Oxazolidinone polymer and its preparation method and application

Abstract

The present invention belongs to the field of polymer synthesis and materials, and specifically relates to an oxazolidinone polymer, its preparation method, and application. The present invention uses a diacetylene monomer, a dialdehyde monomer, carbon dioxide, and a monoamine as raw materials, and reacts in the presence of cuprous iodide and a polar aprotic solvent to obtain the polymer. The oxazolidinone polymer has the following general structural formula: R1, R2, and R3 are the same or different organic groups. The above-mentioned synthesis method has readily available reaction raw materials, mild reaction conditions, and does not require the use of precious metal catalysts, which greatly reduces the reaction cost. In addition, the reaction has a wide range of substrate applicability and good functional group compatibility, and a variety of functional groups can be introduced. The oxazolidinone polymer prepared by the present invention has good processability, high thermal stability, and aggregation-induced emission properties, and has important application value in optical plastics, biomedical materials, optical anti-counterfeiting, fluorescence sensing, and other aspects.

Description

Technical Field

[0001] The invention belongs to the field of polymer synthesis and materials, and particularly relates to an oxazolidinone polymer and a preparation method and application thereof. Background Art

[0002] The preparation of polymer materials with new structures based on renewable materials has important application prospects. Carbon dioxide, as an abundant, inexpensive, non-toxic, environmentally friendly, and renewable C1 resource, has attracted increasing attention from researchers. In recent years, there have been more and more reports on the preparation of polymer materials using polymerization reactions involving carbon dioxide. Lv Xiaobing et al. from Dalian University of Technology published a method for synthesizing polycarbonate from cyclohexene oxide and benzyl glycidyl ether (Sci China Chem., 2015, 58, 999-1004). However, this method requires three steps to obtain the final product, and the reaction process is relatively cumbersome. Yves Gnanou et al. from King Abraham University of Science and Technology published a method for preparing polycarbonate from carbon dioxide, diols, and dihalides catalyzed by cesium carbonate (Polym. Chem., 2016, 7, 4944-4952). However, this method needs to be completed under high pressure conditions, and the reaction conditions are relatively harsh. Qin Anjun et al. from South China University of Technology reported a method for synthesizing cyclic carbonate-based polymers from carbon dioxide, propargyl alcohol, and halogenated aromatic hydrocarbons under atmospheric pressure using palladium acetate as a catalyst (Macromolecules, 2019, 52, 5546-5554). However, this method requires a precious metal catalyst, and the presence of internal alkyne monomers limits the application of this type of polymerization reaction. Wang Xianhong et al. from the Changchun Institute of Applied Chemistry reported a method for copolymerizing carbon dioxide and epoxy compounds to produce polypropylene carbonate using a polymer porphyrin as a catalyst (ACS Catal., 2022, 12, 481-490). However, the catalyst used in this method is not commercially available and must be synthesized in-house. Therefore, developing polymerization reactions with relatively mild reaction conditions, simple operation steps, low reaction costs, and readily available monomers and catalysts, as well as preparing polymer materials with novel structures, has important application value. Among the synthetic functional polymerization methods developed in recent years, multicomponent polymerization reactions have attracted widespread attention due to their advantages such as high synthesis efficiency, simple operation, atom economy, and diverse product structures. In addition, multicomponent polymerization reactions can construct new structures such as heterocycles in situ, which is difficult to achieve with other polymerization methods.

[0003] Traditional organic and polymer luminescent materials emit intense light in solution, but their emission is weakened or absent in the aggregated or solid state, limiting their use in the solid state. In 2001, Tang Benzhong's research group at the Hong Kong University of Science and Technology reported a novel photophysical phenomenon, aggregation-induced emission (AIE): small organic molecule silole derivatives exhibit almost no luminescence in solution, but once formed into nanoparticles or films, their fluorescence intensity increases significantly (Chem. Commun., 2001, 1740-1741). Materials exhibiting AIE properties have been widely used in fields such as displays, chemical detection, and biosensing (Chem. Rev., 2015, 115, 11718-11940). Compared to small molecule materials, reports on AIE-active polymer materials are relatively rare (Prog. Polym. Sci., 2020, 100, 101-176). The preparation of novel AIE polymers based on novel polymerization reactions has important application value. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide an oxazolidinone polymer, a preparation method and application thereof. The present invention uses a diacetylene monomer, a dialdehyde monomer, a monoamine monomer and carbon dioxide as raw materials, and reacts in the presence of cuprous iodide and a polar aprotic solvent to obtain the oxazolidinone polymer. The preparation method is simple, has wide substrate applicability and good functional group compatibility, and is convenient for introducing various functional groups. Different polymer functional materials can be prepared by combining polymer structure design with the above preparation method, and has important scientific significance and application value.

[0005] In order to solve the above-mentioned technical problems, this application provides the following technical solutions:

[0006] The first aspect of the present invention provides an oxazolidinone polymer having the following general structural formula:

[0007]

[0008] Wherein, n is an integer from 2 to 200;

[0009] R1 is selected from any one of the groups represented by Formula 1 to Formula 20, R2 is selected from any one of the groups represented by Formula 1 to Formula 20, and R3 is selected from any one of the groups represented by Formula 21 to Formula 23;

[0010] The structures of the above formulas 1 to 23 are as follows:

[0011]

[0012] wherein m is any integer from 1 to 18, * represents the substitution position, and X = (F, Cl, Br, I).

[0013] The second aspect of the present invention provides a method for preparing the oxazolidinone polymer described in the first aspect, comprising reacting a diacetylene monomer represented by formula (I), a dialdehyde monomer represented by formula (II), a monoamine represented by formula (III), and carbon dioxide in the presence of cuprous iodide and a polar aprotic solvent to obtain the oxazolidinone polymer;

[0014] The structures of formula (I), formula (II) and formula (III) are shown below:

[0015]

[0016] The general reaction formula of the above reaction is as follows:

[0017]

[0018] Furthermore, the molar ratio of the diacetylene monomer, the dialdehyde monomer, the monoamine monomer and cuprous iodide is 1:1:4:0.1-0.8, and is finally selected as 1:1:4:0.35.

[0019] Furthermore, the molar volume ratio of the diacetylene monomer to the polar aprotic solvent is 0.1-0.8 mol:1L, and is finally selected to be 0.1-0.4 mol:1L.

[0020] Furthermore, the polar aprotic solvent is one or more of 1,2,4-trichlorobenzene, o-dichlorobenzene, chlorobenzene, and toluene.

[0021] Furthermore, the reaction is carried out in a carbon dioxide gas atmosphere.

[0022] Furthermore, the reaction temperature is 60-180°C, and is finally selected to be 80-160°C.

[0023] Furthermore, the reaction time is 0.5-24h, and is finally selected to be 1-12h.

[0024] Furthermore, after the reaction is completed, the product is diluted with chloroform and then dropped into petroleum ether to precipitate to obtain an oxazolidinone polymer.

[0025] The third aspect of the present invention provides an oxazolidinone polymer as described in the first aspect as a fluorescent sensor for detecting Fe 3+ Application in this area.

[0026] Furthermore, the oxazolidinone polymer has AIE properties.

[0027] Furthermore, the structure of the oxazolidinone polymer contains one or two of the groups represented by Formulae 15 to 20.

[0028] The fourth aspect of the present invention provides an anti-counterfeiting application of the oxazolidinone polymer described in the first aspect as a luminescent material.

[0029] Furthermore, oxazolidinone polymers with long phosphorescence lifetime and high quantum yield were finally selected for anti-counterfeiting application.

[0030] The technical solution of the present invention has the following advantages over the prior art:

[0031] 1. The present invention uses binary acetylene monomers, binary aldehyde monomers, monoamine monomers and carbon dioxide as reaction raw materials, constructs oxazolidinone polymers in situ under the mediation of cuprous iodide, and directly synthesizes nitrogen-containing and oxygen-containing heterocyclic polymers. The oxazolidinone polymers prepared by the present invention have good thermal stability, and have good solubility in organic solvents such as chloroform, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, etc., and have good processability and film-forming properties. In addition, the oxazolidinone polymers containing AIE active units (such as tetraphenylethylene, etc.) prepared by the present invention have AIE properties and can be used as fluorescent sensors for Fe 3+ Detection of Fe in industrial wastewater 3+ In addition, the film prepared by mixing the oxazolidinone polymer and nylon 6 (PA6) and heating them together has phosphorescence at room temperature and can be used in anti-counterfeiting.

[0032] 2. The present invention uses a polymerization reaction mediated by cuprous iodide, and the reaction raw materials are readily available and no noble metal catalyst is required, which can greatly reduce the reaction cost. In addition, the multi-component polymerization reaction has a wide range of substrate applicability and good functional group compatibility, which is convenient for introducing a variety of functional groups, and is conducive to the design and preparation of different functional polymer materials. The polymerization reaction method provided by the present invention and the oxazolidinone polymer prepared by the method have important scientific significance and application value in the fields of polymer synthesis and materials science.

[0033] 3. The present invention utilizes mild reaction conditions. Carbon dioxide can react with diacetylenes, dialdehydes, and monoamines at atmospheric pressure, eliminating the need for high-pressure reactors and improving reaction safety. Furthermore, the invention utilizes renewable, inexpensive, and readily available carbon dioxide as a raw material to prepare polymeric materials through polymerization. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 This is the H NMR spectrum of the oxazolidinone polymer and its corresponding monomer prepared in Example 17 in CD2Cl2;

[0035] Figure 2This is a thermogravimetric curve of the oxazolidinone polymer prepared in Example 17; the test conditions are: nitrogen atmosphere, heating rate of 10°C / min;

[0036] Figure 3 This is the AIE curve of the oxazolidinone polymer prepared in Example 17;

[0037] Figure 4 Fe was detected for the oxazolidinone polymer prepared in Example 17. 3+ Fluorescence spectrum of

[0038] Figure 5 Schematic diagram of the selectivity of the oxazolidinone polymer prepared in Example 17 for different metal ions;

[0039] Figure 6 These are the fluorescence and phosphorescence patterns of the oxazolidinone polymer prepared in Example 17 under 365 nm excitation light. DETAILED DESCRIPTION

[0040] The present invention will be further described below with reference to the accompanying drawings and specific embodiments so that those skilled in the art can better understand the present invention and implement it. However, the embodiments are not intended to limit the present invention.

[0041] Example 1

[0042] This embodiment relates to the preparation of an oxazolidinone polymer, and the reaction equation is as follows:

[0043]

[0044] The specific steps include:

[0045] (1) Preparation of diacetylene monomers

[0046] The synthesis of the first monomer, the diacetylene monomer, was synthesized according to the preparation method of the published literature (Polym.Chem., 2021, 12, 1078-1085).

[0047] (2) Preparation of dialdehyde monomers

[0048] The second monomer, a dialdehyde monomer, was synthesized according to the preparation method in a published literature (J. Mater. Chem., 2012, 22, 232-240).

[0049] (3) Carbon dioxide (purity 99.99%) and monoamine monomers were purchased from the market. Carbon dioxide was purchased from Jinhong Gas Co., Ltd., and monoamine monomers were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0050] (4) Preparation of oxazolidinone polymers

[0051] To a 10 mL polymerization tube with a side arm, add 45.6 mg (0.1 mmol) of the first monomer, a diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer, a dialdehyde monomer, and 6.7 mg (0.035 mmol) of cuprous iodide. Vacuum and charge with carbon dioxide three times, then add 0.25 mL of ultra-dry 1,2,4-trichlorobenzene. After the monomers are completely dissolved, insert a carbon dioxide balloon and add 29.2 mg (0.4 mmol) of the third monomer, a monoamine monomer. React at 140°C for 7.5 hours. After the reaction is completed and returned to room temperature, dilute with 10 mL of chloroform and add the solution dropwise to 200 mL of vigorously stirred petroleum ether through a dropper plugged with cotton. Let stand, filter, and dry to constant weight to obtain the target polymer. Pale yellow solid with a yield of 68%. GPC results show: M w =10400,PDI=1.35. 1 H NMR (400MHz, CD2Cl2) δ7.40,7.13,6.85,5.54,5.03,3.61,2.81,1.63,0.93.

[0052] The polymer prepared in this example has good solubility and thermal stability; due to the presence of tetraphenylethylene groups, which are active in aggregation-induced emission, the polymer also exhibits aggregation-induced emission. Furthermore, a film made by mixing the oxazolidinone polymer prepared in this invention with nylon 6 (PA6) and co-heating it exhibits phosphorescence at room temperature, which can be used in anti-counterfeiting applications.

[0053] Example 2

[0054] This example uses the same reactants as in Example 1 to prepare an oxazolidinone polymer. The specific steps are as follows:

[0055] To a 10 mL polymerization tube with a side arm, add 45.6 mg (0.1 mmol) of the first monomer, a diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer, a dialdehyde monomer, and 6.7 mg (0.035 mmol) of cuprous iodide. Vacuum and charge with carbon dioxide three times, then add 0.25 mL of ultra-dry 1,2,4-trichlorobenzene. After the monomers are completely dissolved, insert a carbon dioxide balloon and add 29.2 mg (0.4 mmol) of the third monomer, a monoamine monomer. React at 130°C for 7.5 hours. After the reaction is completed and returned to room temperature, dilute with 10 mL of chloroform and add the solution dropwise to 200 mL of vigorously stirred petroleum ether through a dropper plugged with cotton. Let stand, filter, and dry to constant weight to obtain the target polymer. Pale yellow solid with a yield of 72%. GPC results show: M w =9600,PDI=1.76.

[0056] The polymer prepared in this example also has good solubility and thermal stability; due to the presence of tetraphenylethylene groups, which are active in aggregation-induced emission, the polymer also exhibits aggregation-induced emission. Furthermore, a film made by mixing the oxazolidinone polymer prepared in this invention with nylon 6 (PA6) and co-heating it exhibits phosphorescence at room temperature, which can be used in anti-counterfeiting applications.

[0057] Example 3

[0058] This example uses the same reactants as in Example 1 to prepare an oxazolidinone polymer. The specific steps are as follows:

[0059] To a 10 mL polymerization tube with a side arm, add 45.6 mg (0.1 mmol) of the first monomer, a diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer, a dialdehyde monomer, and 6.7 mg (0.035 mmol) of cuprous iodide. Vacuum and charge with carbon dioxide three times, then add 0.25 mL of ultra-dry 1,2,4-trichlorobenzene. After the monomers are completely dissolved, insert a carbon dioxide balloon and add 29.2 mg (0.4 mmol) of the third monomer, a monoamine monomer. React at 120°C for 7.5 hours. After the reaction is completed and returned to room temperature, dilute with 10 mL of chloroform and add the solution dropwise to 200 mL of vigorously stirred petroleum ether through a dropper plugged with cotton. Let stand, filter, and dry to constant weight to obtain the target polymer. A light yellow solid with a yield of 62%. GPC results show: M w =8900,PDI=2.06.

[0060] The polymer prepared in this example also has good solubility and thermal stability; due to the presence of tetraphenylethylene groups, which are active in aggregation-induced emission, the polymer also exhibits aggregation-induced emission. Furthermore, a film made by mixing the oxazolidinone polymer prepared in this invention with nylon 6 (PA6) and co-heating it exhibits phosphorescence at room temperature, which can be used in anti-counterfeiting applications.

[0061] Example 4

[0062] This example uses the same reactants as in Example 1 to prepare an oxazolidinone polymer. The specific steps are as follows:

[0063] To a 10 mL polymerization tube with a side arm, add 45.6 mg (0.1 mmol) of the first monomer, a diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer, a dialdehyde monomer, and 6.7 mg (0.035 mmol) of cuprous iodide. Vacuum and charge with carbon dioxide three times, then add 0.25 mL of ultra-dry 1,2,4-trichlorobenzene. After the monomers are completely dissolved, insert a carbon dioxide balloon and add 29.2 mg (0.4 mmol) of the third monomer, a monoamine monomer. React at 110°C for 7.5 hours. After the reaction is completed and returned to room temperature, dilute with 10 mL of chloroform and add the solution dropwise to 200 mL of vigorously stirred petroleum ether through a dropper plugged with cotton. Let stand, filter, and dry to constant weight to obtain the target polymer. Pale yellow solid with a yield of 65%. GPC results show: M w =8700,PDI=2.23.

[0064] The polymer prepared in this example also has good solubility and thermal stability; due to the presence of tetraphenylethylene groups, which are active in aggregation-induced emission, the polymer also exhibits aggregation-induced emission. Furthermore, a film made by mixing the oxazolidinone polymer prepared in this invention with nylon 6 (PA6) and co-heating it exhibits phosphorescence at room temperature, which can be used in anti-counterfeiting applications.

[0065] Example 5

[0066] This example uses the same reactants as in Example 1 to prepare an oxazolidinone polymer. The specific steps are as follows:

[0067] To a 10 mL polymerization tube with a side arm, add 45.6 mg (0.1 mmol) of the first monomer, a diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer, a dialdehyde monomer, and 6.7 mg (0.035 mmol) of cuprous iodide. Vacuum and charge with carbon dioxide three times, then add 0.25 mL of ultra-dry 1,2,4-trichlorobenzene. After the monomers are completely dissolved, insert a carbon dioxide balloon and add 29.2 mg (0.4 mmol) of the third monomer, a monoamine monomer. React at 150 ° C for 7.5 hours. After the reaction is completed and returned to room temperature, dilute with 10 mL of chloroform and add the solution dropwise to 200 mL of vigorously stirred petroleum ether through a dropper plugged with cotton. Let stand, filter, and dry to constant weight to obtain the target polymer. Pale yellow solid with a yield of 57%. GPC results show: M w =10800,PDI=1.43.

[0068] The polymer prepared in this example also has good solubility and thermal stability; due to the presence of tetraphenylethylene groups, which are active in aggregation-induced emission, the polymer also exhibits aggregation-induced emission. Furthermore, a film made by mixing the oxazolidinone polymer prepared in this invention with nylon 6 (PA6) and co-heating it exhibits phosphorescence at room temperature, which can be used in anti-counterfeiting applications.

[0069] Example 6

[0070] This example uses the same reactants as in Example 1 to prepare an oxazolidinone polymer. The specific steps are as follows:

[0071] To a 10 mL polymerization tube with a side arm, add 45.6 mg (0.1 mmol) of the first monomer, a diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer, a dialdehyde monomer, and 3.8 mg (0.02 mmol) of cuprous iodide. Vacuum and charge with carbon dioxide three times, then add 0.25 mL of ultra-dry 1,2,4-trichlorobenzene. After the monomers are completely dissolved, insert a carbon dioxide balloon and add 29.2 mg (0.4 mmol) of the third monomer, a monoamine monomer. React at 140 ° C for 7.5 hours. After the reaction is completed and returned to room temperature, dilute with 10 mL of chloroform and add the solution dropwise to 200 mL of vigorously stirred petroleum ether through a dropper plugged with cotton. Let stand, filter, and dry to constant weight to obtain the target polymer. Pale yellow solid with a yield of 56%. GPC results show: M w =8700,PDI=1.53.

[0072] The polymer prepared in this example also has good solubility and thermal stability; due to the presence of tetraphenylethylene groups, which are active in aggregation-induced emission, the polymer also exhibits aggregation-induced emission. Furthermore, a film made by mixing the oxazolidinone polymer prepared in this invention with nylon 6 (PA6) and co-heating it exhibits phosphorescence at room temperature, which can be used in anti-counterfeiting applications.

[0073] Example 7

[0074] This example uses the same reactants as in Example 1 to prepare an oxazolidinone polymer. The specific steps are as follows:

[0075] To a 10 mL polymerization tube with a side arm, add 45.6 mg (0.1 mmol) of the first monomer, a diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer, a dialdehyde monomer, and 5.7 mg (0.03 mmol) of cuprous iodide. Vacuum and charge with carbon dioxide three times, then add 0.25 mL of ultra-dry 1,2,4-trichlorobenzene. After the monomers are completely dissolved, insert a carbon dioxide balloon and add 29.2 mg (0.4 mmol) of the third monomer, a monoamine monomer. React at 140°C for 7.5 hours. After the reaction is completed and returned to room temperature, dilute with 10 mL of chloroform and add the solution dropwise to 200 mL of vigorously stirred petroleum ether through a dropper plugged with cotton. Let stand, filter, and dry to constant weight to obtain the target polymer. Pale yellow solid with a yield of 63%. GPC results show: M w =9600,PDI=1.60.

[0076] The polymer prepared in this example also has good solubility and thermal stability; due to the presence of tetraphenylethylene groups, which are active in aggregation-induced emission, the polymer also exhibits aggregation-induced emission. Furthermore, a film made by mixing the oxazolidinone polymer prepared in this invention with nylon 6 (PA6) and co-heating it exhibits phosphorescence at room temperature, which can be used in anti-counterfeiting applications.

[0077] Example 8

[0078] This example uses the same reactants as in Example 1 to prepare an oxazolidinone polymer. The specific steps are as follows:

[0079] To a 10 mL polymerization tube with a side arm, add 45.6 mg (0.1 mmol) of the first monomer, a diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer, a dialdehyde monomer, and 7.6 mg (0.04 mmol) of cuprous iodide. Vacuum and charge with carbon dioxide three times, then add 0.25 mL of ultra-dry 1,2,4-trichlorobenzene. After the monomers are completely dissolved, insert a carbon dioxide balloon and add 29.2 mg (0.4 mmol) of the third monomer, a monoamine monomer. React at 140 ° C for 7.5 hours. After the reaction is completed and returned to room temperature, dilute with 10 mL of chloroform and add the solution dropwise to 200 mL of vigorously stirred petroleum ether through a dropper plugged with cotton. Let stand, filter, and dry to constant weight to obtain the target polymer. Pale yellow solid with a yield of 60%. GPC results show: M w =10400,PDI=1.36.

[0080] The polymer prepared in this example also has good solubility and thermal stability; due to the presence of tetraphenylethylene groups, which are active in aggregation-induced emission, the polymer also exhibits aggregation-induced emission. Furthermore, a film made by mixing the oxazolidinone polymer prepared in this invention with nylon 6 (PA6) and co-heating it exhibits phosphorescence at room temperature, which can be used in anti-counterfeiting applications.

[0081] Example 9

[0082] This example uses the same reactants as in Example 1 to prepare an oxazolidinone polymer. The specific steps are as follows:

[0083] To a 10 mL polymerization tube with a side arm, add 45.6 mg (0.1 mmol) of the first monomer, a diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer, a dialdehyde monomer, and 6.7 mg (0.035 mmol) of cuprous iodide. Vacuum and charge with carbon dioxide three times, then add 0.25 mL of ultra-dry 1,2,4-trichlorobenzene. After the monomers are completely dissolved, insert a carbon dioxide balloon and add 29.2 mg (0.4 mmol) of the third monomer, a monoamine monomer. React at 140°C for 6.0 hours. After the reaction is completed and returned to room temperature, dilute with 10 mL of chloroform and add the solution dropwise to 200 mL of vigorously stirred petroleum ether through a dropper plugged with cotton. Let stand, filter, and dry to constant weight to obtain the target polymer. Pale yellow solid with a yield of 56%. GPC results show: M w =8600,PDI=1.56.

[0084] The polymer prepared in this example also has good solubility and thermal stability; due to the presence of tetraphenylethylene groups, which are active in aggregation-induced emission, the polymer also exhibits aggregation-induced emission. Furthermore, a film made by mixing the oxazolidinone polymer prepared in this invention with nylon 6 (PA6) and co-heating it exhibits phosphorescence at room temperature, which can be used in anti-counterfeiting applications.

[0085] Example 10

[0086] This example uses the same reactants as in Example 1 to prepare an oxazolidinone polymer. The specific steps are as follows:

[0087] To a 10 mL polymerization tube with a side arm, add 45.6 mg (0.1 mmol) of the first monomer, a diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer, a dialdehyde monomer, and 6.7 mg (0.035 mmol) of cuprous iodide. Vacuum and charge with carbon dioxide three times, then add 0.25 mL of ultra-dry 1,2,4-trichlorobenzene. After the monomers are completely dissolved, insert a carbon dioxide balloon and add 29.2 mg (0.4 mmol) of the third monomer, a monoamine monomer. React at 140 ° C for 7.0 hours. After the reaction is completed and returned to room temperature, dilute with 10 mL of chloroform and add the solution dropwise to 200 mL of vigorously stirred petroleum ether through a dropper plugged with cotton. Let stand, filter, and dry to constant weight to obtain the target polymer. Pale yellow solid with a yield of 67%. GPC results show: M w =9100,PDI=1.46.

[0088] The polymer prepared in this example also has good solubility and thermal stability; due to the presence of tetraphenylethylene groups, which are active in aggregation-induced emission, the polymer also exhibits aggregation-induced emission. Furthermore, a film made by mixing the oxazolidinone polymer prepared in this invention with nylon 6 (PA6) and co-heating it exhibits phosphorescence at room temperature, which can be used in anti-counterfeiting applications.

[0089] Example 11

[0090] This example uses the same reactants as in Example 1 to prepare an oxazolidinone polymer. The specific steps are as follows:

[0091] To a 10 mL polymerization tube with a side arm, add 45.6 mg (0.1 mmol) of the first monomer, a diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer, a dialdehyde monomer, and 6.7 mg (0.035 mmol) of cuprous iodide. Vacuum and charge with carbon dioxide three times, then add 0.25 mL of ultra-dry 1,2,4-trichlorobenzene. After the monomers are completely dissolved, insert a carbon dioxide balloon and add 29.2 mg (0.4 mmol) of the third monomer, a monoamine monomer. React at 140°C for 8.0 hours. After the reaction is completed and returned to room temperature, dilute with 10 mL of chloroform and add the solution dropwise to 200 mL of vigorously stirred petroleum ether through a dropper plugged with cotton. Let stand, filter, and dry to constant weight to obtain the target polymer. Pale yellow solid with a yield of 53%. GPC results show: M w =11000,PDI=1.53.

[0092] The polymer prepared in this example also has good solubility and thermal stability; due to the presence of tetraphenylethylene groups, which are active in aggregation-induced emission, the polymer also exhibits aggregation-induced emission. Furthermore, a film made by mixing the oxazolidinone polymer prepared in this invention with nylon 6 (PA6) and co-heating it exhibits phosphorescence at room temperature, which can be used in anti-counterfeiting applications.

[0093] Example 12

[0094] This example uses the same reactants as in Example 1 to prepare an oxazolidinone polymer. The specific steps are as follows:

[0095] To a 10 mL polymerization tube with a side arm, add 45.6 mg (0.1 mmol) of the first monomer, a diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer, a dialdehyde monomer, and 6.7 mg (0.035 mmol) of cuprous iodide. Vacuum and charge with carbon dioxide three times, then add 0.3 mL of ultra-dry 1,2,4-trichlorobenzene. After the monomers are completely dissolved, insert a carbon dioxide balloon and add 29.2 mg (0.4 mmol) of the third monomer, a monoamine monomer. React at 140 ° C for 6.0 hours. After the reaction is completed and returned to room temperature, dilute with 10 mL of chloroform and add the solution dropwise to 200 mL of vigorously stirred petroleum ether through a dropper plugged with cotton. Let stand, filter, and dry to constant weight to obtain the target polymer. Pale yellow solid with a yield of 59%. GPC results show: M w =8900,PDI=1.49.

[0096] The polymer prepared in this example also has good solubility and thermal stability; due to the presence of tetraphenylethylene groups, which are active in aggregation-induced emission, the polymer also exhibits aggregation-induced emission. Furthermore, a film made by mixing the oxazolidinone polymer prepared in this invention with nylon 6 (PA6) and co-heating it exhibits phosphorescence at room temperature, which can be used in anti-counterfeiting applications.

[0097] Example 13

[0098] This example uses the same reactants as in Example 1 to prepare an oxazolidinone polymer. The specific steps are as follows:

[0099] To a 10 mL polymerization tube with a side arm, add 45.6 mg (0.1 mmol) of the first monomer, a diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer, a dialdehyde monomer, and 6.7 mg (0.035 mmol) of cuprous iodide. Vacuum and charge with carbon dioxide three times, then add 0.4 mL of ultra-dry 1,2,4-trichlorobenzene. After the monomers are completely dissolved, insert a carbon dioxide balloon and add 29.2 mg (0.4 mmol) of the third monomer, a monoamine monomer. React at 140°C for 6.0 hours. After the reaction is completed and returned to room temperature, dilute with 10 mL of chloroform and add the solution dropwise to 200 mL of vigorously stirred petroleum ether through a dropper plugged with cotton. Let stand, filter, and dry to constant weight to obtain the target polymer. Pale yellow solid with a yield of 59%. GPC results show: M w =8100,PDI=1.46.

[0100] The polymer prepared in this example also has good solubility and thermal stability; due to the presence of tetraphenylethylene groups, which are active in aggregation-induced emission, the polymer also exhibits aggregation-induced emission. Furthermore, a film made by mixing the oxazolidinone polymer prepared in this invention with nylon 6 (PA6) and co-heating it exhibits phosphorescence at room temperature, which can be used in anti-counterfeiting applications.

[0101] Example 14

[0102] This example uses the same reactants as in Example 1 to prepare an oxazolidinone polymer. The specific steps are as follows:

[0103] To a 10 mL polymerization tube with a side arm, add 45.6 mg (0.1 mmol) of the first monomer, a diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer, a dialdehyde monomer, and 6.7 mg (0.035 mmol) of cuprous iodide. Vacuum and charge with carbon dioxide three times, then add 0.2 mL of ultra-dry 1,2,4-trichlorobenzene. After the monomers are completely dissolved, insert a carbon dioxide balloon and add 29.2 mg (0.4 mmol) of the third monomer, a monoamine monomer. React at 140°C for 6.0 hours. After the reaction is completed and returned to room temperature, dilute with 10 mL of chloroform and add the solution dropwise to 200 mL of vigorously stirred petroleum ether through a dropper plugged with cotton. Let stand, filter, and dry to constant weight to obtain the target polymer. Pale yellow solid with a yield of 54%. GPC results show: M w =8700,PDI=1.46.

[0104] The polymer prepared in this example also has good solubility and thermal stability; due to the presence of tetraphenylethylene groups, which are active in aggregation-induced emission, the polymer also exhibits aggregation-induced emission. Furthermore, films made by mixing the polyoxazolidinone polymer prepared in this invention with nylon 6 (PA6) and thermally heating them exhibit phosphorescence at room temperature, potentially enabling anti-counterfeiting applications.

[0105] Example 15

[0106] This embodiment relates to the preparation of an oxazolidinone polymer, and the reaction equation is as follows:

[0107]

[0108] The specific steps include:

[0109] (1) Diacetylene monomer: the same as in Example 1.

[0110] (2) Dialdehyde monomer: the same as in Example 1.

[0111] (3) Carbon dioxide (purity 99.99%) and monoamine monomers were purchased from the market. Carbon dioxide was purchased from Jinhong Gas Co., Ltd., and monoamine monomers were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0112] (4) Preparation of oxazolidinone polymers

[0113] To a 10 mL polymerization tube with a side arm, add 45.6 mg (0.1 mmol) of the first monomer, a diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer, a dialdehyde monomer, and 6.7 mg (0.035 mmol) of cuprous iodide. Vacuum and charge with carbon dioxide three times, then add 0.25 mL of ultra-dry 1,2,4-trichlorobenzene. After the monomers are completely dissolved, insert a carbon dioxide balloon and add 42.8 mg (0.4 mmol) of the third monomer, a monoamine monomer. React at 140 ° C for 7.5 hours. After the reaction is completed and returned to room temperature, dilute with 10 mL of chloroform and add the solution dropwise to 200 mL of vigorously stirred petroleum ether through a dropper plugged with cotton. Let stand, filter, and dry to constant weight to obtain the target polymer. Pale yellow solid with a yield of 70%. GPC results show: M w =13800,PDI=1.80. 1 H NMR (400MHz, CD2Cl2) δ7.63,7.40,7.14,6.85,5.05,3.96,3.65,1.63,0.96.

[0114] The polymer prepared in this example also has good solubility and thermal stability; due to the presence of tetraphenylethylene groups, which are active in aggregation-induced emission, the polymer also exhibits aggregation-induced emission. Furthermore, films made by mixing the polyoxazolidinone polymer prepared in this invention with nylon 6 (PA6) and thermally heating them exhibit phosphorescence at room temperature, potentially enabling anti-counterfeiting applications.

[0115] Example 16

[0116] This embodiment relates to the preparation of an oxazolidinone polymer, and the reaction equation is as follows:

[0117]

[0118] (1) Diacetylene monomers:

[0119] The first monomer, a diacetylene monomer, was synthesized according to the preparation method of the published literature (Polym. Chem., 2018, 9, 4404-4412).

[0120] (2) Dialdehyde monomer: the same as in Example 1.

[0121] (3) Carbon dioxide (purity 99.99%) and monoamine monomers were purchased from the market. Carbon dioxide was purchased from Jinhong Gas Co., Ltd., and monoamine monomers were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0122] (4) Preparation of oxazolidinone polymers

[0123] To a 10 mL polymerization tube with a side arm, add 38.0 mg (0.1 mmol) of the first monomer, a diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer, a dialdehyde monomer, and 6.7 mg (0.035 mmol) of cuprous iodide. Vacuum and charge with carbon dioxide three times, then add 0.25 mL of ultra-dry 1,2,4-trichlorobenzene. After the monomers are completely dissolved, insert a carbon dioxide balloon and add 29.2 mg (0.4 mmol) of the third monomer, a monoamine monomer. React at 140°C for 7.5 hours. After the reaction is completed and returned to room temperature, dilute with 10 mL of chloroform and add the solution dropwise to 200 mL of vigorously stirred petroleum ether through a dropper plugged with cotton. Let stand, filter, and dry to constant weight to obtain the target polymer. A light yellow solid with a yield of 68%. GPC results show: M w =10100,PDI=1.27. 1 HNMR (400MHz, CD2Cl2) δ8.08,7.61,7.41,7.11,5.53,5.10,3.98,3.61,0.94,0.17,0.11.

[0124] The polymer prepared in this example also has good solubility and thermal stability; due to the presence of tetraphenylethylene groups, which are active in aggregation-induced emission, the polymer also exhibits aggregation-induced emission. Furthermore, a film made by mixing the oxazolidinone polymer prepared in this invention with nylon 6 (PA6) and co-heating it exhibits phosphorescence at room temperature, which can be used in anti-counterfeiting applications.

[0125] Example 17

[0126] This embodiment relates to the preparation of an oxazolidinone polymer, and the reaction equation is as follows:

[0127]

[0128] (1) Diacetylene monomer: the same as in Example 16.

[0129] (2) Dialdehyde monomer: the same as in Example 1.

[0130] (3) Carbon dioxide (purity 99.99%) and monoamine monomers were purchased from the market. Carbon dioxide was purchased from Jinhong Gas Co., Ltd., and monoamine monomers were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0131] (4) Preparation of oxazolidinone polymers

[0132] To a 10 mL polymerization tube equipped with a sidearm, 38.0 mg (0.1 mmol) of the first diacetylene monomer, 54.1 mg (0.1 mmol) of the second dialdehyde monomer, and 6.7 mg (0.035 mmol) of cuprous iodide were added. The tube was evacuated and filled with carbon dioxide three times. Then, 0.25 mL of ultra-dry 1,2,4-trichlorobenzene was added. After the monomers were completely dissolved, a carbon dioxide balloon was inserted. 42.8 mg (0.4 mmol) of the third monoamine monomer was added. The reaction was continued at 140°C for 7.5 hours. After the reaction was complete and the tube returned to room temperature, the solution was diluted with 10 mL of chloroform and added dropwise to 200 mL of vigorously stirred petroleum ether via a cotton-lined dropper. The mixture was allowed to stand, filtered, and dried to a constant weight to obtain the desired polymer as a pale yellow solid in a 74% yield. 1 H NMR (400MHz, CD2Cl2) δ7.63,7.35,7.12,5.09,4.18,3.98,1.64,0.86.

[0133] The H NMR spectra of the products prepared in steps (1), (2) and (4) are as follows: Figure 1As shown, the diacetylene monomer has a resonance peak at δ3.10, the dialdehyde monomer has a resonance peak at δ10.01, and the monoamine monomer has a resonance peak at δ2.00. However, in the polymer, the peak disappears, and a new resonance peak appears at δ4.81 (#), which is attributed to the resonance peak of hydrogen on the oxazolidinone ring. Therefore, it can be seen that the prepared polymer is an oxazolidinone polymer. The gel permeation chromatography (GPC) results show that the weight average molecular weight (M) of the polymer prepared in this example is w ) is 12800 and the molecular weight distribution (PDI) is 1.70.

[0134] Performance research and application:

[0135] (1) Solubility

[0136] The oxazolidinone polymer prepared in this example is easily soluble in common organic solvents such as chloroform, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide and dimethyl sulfoxide at room temperature and has good processability and film-forming properties.

[0137] (2) Thermal stability

[0138] The oxazolidinone polymer prepared in this example was subjected to thermogravimetric analysis test, and the test results are as follows: Figure 2 As shown, the poly-1,5-substituted triazole polymer loses only 5% of its weight when heated to 359° C., which also shows that the poly-1,5-substituted triazole prepared in this example has good thermal stability.

[0139] (3) AIE performance

[0140] The polyoxazolidinone polymer prepared in this example was dispersed in tetrahydrofuran solutions with different water contents, such as Figure 3 As shown, the polymer emits extremely weak light in tetrahydrofuran solution, but the fluorescence is significantly enhanced after adding poor solvent water, and the fluorescence is enhanced with the increase of water content, showing excellent aggregation-induced emission properties.

[0141] (4) Oxazolidinone polymers in Fe 3+ Application in detection

[0142] Preparation 10 -5 mol / L tetrahydrofuran aqueous solution of oxazolidinone polymer (water volume fraction is 10%) is used as the test substance, and different contents of the test substance Fe are added in sequence. 3+ , quickly test the fluorescence spectrum. The results are as follows Figure 4 As shown, when no Fe is added 3+ When Fe 3+ The fluorescence intensity begins to weaken, and with the addition of Fe 3+The fluorescence intensity gradually weakened with the increase of the content. + 、Na + 、Al 3+ 、Ni 2+ 、Ln 3+ 、Co 2+ 、Cu 2+ 、Zn 2+ 、Fe 3+ ) on the fluorescence quenching effect of oxazolidinone polymers. Figure 5 As shown, only Fe 3+ Ions can greatly quench the fluorescence of oxazolidinone polymers, showing excellent ion selectivity. The above experimental results show that the polyoxazolidinone polymers of the present invention can be used as a Fe 3+ sensor.

[0143] (5) Oxazolidinone polymer room temperature phosphorescence

[0144] The oxazolidinone polymer prepared in this example was thoroughly mixed and ground with nylon 6 (PA6) at a mass ratio of 1:1000 to form a solid mixture. A small amount of the mixture was spread on a glass plate and heated on a hot plate. When the mixture reached a molten state, the heating was stopped and the glass plate was allowed to cool naturally to room temperature. Figure 6 As shown, a glass slide was irradiated with a UV lamp of 365 nm wavelength, and the UV lamp was turned off after 10 seconds, and green phosphorescence was observed in a dark environment.

[0145] Example 18

[0146] This embodiment relates to the preparation of an oxazolidinone polymer, and the reaction equation is as follows:

[0147]

[0148] The specific steps include:

[0149] (1) Diacetylene monomers:

[0150] The first monomer, a diacetylene monomer, was synthesized according to the preparation method of the published literature (Polym. Chem., 2018, 9, 4404-4412).

[0151] (2) Dialdehyde monomer: the same as in Example 1.

[0152] (3) Carbon dioxide (purity 99.99%) and monoamine monomers were purchased from the market. Carbon dioxide was purchased from Jinhong Gas Co., Ltd., and monoamine monomers were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0153] (4) Preparation of oxazolidinone polymers

[0154] To a 10 mL polymerization tube with a side arm, add 32.0 mg (0.1 mmol) of the first monomer, a diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer, a dialdehyde monomer, and 6.7 mg (0.035 mmol) of cuprous iodide. Vacuum and charge with carbon dioxide three times, then add 0.25 mL of ultra-dry 1,2,4-trichlorobenzene. After the monomers are completely dissolved, insert a carbon dioxide balloon and add 29.2 mg (0.4 mmol) of the third monomer, a monoamine monomer. React at 140°C for 7.5 hours. After the reaction is completed and returned to room temperature, dilute with 10 mL of chloroform and add the solution dropwise to 200 mL of vigorously stirred petroleum ether through a dropper plugged with cotton. Let stand, filter, and dry to constant weight to obtain the target polymer. Pale yellow solid with a yield of 66%. GPC results show: M w =10000,PDI=1.18. 1 H NMR (400MHz, CD2Cl2) δ8.12,7.44,7.14,5.53,5.11,3.93,1.54,0.97.

[0155] The polymer prepared in this example also has good solubility and thermal stability; due to the presence of tetraphenylethylene groups, which are active in aggregation-induced emission, the polymer also exhibits aggregation-induced emission. Furthermore, a film made by mixing the oxazolidinone polymer prepared in this invention with nylon 6 (PA6) and co-heating it exhibits phosphorescence at room temperature, which can be used in anti-counterfeiting applications.

[0156] Example 19

[0157] This embodiment relates to the preparation of an oxazolidinone polymer, and the reaction equation is as follows:

[0158]

[0159] The specific steps include:

[0160] (1) Diacetylene monomer: the same as in Example 18.

[0161] (2) Dialdehyde monomer: the same as in Example 1.

[0162] (3) Carbon dioxide (purity 99.99%) and monoamine monomers were purchased from the market. Carbon dioxide was purchased from Jinhong Gas Co., Ltd., and monoamine monomers were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0163] (4) Preparation of oxazolidinone polymers

[0164] To a 10 mL polymerization tube with a side arm, add 32.0 mg (0.1 mmol) of the first monomer, a diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer, a dialdehyde monomer, and 6.7 mg (0.035 mmol) of cuprous iodide. Vacuum and charge with carbon dioxide three times, then add 0.25 mL of ultra-dry 1,2,4-trichlorobenzene. After the monomers are completely dissolved, insert a carbon dioxide balloon and add 42.8 mg (0.4 mmol) of the third monomer, a monoamine monomer. React at 140°C for 7.5 hours. After the reaction is completed and returned to room temperature, dilute with 10 mL of chloroform and add the solution dropwise to 200 mL of vigorously stirred petroleum ether through a dropper plugged with cotton. Let stand, filter, and dry to constant weight to obtain the target polymer. Pale yellow solid with a yield of 83%. GPC results show: M w =11100,PDI=1.80. 1 HNMR (400MHz, CD2Cl2) δ8.20,7.44,7.14,5.11,4.80,3.97,1.54.

[0165] The polymer prepared in this example also has good solubility and thermal stability; due to the presence of tetraphenylethylene groups, which are active in aggregation-induced emission, the polymer also exhibits aggregation-induced emission. Furthermore, a film made by mixing the oxazolidinone polymer prepared in this invention with nylon 6 (PA6) and co-heating it exhibits phosphorescence at room temperature, which can be used in anti-counterfeiting applications.

[0166] Obviously, the above embodiments are merely examples for clarity of explanation and are not intended to limit the implementation methods. Those skilled in the art will appreciate that other variations or modifications can be made based on the above description. It is not necessary and impossible to enumerate all implementation methods here. Obvious variations or modifications arising therefrom remain within the scope of protection of the present invention.

Claims

1. An oxazolidinone polymer, characterized in that The oxazolidinone polymer has the following general structural formula: ； Wherein, n is an integer from 2 to 200; R1 is selected from any one of the groups represented by Formula 4, Formula 14, and Formula 15, R2 is selected from Formula 17, and R3 is selected from any one of the groups represented by Formula 21 and Formula 22; The structures of the above formulas 4, 14, 15, 17, 21 and 22 are as follows: ； Wherein, m is any integer from 1 to 18, and * represents the substitution position.

2. A method for preparing the oxazolidinone polymer according to claim 1, characterized in that: The steps include: In a carbon dioxide gas atmosphere, a diacetylene monomer represented by formula (I), a dialdehyde monomer represented by formula (II), and a monoamine monomer represented by formula (III) are reacted in the presence of cuprous iodide and a polar aprotic solvent to obtain the oxazolidinone polymer; The structures of formula (I), formula (II) and formula (III) are shown below: 。 3. The preparation method according to claim 2, characterized in that The molar ratio of the diacetylene monomer, the dialdehyde monomer, the monoamine monomer and cuprous iodide is 1:1:4:0.1-0.

8.

4. The preparation method according to claim 2, characterized in that The molar volume ratio of the dibasic acetylene monomer to the polar aprotic solvent is 0.1-0.8 mol / L.

5. The preparation method according to claim 2, characterized in that The polar aprotic solvent is one or more of 1,2,4-trichlorobenzene, o-dichlorobenzene, chlorobenzene and toluene.

6. The preparation method according to claim 2, characterized in that The reaction temperature is 60-180°C.

7. The preparation method according to claim 2, characterized in that The reaction time of the reaction is 0.5-24 h.

8. The preparation method according to claim 2, characterized in that After the reaction is complete, the product is diluted with chloroform and dropped into petroleum ether to precipitate to obtain the oxazolidinone polymer.

9. The oxazolidinone polymer according to claim 1 is used as a fluorescent sensor to detect Fe 3+ The application of aspect is characterized in that The structure of the oxazolidinone polymer contains one or two of the groups represented by Formula 15 and Formula 17.

10. Use of the oxazolidinone polymer according to claim 1 in optical anti-counterfeiting materials.

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