Oxazolidinone polymer as well as preparation method and application thereof

Abstract

The invention belongs to the field of polymer synthesis and materials, and particularly relates to an oxazolidinone polymer as well as a preparation method and application thereof. A binary alkyne monomer, a binary aldehyde monomer, carbon dioxide and monoamine are used as raw materials and react in the presence of cuprous iodide and a polar aprotic solvent to obtain the polymer, and the oxazolidinone polymer has the following structural general formula: # imgabs0 # R1, R2 and R3 are same or different organic groups. The reaction raw materials of the synthesis method are easy to obtain, the reaction condition is mild, a precious metal catalyst is not needed, and the reaction cost is reduced to a great extent. In addition, the reaction has wide substrate applicability and good functional group compatibility, and various functional groups can be introduced. The oxazolidinone polymer prepared by the invention has good processability, relatively high thermal stability and aggregation-induced emission performance, and has important application value in the aspects of optical plastics, biomedical materials, optical anti-counterfeiting, fluorescence sensing and the like.

Description

Technical Field

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

[0002] The preparation of new structure polymer materials based on renewable materials has important application prospects. Carbon dioxide, as a rich, cheap, non-toxic, green and renewable C1 resource, has attracted more and more 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 of reaction 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 and others from South China University of Technology published a method for synthesizing cyclic carbonate-based polymers from carbon dioxide, propargyl alcohol and halogenated aromatics under normal pressure conditions catalyzed by palladium acetate (Macromolecules, 2019, 52, 5546-5554). However, this method requires the use of precious metal catalysts, and the internal alkyne monomer limits the application of this type of polymerization reaction. Wang Xianhong and others from Changchun Institute of Applied Chemistry published a method for copolymerizing carbon dioxide and epoxy compounds catalyzed by polymer porphyrin to generate polypropylene carbonate (ACS Catal., 2022, 12, 481-490). However, the catalyst used in this method cannot be purchased commercially and needs to be synthesized by itself. Therefore, it is of great application value to develop polymerization reactions with relatively mild reaction conditions, simple operation steps, low reaction cost, simple and easy-to-obtain monomers and catalysts, and to prepare polymer materials with new structures. Among the synthetic functional polymerization methods developed in recent years, multi-component polymerization reactions have received widespread attention for 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 strong light in solution, but the light emission is weakened or non-emitted in the aggregated state or solid state, which limits the use of such materials 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, namely aggregation-induced emission (AIE): organic small molecule thiole derivatives are almost not observed to emit light in solution, but once they form nanoparticles or films, the fluorescence intensity shows a significant increase (Chem. Commun., 2001, 1740-1741). Materials with AIE properties have been widely used in display, chemical detection and biosensing fields (Chem. Rev., 2015, 115, 11718-11940). Compared with small molecule materials, there are fewer reports on AIE-active polymer materials (Prog. Polym. Sci., 2020, 100, 101176). The preparation of new structure AIE polymers based on new 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 and a preparation method and application thereof. The present invention uses diacetylene monomers, dialdehyde monomers, monoamine monomers and carbon dioxide as raw materials, and reacts in the presence of cuprous iodide and a polar aprotic solvent to obtain an oxazolidinone polymer. The preparation method is simple, has wide substrate applicability and good functional group compatibility, is convenient for introducing a variety of functional groups, can realize the preparation of different polymer functional materials by combining the polymer structure design with the 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, wherein the polymer has 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 shown in Formula 1 to Formula 20, R2 is selected from any one of the groups shown in Formula 1 to Formula 20, and R3 is selected from any one of the groups shown in 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, * is 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, wherein a dibasic acetylene monomer represented by formula (I), a dibasic aldehyde monomer represented by formula (II), a monoamine represented by formula (III) and carbon dioxide are reacted 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 to be 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 of the reaction is 60-180°C, and is finally selected to be 80-160°C.

[0023] Furthermore, the reaction time of the reaction is 0.5-24h, and 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 application of the oxazolidinone polymer described in the first aspect as a luminescent material in anti-counterfeiting.

[0029] Furthermore, oxazolidinone polymers with longer phosphorescence lifetime and higher quantum yield are 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- 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 the present invention by mixing the oxazolidinone polymer and nylon 6 (PA6) and heating it 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 easily 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 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 material science.

[0033] 3. The reaction conditions of the present invention are mild. Carbon dioxide can react with diacetylene, dialdehyde and monoamine under normal pressure, and no high-pressure-resistant reaction device is required, which improves the safety of the reaction. In addition, renewable, cheap and easily available carbon dioxide is used as a reaction raw material to prepare polymer materials based on polymerization reaction. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the oxazolidinone polymer prepared in Example 17 and its corresponding monomer in CD2Cl2;

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

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

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

[0038] Figure 5 This is a schematic diagram of the selectivity of the oxazolidinone polymer prepared in Example 17 to different metal ions;

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

[0040] The present invention is further described below in conjunction with the accompanying drawings and specific embodiments so that those skilled in the art can better understand the present invention and implement it, but 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 diacetylene monomer is synthesized according to the preparation method of the published literature (Polym.Chem., 2021, 12, 1078-1085).

[0047] (2) Preparation of dialdehyde monomers

[0048] The synthesis of the second monomer, a dialdehyde monomer, was performed by referring to the preparation method in a published document (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] Add 45.6 mg (0.1 mmol) of the first monomer diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer dialdehyde monomer, and 6.7 mg (0.035 mmol) of cuprous iodide to a 10 mL polymerization tube with a side arm, evacuate and charge with carbon dioxide three times, then add 0.25 mL of ultra-dry 1,2,4-trichlorobenzene, and after the monomers are completely dissolved, insert a carbon dioxide balloon, add 29.2 mg (0.4 mmol) of the third monomer monoamine monomer, react at 140 ° C for 7.5 hours, and after the reaction is completed and restored 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, yield 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 embodiment has good solubility and thermal stability; because it contains tetraphenylvinyl groups with aggregation-induced emission activity, the polymer also has aggregation-induced emission performance. In addition, the film prepared by mixing the oxazolidinone polymer prepared in the present invention with nylon 6 (PA6) and heating it has phosphorescence at room temperature, which can be used in anti-counterfeiting.

[0053] Example 2

[0054] This example uses the same reactants as in Example 1 to prepare an oxazolidinone polymer, and the specific operation is as follows:

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

[0056] The polymer prepared in this embodiment also has good solubility and thermal stability; because it contains tetraphenylvinyl groups with aggregation-induced emission activity, the polymer also has aggregation-induced emission performance. In addition, the film prepared by mixing the oxazolidinone polymer prepared in the present invention with nylon 6 (PA6) and heating it has phosphorescence at room temperature, which can be used in anti-counterfeiting.

[0057] Example 3

[0058] This example uses the same reactants as in Example 1 to prepare an oxazolidinone polymer, and the specific operation is as follows:

[0059] Add 45.6 mg (0.1 mmol) of the first monomer diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer dialdehyde monomer, and 6.7 mg (0.035 mmol) of cuprous iodide to a 10 mL polymerization tube with a side arm, evacuate and charge with carbon dioxide three times, then add 0.25 mL of ultra-dry 1,2,4-trichlorobenzene, and after the monomers are completely dissolved, insert a carbon dioxide balloon, add 29.2 mg (0.4 mmol) of the third monomer monoamine monomer, react at 120 ° C for 7.5 hours, and after the reaction is completed and restored 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, yield 62%. GPC results show: M w =8900,PDI=2.06.

[0060] The polymer prepared in this embodiment also has good solubility and thermal stability; because it contains tetraphenylvinyl groups with aggregation-induced emission activity, the polymer also has aggregation-induced emission performance. In addition, the film prepared by mixing the oxazolidinone polymer prepared in the present invention with nylon 6 (PA6) and heating it has phosphorescence at room temperature, which can be used in anti-counterfeiting.

[0061] Example 4

[0062] This example uses the same reactants as in Example 1 to prepare an oxazolidinone polymer, and the specific operation is as follows:

[0063] Add 45.6 mg (0.1 mmol) of the first monomer diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer dialdehyde monomer, and 6.7 mg (0.035 mmol) of cuprous iodide to a 10 mL polymerization tube with a side arm, evacuate and charge with carbon dioxide three times, then add 0.25 mL of ultra-dry 1,2,4-trichlorobenzene, and after the monomers are completely dissolved, insert a carbon dioxide balloon, add 29.2 mg (0.4 mmol) of the third monomer monoamine monomer, react at 110 ° C for 7.5 hours, and after the reaction is completed and restored 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, yield 65%. GPC results show: M w =8700,PDI=2.23.

[0064] The polymer prepared in this embodiment also has good solubility and thermal stability; because it contains tetraphenylvinyl groups with aggregation-induced emission activity, the polymer also has aggregation-induced emission performance. In addition, the film prepared by mixing the oxazolidinone polymer prepared in the present invention with nylon 6 (PA6) and heating it has phosphorescence at room temperature, which can be used in anti-counterfeiting.

[0065] Example 5

[0066] This example uses the same reactants as in Example 1 to prepare an oxazolidinone polymer, and the specific operation is as follows:

[0067] Add 45.6 mg (0.1 mmol) of the first monomer diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer dialdehyde monomer, and 6.7 mg (0.035 mmol) of cuprous iodide to a 10 mL polymerization tube with a side arm, evacuate and charge with carbon dioxide three times, then add 0.25 mL of ultra-dry 1,2,4-trichlorobenzene, and after the monomers are completely dissolved, insert a carbon dioxide balloon, add 29.2 mg (0.4 mmol) of the third monomer monoamine monomer, react at 150 ° C for 7.5 hours, and after the reaction is completed and restored 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, yield 57%. GPC results show: M w =10800,PDI=1.43.

[0068] The polymer prepared in this embodiment also has good solubility and thermal stability; because it contains tetraphenylvinyl groups with aggregation-induced emission activity, the polymer also has aggregation-induced emission performance. In addition, the film prepared by mixing the oxazolidinone polymer prepared in the present invention with nylon 6 (PA6) and heating it has phosphorescence at room temperature, which can be used in anti-counterfeiting.

[0069] Example 6

[0070] This example uses the same reactants as in Example 1 to prepare an oxazolidinone polymer, and the specific operation is as follows:

[0071] Add 45.6 mg (0.1 mmol) of the first monomer diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer dialdehyde monomer, and 3.8 mg (0.02 mmol) of cuprous iodide to a 10 mL polymerization tube with a side arm, evacuate and charge with carbon dioxide three times, then add 0.25 mL of ultra-dry 1,2,4-trichlorobenzene, and after the monomers are completely dissolved, insert a carbon dioxide balloon, add 29.2 mg (0.4 mmol) of the third monomer monoamine monomer, react at 140 ° C for 7.5 hours, and after the reaction is completed and restored 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, yield 56%. GPC results show: M w =8700,PDI=1.53.

[0072] The polymer prepared in this embodiment also has good solubility and thermal stability; because it contains tetraphenylvinyl groups with aggregation-induced emission activity, the polymer also has aggregation-induced emission performance. In addition, the film prepared by mixing the oxazolidinone polymer prepared in the present invention with nylon 6 (PA6) and heating it has phosphorescence at room temperature, which can be used in anti-counterfeiting.

[0073] Example 7

[0074] This example uses the same reactants as in Example 1 to prepare an oxazolidinone polymer, and the specific operation is as follows:

[0075] Add 45.6 mg (0.1 mmol) of the first monomer diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer dialdehyde monomer, and 5.7 mg (0.03 mmol) of cuprous iodide to a 10 mL polymerization tube with a side arm, evacuate and charge with carbon dioxide three times, then add 0.25 mL of ultra-dry 1,2,4-trichlorobenzene, and after the monomers are completely dissolved, insert a carbon dioxide balloon, add 29.2 mg (0.4 mmol) of the third monomer monoamine monomer, and react at 140 ° C for 7.5 hours. After the reaction is completed and restored 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, yield 63%. GPC results show: M w =9600,PDI=1.60.

[0076] The polymer prepared in this embodiment also has good solubility and thermal stability; because it contains tetraphenylvinyl groups with aggregation-induced emission activity, the polymer also has aggregation-induced emission performance. In addition, the film prepared by mixing the oxazolidinone polymer prepared in the present invention with nylon 6 (PA6) and heating it has phosphorescence at room temperature, which can be used in anti-counterfeiting.

[0077] Example 8

[0078] This example uses the same reactants as in Example 1 to prepare an oxazolidinone polymer, and the specific operation is as follows:

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

[0080] The polymer prepared in this embodiment also has good solubility and thermal stability; because it contains tetraphenylvinyl groups with aggregation-induced emission activity, the polymer also has aggregation-induced emission performance. In addition, the film prepared by mixing the oxazolidinone polymer prepared in the present invention with nylon 6 (PA6) and heating it has phosphorescence at room temperature, which can be used in anti-counterfeiting.

[0081] Example 9

[0082] This example uses the same reactants as in Example 1 to prepare an oxazolidinone polymer, and the specific operation is as follows:

[0083] Add 45.6 mg (0.1 mmol) of the first monomer diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer dialdehyde monomer, and 6.7 mg (0.035 mmol) of cuprous iodide to a 10 mL polymerization tube with a side arm, evacuate and charge with carbon dioxide three times, then add 0.25 mL of ultra-dry 1,2,4-trichlorobenzene, and after the monomers are completely dissolved, insert a carbon dioxide balloon, add 29.2 mg (0.4 mmol) of the third monomer monoamine monomer, react at 140 ° C for 6.0 hours, and after the reaction is completed and restored 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, yield 56%. GPC results show: M w =8600,PDI=1.56.

[0084] The polymer prepared in this embodiment also has good solubility and thermal stability; because it contains tetraphenylvinyl groups with aggregation-induced emission activity, the polymer also has aggregation-induced emission performance. In addition, the film prepared by mixing the oxazolidinone polymer prepared in the present invention with nylon 6 (PA6) and heating it has phosphorescence at room temperature, which can be used in anti-counterfeiting.

[0085] Example 10

[0086] This example uses the same reactants as in Example 1 to prepare an oxazolidinone polymer, and the specific operation is as follows:

[0087] Add 45.6 mg (0.1 mmol) of the first monomer diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer dialdehyde monomer, and 6.7 mg (0.035 mmol) of cuprous iodide to a 10 mL polymerization tube with a side arm, evacuate and charge with carbon dioxide three times, then add 0.25 mL of ultra-dry 1,2,4-trichlorobenzene, and after the monomers are completely dissolved, insert a carbon dioxide balloon, add 29.2 mg (0.4 mmol) of the third monomer monoamine monomer, and react at 140 ° C for 7.0 hours. After the reaction is completed and restored 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, yield 67%. GPC results show: M w =9100,PDI=1.46.

[0088] The polymer prepared in this embodiment also has good solubility and thermal stability; because it contains tetraphenylvinyl groups with aggregation-induced emission activity, the polymer also has aggregation-induced emission performance. In addition, the film prepared by mixing the oxazolidinone polymer prepared in the present invention with nylon 6 (PA6) and heating it has phosphorescence at room temperature, which can be used in anti-counterfeiting.

[0089] Embodiment 11

[0090] This example uses the same reactants as in Example 1 to prepare an oxazolidinone polymer, and the specific operation is as follows:

[0091] Add 45.6 mg (0.1 mmol) of the first monomer diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer dialdehyde monomer, and 6.7 mg (0.035 mmol) of cuprous iodide to a 10 mL polymerization tube with a side arm, evacuate and charge with carbon dioxide three times, then add 0.25 mL of ultra-dry 1,2,4-trichlorobenzene, and after the monomers are completely dissolved, insert a carbon dioxide balloon, add 29.2 mg (0.4 mmol) of the third monomer monoamine monomer, and react at 140 ° C for 8.0 hours. After the reaction is completed and restored 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, yield 53%. GPC results show: M w =11000,PDI=1.53.

[0092] The polymer prepared in this embodiment also has good solubility and thermal stability; because it contains tetraphenylvinyl groups with aggregation-induced emission activity, the polymer also has aggregation-induced emission performance. In addition, the film prepared by mixing the oxazolidinone polymer prepared in the present invention with nylon 6 (PA6) and heating it has phosphorescence at room temperature, which can be used in anti-counterfeiting.

[0093] Example 12

[0094] This example uses the same reactants as in Example 1 to prepare an oxazolidinone polymer, and the specific operation is as follows:

[0095] Add 45.6 mg (0.1 mmol) of the first monomer diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer dialdehyde monomer, and 6.7 mg (0.035 mmol) of cuprous iodide to a 10 mL polymerization tube with a side arm, evacuate and charge with carbon dioxide three times, then add 0.3 mL of ultra-dry 1,2,4-trichlorobenzene, and after the monomers are completely dissolved, insert a carbon dioxide balloon, add 29.2 mg (0.4 mmol) of the third monomer monoamine monomer, react at 140 ° C for 6.0 hours, and after the reaction is completed and restored 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, yield 59%. GPC results show: M w =8900,PDI=1.49.

[0096] The polymer prepared in this embodiment also has good solubility and thermal stability; because it contains tetraphenylvinyl groups with aggregation-induced emission activity, the polymer also has aggregation-induced emission performance. In addition, the film prepared by mixing the oxazolidinone polymer prepared in the present invention with nylon 6 (PA6) and heating it has phosphorescence at room temperature, which can be used in anti-counterfeiting.

[0097] Embodiment 13

[0098] This example uses the same reactants as in Example 1 to prepare an oxazolidinone polymer, and the specific operation is as follows:

[0099] Add 45.6 mg (0.1 mmol) of the first monomer diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer dialdehyde monomer, and 6.7 mg (0.035 mmol) of cuprous iodide to a 10 mL polymerization tube with a side arm, evacuate and charge with carbon dioxide three times, then add 0.4 mL of ultra-dry 1,2,4-trichlorobenzene, and after the monomers are completely dissolved, insert a carbon dioxide balloon, add 29.2 mg (0.4 mmol) of the third monomer monoamine monomer, react at 140 ° C for 6.0 hours, and after the reaction is completed and restored 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, yield 59%. GPC results show: M w =8100,PDI=1.46.

[0100] The polymer prepared in this embodiment also has good solubility and thermal stability; because it contains tetraphenylvinyl groups with aggregation-induced emission activity, the polymer also has aggregation-induced emission performance. In addition, the film prepared by mixing the oxazolidinone polymer prepared in the present invention with nylon 6 (PA6) and heating it has phosphorescence at room temperature, which can be used in anti-counterfeiting.

[0101] Embodiment 14

[0102] This example uses the same reactants as in Example 1 to prepare an oxazolidinone polymer, and the specific operation is as follows:

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

[0104] The polymer prepared in this embodiment also has good solubility and thermal stability; because it contains tetraphenylvinyl groups with aggregation-induced emission activity, the polymer also has aggregation-induced emission performance. In addition, the film prepared by mixing the polyoxazolidinone polymer prepared in the present invention with nylon 6 (PA6) and heating it has phosphorescence at room temperature, which can be used in anti-counterfeiting.

[0105] Embodiment 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] Add 45.6 mg (0.1 mmol) of the first monomer diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer dialdehyde monomer, and 6.7 mg (0.035 mmol) of cuprous iodide to a 10 mL polymerization tube with a side arm, evacuate and charge with carbon dioxide three times, then add 0.25 mL of ultra-dry 1,2,4-trichlorobenzene, and after the monomers are completely dissolved, insert a carbon dioxide balloon, add 42.8 mg (0.4 mmol) of the third monomer monoamine monomer, react at 140 ° C for 7.5 hours, and after the reaction is completed and restored to room temperature, dilute with 10 mL of chloroform, and add the solution through a dropper plugged with cotton to 200 mL of vigorously stirred petroleum ether, let stand, filter, and dry to constant weight to obtain the target polymer. Pale yellow solid, yield 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 embodiment also has good solubility and thermal stability; because it contains tetraphenylvinyl groups with aggregation-induced emission activity, the polymer also has aggregation-induced emission performance. In addition, the film prepared by mixing the polyoxazolidinone polymer prepared in the present invention with nylon 6 (PA6) and heating it has phosphorescence at room temperature, which can be used in anti-counterfeiting.

[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 synthesis of the first monomer 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] Add 38.0 mg (0.1 mmol) of the first monomer diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer dialdehyde monomer, and 6.7 mg (0.035 mmol) of cuprous iodide to a 10 mL polymerization tube with a side arm, evacuate and charge with carbon dioxide three times, then add 0.25 mL of ultra-dry 1,2,4-trichlorobenzene, and after the monomers are completely dissolved, insert a carbon dioxide balloon, add 29.2 mg (0.4 mmol) of the third monomer monoamine monomer, react at 140 ° C for 7.5 hours, and after the reaction is completed and restored 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, yield 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 embodiment also has good solubility and thermal stability; because it contains tetraphenylvinyl groups with aggregation-induced emission activity, the polymer also has aggregation-induced emission performance. In addition, the film prepared by mixing the oxazolidinone polymer prepared in the present invention with nylon 6 (PA6) and heating it has phosphorescence at room temperature, which can be used in anti-counterfeiting.

[0125] Embodiment 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] Add 38.0 mg (0.1 mmol) of the first monomer diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer dialdehyde monomer, and 6.7 mg (0.035 mmol) of cuprous iodide to a 10 mL polymerization tube with a side arm, evacuate and charge with carbon dioxide three times, then add 0.25 mL of ultra-dry 1,2,4-trichlorobenzene, insert a carbon dioxide balloon after the monomer is completely dissolved, add 42.8 mg (0.4 mmol) of the third monomer monoamine monomer, react at 140°C for 7.5 hours, and dilute with 10 mL of chloroform after the reaction is completed and restored to room temperature, 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, yield 74%. 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, but the peak disappears in the polymer, and a new resonance peak appears at δ4.81 (#), which is attributed to the resonance peak of hydrogen on the oxazolidinone ring. 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 a thermogravimetric analysis test. The test results are as follows: Figure 2 As shown, the poly 1,5-substituted triazole polymer loses only 5% of its weight when the temperature rises 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 as the water content increases, 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%) was used as the test object, and different contents of the test object Fe were 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 increases with the addition of Fe 3+The fluorescence intensity gradually weakened as the content of 9 different metal ions (Ag + 、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 Fe 3+ of sensors.

[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 prepare 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 naturally cooled to room temperature. Figure 6 As shown, a glass slide was irradiated with an ultraviolet lamp with a wavelength of 365 nm, the ultraviolet lamp was turned off after 10 seconds, and green phosphorescence was observed in a dark environment.

[0145] Embodiment 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 synthesis of the first monomer 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] Add 32.0 mg (0.1 mmol) of the first monomer diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer dialdehyde monomer, and 6.7 mg (0.035 mmol) of cuprous iodide to a 10 mL polymerization tube with a side arm, evacuate and charge with carbon dioxide three times, then add 0.25 mL of ultra-dry 1,2,4-trichlorobenzene, and after the monomers are completely dissolved, insert a carbon dioxide balloon, add 29.2 mg (0.4 mmol) of the third monomer monoamine monomer, react at 140 ° C for 7.5 hours, and after the reaction is completed and restored 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, yield 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 embodiment also has good solubility and thermal stability; because it contains tetraphenylvinyl groups with aggregation-induced emission activity, the polymer also has aggregation-induced emission performance. In addition, the film prepared by mixing the oxazolidinone polymer prepared in the present invention with nylon 6 (PA6) and heating it has phosphorescence at room temperature, which can be used in anti-counterfeiting.

[0156] Embodiment 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] Add 32.0 mg (0.1 mmol) of the first monomer diacetylene monomer, 54.1 mg (0.1 mmol) of the second monomer dialdehyde monomer, and 6.7 mg (0.035 mmol) of cuprous iodide to a 10 mL polymerization tube with a side arm, evacuate and charge with carbon dioxide three times, then add 0.25 mL of ultra-dry 1,2,4-trichlorobenzene, and after the monomer is completely dissolved, insert a carbon dioxide balloon, add 42.8 mg (0.4 mmol) of the third monomer monoamine monomer, react at 140 ° C for 7.5 hours, and after the reaction is completed and restored to room temperature, dilute with 10 mL of chloroform, and add the solution through a dropper plugged with cotton to 200 mL of vigorously stirred petroleum ether, let stand, filter, and dry to constant weight to obtain the target polymer. Pale yellow solid, yield 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 embodiment also has good solubility and thermal stability; because it contains tetraphenylvinyl groups with aggregation-induced emission activity, the polymer also has aggregation-induced emission performance. In addition, the film prepared by mixing the oxazolidinone polymer prepared in the present invention with nylon 6 (PA6) and heating it has phosphorescence at room temperature, which can be used in anti-counterfeiting.

[0166] Obviously, the above embodiments are merely examples for clear explanation and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived from these are still within the protection scope of the invention.

Claims

1. An oxazolidinone polymer, It is characterized in that The oxazolidinone polymer has the following general structural formula: Wherein, n is an integer from 2 to 200; R 1 Any one selected from the groups shown in Formula 1 to Formula 20, R 2 Any one selected from the groups shown in Formula 1 to Formula 20, R 3 Any one selected from the groups represented by Formula 21 to Formula 23; The structures of the above formulas 1 to 23 are as follows: Wherein, m is any integer of 1-18, * is the substitution position, and X is selected from F, Cl, Br or I.

2. A method for preparing the oxazolidinone polymer according to claim 1, It is characterized in that The steps include: In a carbon dioxide 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, It is characterized in that The molar ratio of the dibasic acetylene monomer, the dibasic aldehyde monomer, the monobasic amine monomer and cuprous iodide is 1:1:4:0.1-0.

8.

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

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

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

8. The preparation method according to claim 2, It is 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 of claim 1 is used as a fluorescent sensor to detect Fe 3+ Applications in this area, It is characterized in that The structure of the oxazolidinone polymer comprises one or two of the groups shown in Formulae 15 to 20.

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

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