A yellow light emitting pyrrole-based polymer and one-step synthesis preparation method and application

Abstract

The present invention relates to a yellow light emitting pyrrolyl polymer and a one-step synthesis preparation method and application. Under the protection of an inert gas, a diisocyanate and a diacetylenic ketone are dissolved, and a polymerization reaction is carried out by the catalytic action of cuprous iodide and potassium acetate; the obtained polymer is precipitated and dried to a constant weight to obtain a pyrrolyl polymer. The present invention obtains a pyrrolyl polymer by a [3+2] cycloaddition polymerization reaction between a diisocyanate and a diacetylenic ketone. The polymerization reaction monomer is easy to prepare, the process is simple, the conditions are mild, the efficiency is high, no side reactions are generated during the polymerization process, and the principle of atom economy is met. The pyrrolyl polymer obtained by the present invention has good thermal stability, good solid and liquid luminescence, and the film obtained after mixing with commercial polyvinyl alcohol (PVA) has good mechanical properties without affecting its luminescence characteristics. The film exhibits a luminescence enhancement phenomenon as the tensile stress increases during the stretching process.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials and relates to a yellow light emitting pyrrole-based polymer and a one-step synthesis preparation method and application thereof. Background Art

[0002] The development of new polymerization reaction methods is of great significance for the development of functional materials. Pyrrolyl polymers have very important applications in the field of optoelectronic materials, so exploring simple and efficient preparation methods is particularly important for solving the problem of efficient synthesis of pyrrolyl polymers. However, there are still very limited reports on the synthesis methodology of pyrrolyl polymers. In 2016, Bruce A. Arndtse reported a method for obtaining a series of pyrrolyl polymers by a two-step one-pot polymerization reaction using imines, acyl chlorides, and alkynes. In general, there are few research reports on the synthesis methods of pyrrolyl polymers, so it can be foreseen that the development of a simple and efficient one-step synthesis method for preparing pyrrolyl polymers has important scientific significance and research value.

[0003] Yellow light emitting materials, as long-wavelength luminescent materials, have important applications in the field of full-color display, but currently there are relatively few materials that can achieve yellow light emission through non-doping means. Therefore, it will be of great value to the research and development of luminescent materials to achieve non-doping one-step preparation of long-wavelength yellow light materials by rationally designing the functional monomer structure and screening the optimal reaction conditions. Summary of the invention

[0004] Technical issues to be solved

[0005] In order to avoid the shortcomings of the prior art, the present invention provides a yellow light emitting pyrrole-based polymer and a one-step synthesis preparation method and application.

[0006] The object of the present invention is to provide a one-step method for synthesizing a pyrrole-based polymer emitting yellow light. The preparation method is achieved by a cycloaddition reaction of an acetyl ketone and an isocyanate. The reaction operation is simple and efficient, and no complicated post-processing steps are required.

[0007] Another object of the present invention is to obtain a polymer having long-wavelength yellow light emission by using the above method. The obtained pyrrole-based polymer has good luminescence properties in both solid and liquid states, and can be blended with commercial polyvinyl alcohol (PVA) to obtain a film having both mechanical properties and luminescence properties. During the stretching process, the luminescence of the film gradually increases with the increase of the tensile stress. This discovery provides a new idea for the development and application of functional materials.

[0008] Technical Solution

[0009] A yellow light emitting pyrrole-based polymer characterized by the general structural formula:

[0010]

[0011] Wherein: n is an integer of 2 to 200, and R1 is selected from any one of the following chemical structural formulas:

[0012]

[0013] A is a group with different structures, selected from any one of the following chemical formulas:

[0014]

[0015] A method for preparing the yellow light emitting pyrrole-based polymer by one-step synthesis, characterized in that the steps are as follows:

[0016] Step 1: Under the protection of inert gas nitrogen, diisocyanate and diacetylene ketone are mixed in an organic solvent, and a catalyst cuprous iodide and an inorganic base potassium acetate are added to carry out a cycloaddition polymerization reaction at 110-120° C. for 24 hours;

[0017] The molar ratio of the dibasic isocyanate to the dibasic acetylenic ketone is 1.2:1;

[0018] Step 2: After the reaction is completed, a suitable organic solvent is used to dissolve the obtained product, and then the product is precipitated and washed by a precipitant. The precipitate is collected and dried to a constant weight to obtain a pyrrole-based polymer.

[0019] The organic solvent in step 1 is N-methylpyrrolidone.

[0020] The amount of the catalyst cuprous iodide used is 10% of the molar amount of the dibasic acetylenic ketone.

[0021] The molar ratio of the amount of the inorganic base potassium acetate to the amount of the dibasic acetylenic ketone is 1:1.

[0022] The organic solvent in step 2 includes but is not limited to dichloromethane or DMF solvent.

[0023] The precipitant in step 2 is ether or chloroform.

[0024] An application of the yellow light emitting pyrrole-based polymer is characterized by being used in the field of yellow-green light emitting polymer materials and stimulus-responsive luminescence enhancement.

[0025] Beneficial Effects

[0026] The present invention proposes a yellow light emitting pyrrolyl polymer and a one-step synthesis preparation method and application. Under the protection of an inert gas, a diisocyanate and a diacetylenic ketone are dissolved in an organic solvent, and a polymerization reaction is carried out by the catalytic action of cuprous iodide and potassium acetate; after the reaction is completed, the obtained polymer is precipitated with a precipitant, and dried to a constant weight to obtain a pyrrolyl-containing polymer; the present invention obtains a pyrrolyl polymer by a [3+2] cycloaddition polymerization reaction of a diisocyanate and a diacetylenic ketone. The monomer of the polymerization reaction is easy to prepare, the process is simple, the conditions are mild, the efficiency is high, no side reactions are generated during the polymerization process, and it complies with the principle of atom economy. The pyrrolyl polymer obtained by the present invention has good thermal stability, good solid and liquid luminescence, and the film obtained after mixing with commercial polyvinyl alcohol (PVA) has good mechanical properties without affecting its luminescence characteristics. The film shows a luminescence enhancement phenomenon as the tensile stress increases during the stretching process. The pyrrole-based polymer prepared by the present invention has good thermal stability, good mechanical properties and photophysical properties, and provides a new idea for preparing the pyrrole-based polymer with yellow light emission characteristics in a simple and efficient way in one step.

[0027] Advantages of the present invention:

[0028] 1. The present invention utilizes a difunctional acetylene ketone and a difunctional isocyanate to undergo a polycycloaddition reaction in the presence of a catalyst to synthesize a pyrrole-based polymer in one step. This method is a new method for synthesizing pyrrole-structured polymers and is of great significance for the development of polymerization methodology;

[0029] 2. The monomer of the present invention is easy to prepare, the polymerization conditions are mild, the process is simple, and no complicated post-processing operation is required. A polymer with a high molecular weight and a narrow molecular weight distribution can be obtained in 24 hours;

[0030] 3. The pyrrole-based polymer prepared by the present invention has the property of emitting long-wavelength yellow light. The obtained polymer can emit bright yellow light in both solid and liquid states, which provides a new idea for the non-doped one-step synthesis of long-wavelength yellow light emitting materials;

[0031] 4. The polymer prepared by the present invention has good mechanical properties after being mixed with commercial polyvinyl alcohol (PVA), and the luminescence gradually increases with the increase of stress during the stretching process, which has a good application prospect. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 The pyrrole-based polymer and its corresponding monomer prepared in Example 1 were precipitated in deuterated dimethyl sulfoxide (DMSO-d 6) in Figure 1; a is the H NMR spectrum and C NMR spectrum of the acetyl ketone monomer M1, b is the H NMR spectrum and C NMR spectrum of the isocyanate monomer M2; c is the H NMR spectrum and C NMR spectrum of the model compound 4-benzoyl-1H-pyrrole-2-carboxylic acid ethyl ester; d is the polymer PCP 1 The hydrogen and carbon NMR spectra of

[0033] Figure 2 The infrared comparison images of the pyrrole-based polymer prepared in Example 1 and its corresponding monomer and model compound;

[0034] Figure 3 The thermogravimetric curves of the pyrrole-based polymers prepared in Examples 1 to 7;

[0035] Figure 4 The luminescence images of the pyrrole-based polymers prepared in Examples 1 to 7 in solid and liquid states;

[0036] Figure 5 The stress-strain curves of the mechanical properties of the polymers of Examples 3 to 5; DETAILED DESCRIPTION

[0037] The present invention will now be further described with reference to the embodiments and the accompanying drawings:

[0038] The present invention can be implemented by the following technical solutions:

[0039] (1) Under the protection of inert gas nitrogen, a dibasic isocyanate and a dibasic activated acetylenic ketone are polymerized in an organic solvent by a catalyst and an inorganic base;

[0040] (2) after the reaction is completed, dissolving the obtained product in a suitable organic solvent, precipitating it with a precipitant, washing it, collecting the precipitate, and drying it to a constant weight to obtain a pyrrole-based polymer;

[0041] The general structural formula of the diisocyanate compound is as follows:

[0042]

[0043] The general structural formula of the binary activated alkynone compound is as follows:

[0044]

[0045] The general structural formula of the obtained pyrrole-based polymer is as follows:

[0046]

[0047] The polymerization reaction formula of the obtained pyrrole-based polymer is as follows:

[0048]

[0049] In formulas (I) to (IV), n is an integer of 2 to 200; R1 is selected from any one of the following chemical structural formulas 1 to 3; A is selected from any one of structural formulas 4 to 7;

[0050]

[0051] The organic solvent described in step (1) is N-methylpyrrolidone;

[0052] The precipitant in step (2) is ether / chloroform (V / V=20:1)

[0053] The reaction temperature in step (1) is 110-120°C;

[0054] The reaction catalyst described in step (1) is cuprous iodide;

[0055] The inorganic base described in step (1) is potassium acetate;

[0056] The molar ratio of the diisocyanate to the diacetylene ketone in step (1) is 1.2:1;

[0057] The amount of the catalyst cuprous iodide used in step (1) is 10% of the molar amount of the dibasic acetylenic ketone;

[0058] The pyrrole-based polymer is obtained by the above-mentioned preparation method. The pyrrole-based polymer has good thermal stability and yellow light emitting properties, and can be blended with polyvinyl alcohol to obtain a luminescent elastomer material. The proposal of the polymerization method provides a new strategy for preparing functional materials and has good application prospects.

[0059] [Example 1]

[0060] A yellow light emitting pyrrole-based polymer having a structural formula such as PCP 1 As shown:

[0061]

[0062] The pyrrolyl polymer is prepared by a cycloaddition reaction of an acetylene ketone monomer and an isocyanate monomer, and the reaction equation is as follows:

[0063]

[0064] Among them, the synthesis method of monomers 1a and 1b can be prepared according to the synthesis method in the published literature (Yang Shi, Anjun Qin, Benzhong Tang, et al. Chem. Eur. J. 2017, 23, 10725-10731. Tianyu Cheng, Anjun Qin, Benzhong Tang, et al. Macromolecules 2018, 51, 5638-5645).

[0065] The preparation steps of the pyrrole-based polymer are as follows:

[0066] Add 1a 54.6mg (0.3mmol), 1b 90.7mg (0.3mmol), cuprous iodide 5.7mg (0.3mmol), potassium acetate 29mg (0.03mmol) to a 10mL schlenk tube, and evacuate and replace the air 3 times. Add 1.5mL N-methylpyrrolidone through a disposable syringe, react at 120℃ for 24 hours, and the speed is 500 rpm. After the reaction is completed, add 5mL of dichloromethane to dilute the reaction solution. After dilution, centrifuge the reaction solution at 8000r / min in a high-speed rotating centrifuge. Add the supernatant drop by drop into the stirring ether / chloroform mixed precipitant for precipitation. After precipitation, let it stand for half an hour, filter, and dry the polymer in a vacuum drying oven at 60℃ to constant weight to obtain polymer PCP 1 After determination and analysis, the polymer PCP obtained by the method of the present invention 1 The yield was 83%, the weight average molecular weight was 10100, and the molecular weight distribution was 1.65. Figure 1 For PCP 1 Compared with the NMR of the corresponding monomer in deuterated dimethyl sulfoxide, it can be determined from the figure that PCP 1 It is the ideal target product, pyrrole-based polymer. The characteristic peaks of hydrogen atoms on pyrrole are at chemical shifts of δ12.85, 7.55, and 7.10 ppm. The disappearance of carbon atom peaks at chemical shifts of δ80, 83, and 159 ppm proves the complete disappearance of the reaction monomers acetylenic ketone 1a and isocyanate 1b. The characteristic peaks of pyrrole carbon are newly generated at chemical shifts of δ130, 129, 124, and 116 ppm, thus proving that the obtained polymer is the target polymer. The obtained PCP 1 The polymer is well soluble in N,N-dimethylformamide and dimethyl sulfoxide, indicating that the polymer has excellent solubility; and can be blended with polyvinyl alcohol to obtain a luminescent elastomer, indicating that the polymer has the potential to be used as a functional material.

[0067] [Example 2]

[0068] A yellow light emitting pyrrole-based polymer having a structural formula such as PCP 2 As shown:

[0069]

[0070] The pyrrolyl polymer is prepared by a cycloaddition reaction of an acetylene ketone monomer and an isocyanate monomer, and the reaction equation is as follows:

[0071]

[0072] Among them, the synthesis method of monomers 1a and 2b can be prepared according to the synthesis method in the published literature. The preparation steps of the pyrrolyl polymer are as follows: 1a 54.6mg (0.3mmol), 2b 101mg (0.36mmol), cuprous iodide 5.7mg (0.3mmol), potassium acetate 29mg (0.03mmol) are added to a 10mL schlenk tube. The air is replaced by vacuum for 3 times, 1.5mL N-methylpyrrolidone is added through a disposable syringe, and the reaction is carried out at 120°C for 24 hours at a speed of 500 rpm. After the reaction is completed, 5mL of dichloromethane is added to dilute the reaction solution, and after dilution, the reaction solution is centrifuged by a high-speed rotating centrifuge at 8000r / min, and the supernatant is added drop by drop to the stirring ether / chloroform mixed precipitant for precipitation. After precipitation, it is allowed to stand for half an hour and filtered. The resulting product is placed in a 60°C vacuum drying oven and dried to constant weight to obtain a pyrrolyl polymer PCP. 2 After determination and analysis, the product pyrrole polymer PCP 2 The yield was 49%, the weight average molecular weight was 11600, and the molecular weight distribution was 1.79. 2 The polymer is well soluble in N,N-dimethylformamide and dimethyl sulfoxide, indicating that the polymer has excellent solubility.

[0073] [Example 3]

[0074]

[0075] The pyrrolyl polymer is prepared by a cycloaddition reaction of an acetylene ketone monomer and an isocyanate monomer, and the reaction equation is as follows:

[0076]

[0077] Among them, the synthesis method of monomers 1a and 3b can be prepared according to the synthesis method in the published literature. The preparation steps of the pyrrolyl polymer are as follows: add 1a 54.6mg (0.3mmol), 3b110.8mg (0.36mmol), cuprous iodide 5.7mg (0.3mmol), and potassium acetate 29mg (0.03mmol) into a 10mL schlenk tube. Vacuum and replace the air 3 times, add 1.5mL N-methylpyrrolidone through a disposable syringe, and react at 120°C for 24 hours at a speed of 500 rpm. After the reaction is completed, add 5mL of dichloromethane to dilute the reaction solution, and after dilution, centrifuge the reaction solution through a high-speed rotating centrifuge at 8000r / min, and precipitate the supernatant by dropwise addition to the stirring ether / chloroform mixed precipitant. After precipitation, let it stand for half an hour and filter. The resulting product is dried to constant weight in a 60°C vacuum drying oven to obtain the pyrrolyl polymer PCP 3 After determination and analysis, the product pyrrole polymer PCP 3 The yield was 61%, the weight average molecular weight was 9100, and the molecular weight distribution was 1.58. 3 The polymer is well soluble in N,N-dimethylformamide and dimethyl sulfoxide, indicating that the polymer has excellent solubility.

[0078] [Example 4]

[0079]

[0080] The pyrrolyl polymer is prepared by a cycloaddition reaction of an acetylene ketone monomer and an isocyanate monomer, and the reaction equation is as follows:

[0081]

[0082] Among them, the synthesis method of monomers 2a and 1b can be prepared according to the synthesis method in the published literature. The preparation steps of the pyrrolyl polymer are as follows: add 2a 104.7mg (0.3mmol), 1b 90.7mg (0.36mmol), cuprous iodide 5.7mg (0.3mmol), potassium acetate 29mg (0.03mmol) into a 10mL schlenk tube, evacuate and replace the air 3 times, add 1.5mL N-methylpyrrolidone through a disposable syringe, react at 120°C for 24 hours, and the speed is 500 rpm. After the reaction is completed, add 5mL of dichloromethane to dilute the reaction solution, centrifuge the reaction solution at 8000r / min after dilution, and add the supernatant drop by drop into the ether / chloroform mixed precipitant being stirred for precipitation. After precipitation, let it stand for half an hour, filter, and dry the obtained product in a vacuum drying oven at 60°C to constant weight to obtain the pyrrolyl polymer PCP. 4 After determination and analysis, the product pyrrole polymer PCP 4 The yield was 59%, the weight average molecular weight was 14400, and the molecular weight distribution was 1.99. 4 The polymer is well soluble in N,N-dimethylformamide and dimethyl sulfoxide, indicating that the polymer has excellent solubility.

[0083] [Example 5]

[0084]

[0085] The pyrrolyl polymer is prepared by a cycloaddition reaction of an acetylene ketone monomer and an isocyanate monomer, and the reaction equation is as follows:

[0086]

[0087] Among them, the synthesis method of monomers 3a and 1b can be prepared according to the synthesis method in the published literature. The preparation steps of the pyrrolyl polymer are as follows: add 3a 112.2mg (0.3mmol), 1b 90.7mg (0.3mmol), cuprous iodide 5.7mg (0.3mmol), potassium acetate 29mg (0.03mmol) into a 10mL schlenk tube, evacuate and replace the air 3 times, add 1.5mL N-methylpyrrolidone through a disposable syringe, and react at 120°C for 24 hours at a speed of 500 rpm. After the reaction is completed, add 5mL of dichloromethane to dilute the reaction solution, centrifuge the reaction solution at 8000r / min through a high-speed rotating centrifuge, and add the supernatant drop by drop into the stirring ether / chloroform mixed precipitant for precipitation. After precipitation, let it stand for half an hour and filter. The resulting product is dried to constant weight in a 60°C vacuum drying oven to obtain the pyrrolyl polymer PCP 5 After determination and analysis, the product pyrrole polymer PCP 5 The yield was 87%, the weight average molecular weight was 10300, and the molecular weight distribution was 1.81. 5 The polymer is well soluble in N,N-dimethylformamide and dimethyl sulfoxide, indicating that the polymer has excellent solubility.

[0088] [Example 6]

[0089]

[0090] The pyrrolyl polymer is prepared by a cycloaddition reaction of an acetylene ketone monomer and an isocyanate monomer, and the reaction equation is as follows:

[0091]

[0092] Among them, the synthesis method of monomers 4a and 1b can be prepared according to the synthesis method in the published literature. The preparation steps of the pyrrolyl polymer are as follows: add 4a 66.6mg (0.3mmol), 1b 90.7mg (0.3mmol), cuprous iodide 5.7mg (0.3mmol), potassium acetate 29mg (0.03mmol) into a 10mL schlenk tube, evacuate and replace the air 3 times, add 1.5mL N-methylpyrrolidone through a disposable syringe, and react at 120°C for 24 hours at a speed of 500 rpm. After the reaction is completed, add 5mL of dichloromethane to dilute the reaction solution, centrifuge the reaction solution at 8000r / min after dilution, and add the supernatant drop by drop into the stirring ether / chloroform mixed precipitant for precipitation. After precipitation, let it stand for half an hour and filter. The resulting product is dried to constant weight in a vacuum drying oven at 60°C to obtain the pyrrolyl polymer PCP 6 After determination and analysis, the product pyrrole polymer PCP 6 The yield was 46%, the weight average molecular weight was 18200, and the molecular weight distribution was 1.92. 6 The polymer is well soluble in N,N-dimethylformamide and dimethyl sulfoxide, indicating that the polymer has excellent solubility.

[0093] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the essence and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A method for preparing a yellow light emitting pyrrole-based polymer by one-step synthesis, characterized in that: The general structural formula of the yellow light emitting pyrrole-based polymer is: Wherein: n is an integer from 2 to 200; Here are the steps: Step 1: Under the protection of inert gas nitrogen, diisocyanate and diacetylene ketone are mixed in an organic solvent, and a catalyst cuprous iodide and an inorganic base potassium acetate are added to carry out a cycloaddition polymerization reaction at 110-120° C. for 24 hours; The diisocyanate is selected from any one of the following chemical structural formulas: The dibasic alkynone is selected from any one of the following chemical formulas: The molar ratio of the dibasic isocyanate to the dibasic acetylenic ketone is 1.2:1; Step 2: After the reaction is completed, a suitable organic solvent is used to dissolve the obtained product, and then the product is precipitated and washed by a precipitant. The precipitate is collected and dried to a constant weight to obtain a pyrrole-based polymer.

2. The method according to claim 1, characterized in that: The organic solvent in step 1 is N-methylpyrrolidone.

3. The method according to claim 1, characterized in that: The amount of the catalyst cuprous iodide used is 10% of the molar amount of the dibasic acetylenic ketone.

4. The method according to claim 1, characterized in that: The molar ratio of the amount of the inorganic base potassium acetate to the amount of the dibasic acetylenic ketone is 1:

1.

5. The method according to claim 1, characterized in that: The organic solvent in step 2 includes but is not limited to dichloromethane or DMF solvent.

6. The method according to claim 1, characterized in that: The precipitant in step 2 is ether or chloroform.

7. Use of a yellow light emitting pyrrole-based polymer obtained by the method of claim 1, characterized in that: Used in the field of yellow-green light-emitting polymer materials and stimulus-responsive luminescence enhancement.

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