extracted three times with DCM. The organic phases were combined, and dichloromethane was removed using a rotary evaporator. Finally, the product was obtained by silica gel column chromatography using petroleum ether and dichloromethane as eluents, with a yield of 28%. The structure is as follows:
[0084]
[0085] M4
[0086] In this embodiment, monomer M2 is the same as monomer M2 in Example 1.
[0087] A method for preparing a polyα-oxime amide compound (P3) includes the following steps:
[0088] (1) Add 31.2 mg (0.2 mmol) monomer M4 and 55.9 mg (0.24 mmol) monomer M2 to a 20 mL reaction flask, inject 4.0 mL of tetrahydrofuran with a syringe, and then immediately add 8.0 mL of 0.03 mol / L phosphate buffer solution (PBS). Stir the reaction at room temperature for 6 hours (400 rpm).
[0089] (2) After the reaction is completed, the polymer will precipitate out of the reaction system and the crude polymer product is obtained by centrifugation; the polymer product is washed with deionized water and methanol multiple times, and finally vacuum dried to constant weight (drying temperature is 50 °C) to obtain poly-α-oxime amide compound P3.
[0090] Analysis showed that the yield of poly-α-oxime amide compound P3 was 95%, the weight-average molecular weight was 17,200, and the molecular weight distribution was 1.71.
[0091]
[0092] P3
[0093] Example 4
[0094] In this embodiment, monomer M4 is the same as monomer M4 in Example 3;
[0095] The synthesis method of monomer M5 in this embodiment is consistent with the synthesis method of monomer M2 in Example 1. The specific process is as follows: In a 250 mL flask, isophthalaldehyde (2.68 g, 20 mmol), hydroxylamine hydrochloride (40 mmol, 2.78 g), and a stir bar were added. Methanol solution (40 mL) was added and stirred to dissolve the hydroxylamine. Immediately afterwards, sodium acetate aqueous solution (20 wt%, 10 mL) was added, and the mixture was stirred at room temperature for 1 hour. After the reaction was complete, the methanol solution in the reaction system was removed by rotary evaporation. Ethyl acetate (50 mL) was added, and the mixture was washed three times with saturated brine. The ethyl acetate was then removed by rotary evaporation to obtain the intermediate product isophthalaldehyde oxime. Isophthalaldehyde oxime (20 mmol, 3.28 g), N-chlorosuccinimide (22 mmol, 2.94 g), and a stir bar were added to a 100 mL flask. N,N-dimethylformamide (20 mL) was then added, and the mixture was stirred at room temperature for 1 hour. After the reaction was complete, ethyl acetate (50 mL) was added... The product was washed 10 times with saturated brine, and ethyl acetate was removed by rotary evaporation. Finally, the product was separated by silica gel column chromatography using petroleum ether and ethyl acetate as eluents, with a yield of 73%. The structure is as follows:
[0096]
[0097] M5
[0098] A method for preparing a polyα-oxime amide compound (P4) includes the following steps:
[0099] (1) Add 31.2 mg (0.2 mmol) monomer M4 and 55.9 mg (0.24 mmol) monomer M5 to a 20 mL reaction flask, inject 4.0 mL of tetrahydrofuran with a syringe, and then immediately add 8.0 mL of 0.03 mol / L phosphate buffer solution (PBS). Stir the reaction at room temperature for 6 hours (400 rpm).
[0100] (2) After the reaction is completed, the polymer will precipitate out of the reaction system and the crude polymer product is obtained by centrifugation; the polymer product is washed multiple times with deionized water and methanol, and finally vacuum dried to constant weight (drying temperature is 50 °C) to obtain poly-α-oxime amide compound P4.
[0101] Analysis revealed that the yield of poly-α-oxime amide compound P4 was 84%, with a weight-average molecular weight of 49,300 and a molecular weight distribution of 3.16.
[0102]
[0103] P4
[0104] Example 5
[0105] The synthesis method of monomer M6 in this embodiment is consistent with the synthesis method of monomer M1 in Example 1. The specific process is as follows: 1,3-propanediamine (40 mmol, 2.97 g), ethyl formate (60 mL), and a stir bar are added to a 250 mL flask and stirred overnight at 60 °C. After the reaction is completed, the organic solvent in the reaction system is removed by rotary evaporation to obtain the intermediate product N,N'-diformyl-1,3-diaminopropane. The intermediate N,N'-diformyl-1,3-diaminopropane (40 mmol, 5.21 g) and a stir bar are added to a 250 mL flask, and the mixture is evacuated and purged with nitrogen three times. Then, dichloromethane (60 mL) and triethylamine (60 mL) are added. The reaction apparatus is placed in a low-temperature reaction vessel at -60 °C and cooled for 5 minutes. Phosphorus oxychloride (80 mmol, 7.3 mL) is dissolved in dichloromethane (40 mmol, 5.21 g). The solution was added dropwise to the reaction system in mL, and after the addition was complete, the reaction was carried out at -60 °C for 1 hour, followed by overnight reaction at room temperature. After the reaction was completed, 100 mL of saturated sodium carbonate aqueous solution was added to quench the reaction, and the mixture was extracted with dichloromethane. The organic phases were combined, and dichloromethane was removed by rotary evaporation. Finally, the product was separated by silica gel column chromatography using petroleum ether and dichloromethane as eluents, with a yield of 82%. The structure is as follows:
[0106]
[0107] M6
[0108] In this embodiment, monomer M2 is the same as monomer M2 in Example 1;
[0109] A method for preparing a polyα-oxime amide compound (P5) includes the following steps:
[0110] (1) Add 18.8 mg (0.2 mmol) monomer M6 and 55.9 mg (0.24 mmol) monomer M2 to a 20 mL reaction flask, inject 4.0 mL of tetrahydrofuran with a syringe, and then immediately add 8.0 mL of 0.03 mol / L phosphate buffer solution (PBS). Stir the reaction at room temperature for 6 hours (400 rpm).
[0111] (2) After the reaction is completed, the polymer will precipitate out of the reaction system and the crude polymer product is obtained by centrifugation; the polymer product is washed multiple times with deionized water and methanol, and finally vacuum dried to constant weight (drying temperature is 50 °C) to obtain poly-α-oxime amide compound P5.
[0112] Analysis revealed that the yield of poly-α-oxime amide compound P5 was 75%, with a weight-average molecular weight of 30,400 and a molecular weight distribution of 3.16.
[0113]
[0114] P5
[0115] Example 6
[0116] In this embodiment, monomer M6 is the same as monomer M6 in Example 5;
[0117] In this embodiment, monomer M3 is the same as monomer M3 in Example 2;
[0118] A method for preparing a polyα-oxime amide compound (P6) includes the following steps:
[0119] (1) Add 18.8 mg (0.2 mmol) monomer M6 and 78 mg (0.24 mmol) monomer M3 to a 20 mL reaction flask, inject 4.0 mL of tetrahydrofuran with a syringe, and then immediately add 8.0 mL of 0.03 mol / L phosphate buffer solution (PBS). Stir the reaction at room temperature for 6 hours (400 rpm).
[0120] (2) After the reaction is completed, the polymer will precipitate out of the reaction system and the crude polymer product is obtained by centrifugation; the polymer product is washed with deionized water and methanol multiple times, and finally vacuum dried to constant weight (drying temperature is 50 °C) to obtain poly-α-oxime amide compound P6.
[0121] Analysis revealed that the yield of poly-α-oxime amide compound P6 was 87%, with a weight-average molecular weight of 29,800 and a molecular weight distribution of 2.23.
[0122]
[0123] P6
[0124] Example 7
[0125] A poly-α-oxime amide compound, P3, is used for the production of copper ions (Cu). 2+ The detection method for ( ) is as follows:
[0126] (1) Dissolve P3 in N,N-dimethylformamide to prepare a solution with a concentration of 10. -2 M's P3 solution was used as a fluorescent probe for Cu 2+ Conduct testing;
[0127] (2) Testing for different Cu content 2+ The photofluorescence spectrum of a P3 solution at a concentration of [concentration missing], with an excitation wavelength of 370 nm. For example... Figure 7 The fluorescence intensity of P3 shown in the figure changes with Cu 2+ The fluorescence of P3 decreases significantly with increasing concentration, indicating that copper ions have a significant fluorescence quenching effect on P3.
[0128] The above embodiments of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the implementation of the present invention. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively describe all possible implementations here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.
Claims
1. A method for preparing a polyα-oxime amide compound, characterized in that, Includes the following steps: (1) A diisocyanate compound and a dichlorooxime compound were polymerized in a mixed solvent of organic solvent and water to obtain a crude product; (2) The crude product was further processed to obtain poly-α-oxime amide compounds; The general structural formula of the aforementioned binary isonitrile compounds is shown in formula (II): （Ⅱ）; The general structural formula of the aforementioned binary chlorooxime compounds is shown in formula (Ⅲ): （Ⅲ）; The general structural formula of the polyα-oxime amide compounds is shown in formula (Ⅰ): （Ⅰ）; In equations (I) to (III), n R is an integer greater than or equal to 2. 1 R 2 They are the same or different organic groups; in formulas (I) to (III), R 1 Selected from any one of structural formulas 1 to 28; R 2 Selected from any one of structural formulas 1 to 28; Where m is an integer from 1 to 20; X = NH, O, S or SiH2; * indicates the substitution position.
2. The method for preparing a poly-α-oxime amide compound according to claim 1, characterized in that: The organic solvent in step (1) is one or more of tetrahydrofuran, dichloromethane, chloroform, toluene, 1,4-dioxane, dimethyl sulfoxide, and N,N-dimethylformamide; the volume ratio of the organic solvent in step (1) to water is 4:1 to 1:4; the molar ratio of the diisocyanate compound to the dichlorooxime compound in step (1) is 1:(0.6 to 1.5); the concentration of the diisocyanate compound in step (1) is 0.01 to 5 mol / L.
3. The method for preparing a polyα-oxime amide compound according to claim 1, characterized in that: The polymerization reaction in step (1) is carried out at a temperature of 0~200°C. o C; The polymerization reaction in step (1) takes 5 to 1000 minutes; The polymerization reaction in step (1) is carried out under normal pressure.
4. The method for preparing a polyα-oxime amide compound according to claim 1, characterized in that: The polymerization reaction described in step (1) is carried out under the action of a phosphate catalyst; the phosphate catalyst is one or more of Na2HPO4, K2HPO4, KH2PO4, NaH2PO4, K3PO4, and Na3PO4; the concentration of the phosphate catalyst is 0~5 mol / L.
5. The poly-α-oxime amide compound prepared by the preparation method according to any one of claims 1 to 4.
6. The use of the poly-α-oxime amide compound of claim 5 in the preparation of optical devices.
7. The application of the poly-α-oxime amide compound according to claim 5 in the detection of transition metal ions, characterized in that, Includes the following steps: A poly-α-oxime amide compound is dissolved in its good solvent, and the sample to be tested is added. The change in fluorescence intensity of the mixed solution is observed to determine whether the sample contains transition metal ions. The concentration of the poly-α-oxime amide compound is 1~100 μM. The good solvent is one or more of tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide. The transition metal ion is Cu. 2+ .