CN113943402A - Polyphenothiazine derivative and preparation method and application thereof - Google Patents
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Abstract
The invention relates to a polythiophene derivative, a preparation method and application thereof, wherein the structural formula of the polythiophene derivative is as follows:
wherein X: y is 0.4-2.8; preferably X: y is 0.5 to 2.
Description
Technical Field
The invention relates to a polythieazine derivative and a preparation method and application thereof, belonging to the field of polymer preparation.
Background
Phenothiazine was first discovered and synthesized in 1883 by the german chemist, Bemthsen, who obtained phenothiazine by co-heating diphenylamine and sulfur as starting materials at high temperatures. Phenothiazine and its derivative are electron-rich aromatic heterocyclic compounds containing nitrogen and sulfur atoms. Due to the existence of the heteroatom, the phenothiazine has good electron donating capability and excellent fluorescence property, and is a relatively common strong electron donating group in the field of organic semiconductors.
The phenothiazine material used as the organic photoelectric material has the following characteristics:
(1) the geometrical structure is special. In the six-membered ring in the middle of the phenothiazine, there are two heteroatoms (S and N). The heteroatom will exhibit an sp3 hybridized electronic structure, and thus this six-membered heterocyclic ring will exhibit a dihedral angle of 150 ° to form a space structure resembling a butterfly. The structure can inhibit the tight stacking among molecules while ensuring certain rigidity and flexibility of the group, thereby improving the fluorescence quantum efficiency of the fluorescent molecule;
(2) the electron donating ability is strong. The phenothiazine has two heteroatoms which present an sp3 hybridized electronic structure and has strong electron donating capability;
(3) the substitution pattern is various. Phenothiazine has abundant chemical reaction activity and is very easy to modify and substitute. The N position in the phenothiazine is an electron-rich site, has strong nucleophilicity, and can perform nucleophilic substitution reaction with halogenated hydrocarbon. The 3 and 7 positions of phenothiazine can be subjected to electrophilic substitution reaction, and can be directly subjected to acylation reaction to form aldehyde group. Or aryl substitution is carried out by Suzuki coupling reaction after bromination.
In conclusion, the phenothiazine unit can be used as a good photoelectric material due to the unique structure and various substitution modes of the phenothiazine unit.
Disclosure of Invention
The invention provides a brand-new polymer luminescent material, namely a polythiophene derivative PPTD, a preparation method thereof and a pure organic polymer material which can be used as a luminescent layer of an OLED device.
In one aspect, the invention provides a polythiophene derivative, wherein the structural formula of the polythiophene derivative is as follows:
In the disclosure, the polythiophene derivative belongs to a non-conjugated polythiophene derivative, the film-forming property of a polymer vinyl chain reinforcing material is enhanced, a phenothiazine unit is used as a luminescent chromophore to enhance the luminescent property of the polymer vinyl chain reinforcing material, and a bromine atom is used as a spacer group to have an aggregation quenching effect caused by effective resistance polymerization. Wherein, if X: lower Y, a small number of luminescent chromophores leads to a decrease in the quantum efficiency of the resulting material. If X: the higher Y, the aggregation quenching also causes the quantum efficiency of the material to drop rapidly.
Preferably, the molecular weight of the polythiophene derivative is Mn 7000 to 9000, and Mw 12000 to 16000. Preferably, the molecular weight of the polythiophene derivative is 8000 to 9000, and the Mw is 14000 to 16000.
Preferably, the fluorescence emission peak value of the polythiezine derivative is 445-450 nm, the CIE coordinates are (a, b), wherein a is more than or equal to 0.17 and less than or equal to 0.22, and b is more than or equal to 0.14 and less than or equal to 0.17.
Preferably, the quantum yield of the polythiophene derivative is 6.12-9.23%, and the luminescence life is 4-6 ns.
On the other hand, the invention provides a preparation method of the polythiophene derivative, under the protective atmosphere, after 3-bromopropene is added into a polymerization monomer (3-phenothiazinylpropene) solution, the temperature is firstly reduced to-60 to-80 ℃, then an initiator is added, the reaction is carried out for 1 to 1.5 hours, the temperature is increased to room temperature (preferably 18 to 28 ℃) and the reaction is continued for 3 to 4 hours, and finally the polythiophene derivative is obtained through inactivation, washing and extraction.
In the method, in a protective atmosphere, 3-bromopropylene is added into a polymerized monomer (3-phenothiazinylpropene) solution, then the temperature is reduced to-60 to-80 ℃, an initiator is added and the reaction is carried out for 1 to 1.5 hours, the polymerized monomer is initiated by the initiator to carry out prepolymerization in the process, the temperature is increased to room temperature (18 to 28 ℃) and the reaction is continued for 3 to 4 hours, and the poly-phenothiazine derivative is further polymerized in the process to finally obtain the poly-phenothiazine derivative.
Preferably, the solvent for the solution of the polymerized monomer (3-phenothiazinylpropene) is tetrahydrofuran THF, CH2Cl2And CHCl3At least one of; the molar ratio of the polymerized monomer (3-phenothiazinylpropene) to the 3-bromopropene is 0.4-2.8.
Preferably, the initiator is selected from at least one of butyl lithium and potassium tert-butoxide; the addition amount of the initiator is 0.2-1.5 wt% of the mass of the polymerized monomer (3-phenothiazinylpropene).
Preferably, the preparation method of the polymerized monomer (3-phenothiazinylpropene) comprises the following steps:
(1) adding 3-bromopropylene and an alkali solution into a phenothiazine solution under a protective atmosphere, stirring and reacting for 10-12 hours at 18-28 ℃ (during the reaction, a polymerized monomer 3-phenothiazinylpropene is formed), washing, extracting, drying and filtering to obtain a filtrate;
(2) and mixing the obtained filtrate with silica gel, adsorbing a polymerized monomer (3-phenothiazinylpropene) on the silica gel through a rotary evaporator, and performing column chromatography by using n-hexane/ethyl acetate as an eluent to obtain the polymerized monomer (3-phenothiazinylpropene).
Preferably, the alkali solution is a sodium hydroxide solution, and the concentration is 1-1.5 moL/L; the mass ratio of the phenothiazine to the 3-bromopropylene is (5-7): (6-10). Preferably, the adding amount of the catalyst is 5-15 mL.
Preferably, the solvent of the phenothiazine solution is at least one selected from the group consisting of N, N-dimethylformamide and toluene.
Preferably, the protective atmosphere is a nitrogen atmosphere or an inert atmosphere.
In another aspect, the invention further provides an application of the polythiophene derivative in an electroluminescent device.
Has the advantages that:
in the invention, the advantages of preparing the polythiazine derivatives are that the synthesis method is simple, mass production is facilitated, the raw material source is wide, the price is low, and the preparation cost is effectively reduced. In addition, polymer chains are introduced to improve the film forming property, and the film forming property is easy to dissolve in common organic solvents and good. Therefore, the non-conjugated polythiophene derivative prepared by the preparation method disclosed by the invention has the advantages of low cost, easiness in film formation, good photoelectric property and the like. The emission lifetime is 5ns, the quantum efficiency (or quantum yield) is 7.57%, the fluorescence emission peak is 448nm, the CIE coordinates are (0.19,0.16), and the emission is in the blue region.
Drawings
FIG. 1 shows the fluorescence emission peak of the polythiophene derivative prepared in example 1;
FIG. 2 is the CIE coordinates of the polythiazine derivatives prepared in example 1;
FIG. 3 shows the quantum yield of the polythiazine derivatives prepared in example 1;
FIG. 4 shows the lifetimes of the polythieazine derivatives prepared in example 1.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the disclosure, the structural formula of the polymer luminescent material polythiophene derivative is:
wherein, X and Y are 0.4-2.8, preferably 0.5-2.
In the present invention, vinyl chains are introduced in the phenothiazine group to improve the film-forming properties of the resulting material. In addition, bromine atoms are hydrophobic groups, and the hydrophobicity of the material is enhanced through the introduction of the bromine atoms, so that the polythiophene derivative can form a thin film on the ITO surface more easily.
In one embodiment of the invention, the synthetic method of the phenothiazine derivative is simple and is beneficial to mass production. The following is an exemplary description of the preparation of the polythiezine derivatives.
Preparation of the polymerized monomer (3-phenothiazinylpropene). Under the protection of nitrogen, 0.4-0.6 g of potassium hydroxide is mixed with 10mL of water to form a mixed solution A as a catalyst. 10-14 g of phenothiazine and 100-120 mL of N, N-dimethylformamide are mixed in a 250mL three-neck flask, and the mixture is fully and uniformly stirred to obtain a mixed solution B. And adding 12-20 g of 3-bromopropylene and the mixed solution A into a flask filled with the mixed solution B to obtain a mixed solution C. And heating the mixed solution C to 18-28 ℃ (for example, 20 ℃), and stirring for reaction for 10-12 h to obtain a reaction solution containing 3-phenothiazinylpropene. Further, after the reaction is finished, the reaction solution is washed by brine, then extracted by dichloromethane, dried by anhydrous magnesium sulfate and filtered to obtain a filtrate. The filtrate was mixed with silica gel and the product 3-phenothiazinylpropene was adsorbed on the silica gel by means of a rotary evaporator. And finally, carrying out column chromatography by using n-hexane/ethyl acetate as an eluent to obtain a 3-phenothiazinylpropene product. In the above process, the catalyst may also be selected from other alkali solutions, such as sodium hydroxide and the like.
In a three-necked flask, under the protection of nitrogen, 7-17 g of a polymerization monomer (3-phenothiazinylpropene) and 80-120 mL of tetrahydrofuran THF are thoroughly stirred and mixed, and 3-9 g of 3-bromopropene is added. When the temperature drops to-60 to-80 deg.C (for example, -78 deg.C), butyl lithium is added as an initiator. Reacting for 1-1.5 h at-60 to-80 ℃ (for example, -78 ℃), and then continuing to react for 3-4 h at normal temperature (18-28 ℃). After the reaction is finished, methanol, ethanol and deionized water are added dropwise to inactivate. Washed with brine, after which the reaction was extracted with dichloromethane. Evaporating the extract by using a rotary evaporator, and drying the sample by using a vacuum oven at 40 ℃ to obtain the product of the polythiazine derivative. Mixing liquid nitrogen and acetone to provide a reaction temperature of-60 to-80 ℃. In the above process, the initiator may also be selected from butyl lithium, potassium tert-butoxide, etc. Preferably, the amount of the initiator added is 0.2 to 1.5 wt% based on the mass of the 3-phenothiazinylpropene.
In the invention, AVANCE-500MHZ type gel permeation chromatography is selected to test the molecular weight of the obtained polythiophene ramification to be Mn 7000-9000 and Mw 12000-16000.
In the invention, an FS-5 type transient-steady state fluorescence spectrometer is selected for testing to obtain the polythiophene ramification, the fluorescence emission peak value is 445-450 nm, CIE coordinates are (a, b), wherein a is more than or equal to 0.17 and less than or equal to 0.22, and b is more than or equal to 0.14 and less than or equal to 0.17.
In the invention, the quantum yield of the polythiophene derivative obtained by testing with an FS-5 type transient-steady state fluorescence spectrometer is 6.12-9.23%. The FS-5 type transient-steady state fluorescence spectrometer is selected for testing, and the luminous life of the polythiophene ramification is 4-6 ns.
In the invention, a Q500 thermogravimetric analyzer is selected to test that the thermal decomposition temperature of the phenothiazine derivative is 250-290 ℃.
In the invention, the obtained polythiophene derivative has good solubility, is soluble in various organic solvents such as chloroform, dichloromethane, tetrahydrofuran and the like, and can be conveniently spin-coated into a film by a solution method. The polymer has better photoelectric property and is suitable for being used as a light-emitting layer material of an OLED. The design of the material structure provides a certain guiding idea for further developing the polymer luminescent material.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1:
1) preparation of polymerized monomer (3-phenothiazinylpropene):
under nitrogen, 0.56g (0.01mol) of potassium hydroxide was mixed with 10mL of water to prepare a mixed solution A. In a 250mL three-necked flask, 12g (0.06mol) of phenothiazine and 100mL of N, N-dimethylformamide were mixed, and after stirring sufficiently and uniformly, 14.4g (0.12mol) of 3-bromopropene and mixture A were added to the flask. Heating to 20 ℃, and stirring for reaction for 12 hours;
after the reaction is finished, the reaction solution is washed by brine, then extracted by dichloromethane, dried by anhydrous magnesium sulfate and filtered. The filtrate was mixed with silica gel and the product was adsorbed on silica gel by rotary evaporator. Column chromatography was performed using n-hexane/ethyl acetate (40/1, v/v) as eluent to give 5.85g of a white, transparent, viscous liquid with a yield of 40.79%.
2) Preparation of polythiezine derivative PPTD
Under nitrogen, a reaction temperature of-78 ℃ was set by mixing liquid nitrogen and acetone, and after stirring and mixing 11.95g (0.05mol) of 3-phenothiazinylpropene with 100mL of THF in a three-necked flask, 6g (0.05mol) of 3-bromopropene was added. When the temperature dropped to-78 deg.C, 0.1mL of butyllithium was added. The reaction was carried out at-78 ℃ for 1h, and then continued at ambient temperature for 4 h. And after the reaction is finished, sequentially dropwise adding methanol, ethanol and deionized water for inactivation. Washed with brine, after which the reaction was extracted with dichloromethane. After the extract was evaporated with a rotary evaporator, the sample was dried in a vacuum oven at 40 ℃ to obtain 4.13g of a pale yellow solid with a yield of 23.00%.
The molecular weight of the polythieazine derivative prepared in example 1 was: mn 8100 and Mw 14000. The pure phenothiazine derivatives generate a macroscopic strong blue luminescence phenomenon under the excitation of 360nm ultraviolet light. The quantum yield of the material was 7.57% by integrating sphere method, the emission lifetime was 5.0ns and the CIE coordinates were (0.19, 0.16). The thermal decomposition temperature was 270 ℃. The compound is expected to be applied to the preparation of electroluminescent devices, has better solubility in common organic solvents such as dichloromethane, trichloromethane, tetrahydrofuran and the like, and is easy to form films.
Example 2:
1) preparation of polymerized monomer (3-phenothiazinylpropene):
under nitrogen, 0.56g (0.01mol) of potassium hydroxide was mixed with 10mL of water to prepare a mixed solution A. In a 250mL three-necked flask, 12g (0.06mol) of phenothiazine and 100mL of N, N-dimethylformamide were mixed, and after stirring sufficiently and uniformly, 14.4g (0.12mol) of 3-bromopropene and mixture A were added to the flask. Heating to 20 ℃, and stirring for reaction for 12 hours;
after the reaction is finished, the reaction solution is washed by brine, then extracted by dichloromethane, dried by anhydrous magnesium sulfate and filtered. The filtrate was mixed with silica gel and the product was adsorbed on silica gel by rotary evaporator. Column chromatography was performed using n-hexane/ethyl acetate (40/1, v/v) as eluent to give 5.85g of a white, transparent, viscous liquid with a yield of 40.79%.
2) Preparation of polythiezine derivative PPTD
Under nitrogen, 16.73g (0.07mol) of 3-phenothiazinylpropene was mixed with 100mL of THF in a three-necked flask with stirring to provide a reaction temperature of-78 ℃ by mixing with acetone and liquid nitrogen, and 3g (0.025mol) of 3-bromopropene was added. When the temperature dropped to-78 deg.C, 0.1mL of butyllithium was added. The reaction was carried out at-78 ℃ for 1h, and then continued at ambient temperature for 4 h. And after the reaction is finished, sequentially dropwise adding methanol, ethanol and deionized water for inactivation. Washed with brine, after which the reaction was extracted with dichloromethane. After the extract was evaporated with a rotary evaporator, the sample was dried in a vacuum oven at 40 ℃ to obtain 4.53g of a pale yellow solid with a yield of 22.95%.
The molecular weight of the polythieazine derivative prepared in example 2 is: mn is 7987 and Mw is 12955. The pure phenothiazine derivatives generate a macroscopic strong blue luminescence phenomenon under the excitation of 360nm ultraviolet light. The quantum yield of the material was 6.37% by integrating sphere method, the emission lifetime was 5.0ns, and the CIE coordinates were (0.19, 0.16). The thermal decomposition temperature was 268 ℃. The compound is expected to be applied to the preparation of electroluminescent devices, has better solubility in common organic solvents such as dichloromethane, trichloromethane, tetrahydrofuran and the like, and is easy to form films.
Example 3:
1) preparation of polymerized monomer (3-phenothiazinylpropene):
under nitrogen, 0.56g (0.01mol) of potassium hydroxide was mixed with 10mL of water to prepare a mixed solution A. In a 250mL three-necked flask, 12g (0.06mol) of phenothiazine and 100mL of N, N-dimethylformamide were mixed, and after stirring sufficiently and uniformly, 14.4g (0.12mol) of 3-bromopropene and mixture A were added to the flask. Heating to 20 ℃, and stirring for reaction for 12 hours;
after the reaction is finished, the reaction solution is washed by brine, then extracted by dichloromethane, dried by anhydrous magnesium sulfate and filtered. The filtrate was mixed with silica gel and the product was adsorbed on silica gel by rotary evaporator. Column chromatography was performed using n-hexane/ethyl acetate (40/1, v/v) as eluent to give 5.85g of a white, transparent, viscous liquid with a yield of 40.79%.
2) Preparation of polythiezine derivative PPTD
Under nitrogen, a reaction temperature of-78 ℃ was set by mixing liquid nitrogen and acetone, and after 7.17g (0.03mol) of 3-phenothiazinylpropene was mixed with 100mL of THF in a three-necked flask with stirring, 9g (0.075mol) of 3-bromopropene was added. When the temperature dropped to-78 deg.C, 0.1mL of butyllithium was added. The reaction was carried out at-78 ℃ for 1h, and then continued at ambient temperature for 4 h. And after the reaction is finished, sequentially dropwise adding methanol, ethanol and deionized water for inactivation. Washed with brine, after which the reaction was extracted with dichloromethane. After the extract was evaporated with a rotary evaporator, the sample was dried in a vacuum oven at 40 ℃ to obtain 3.22g of a pale yellow solid with a yield of 19.91%.
The molecular weight of the polythieazine derivative prepared in example 3 is: mn 9000 and Mw 16000. The pure phenothiazine derivatives generate a macroscopic strong blue luminescence phenomenon under the excitation of 360nm ultraviolet light. The quantum yield of the material was 6.27% by integrating sphere method, the emission lifetime was 5.0ns and the CIE coordinates were (0.19, 0.16). The thermal decomposition temperature was 278 ℃. The compound is expected to be applied to the preparation of electroluminescent devices, has better solubility in common organic solvents such as dichloromethane, trichloromethane, tetrahydrofuran and the like, and is easy to form films.
Example 4
The process for the preparation of the polythiezine derivative of example 4 is referred to example 1, with the difference that: the molar ratio of 3-phenothiazinylpropene and 3-bromopropene was 2: 1.
Comparative example 1
The process for the preparation of the polythieazine derivative of this comparative example 1 is as per example 1, with the difference that: the molar ratio of 3-phenothiazinylpropene and 3-bromopropene was 0.2: 1.
Comparative example 2
The process for the preparation of the polythieazine derivative of this comparative example 2 is as described in example 1, with the following differences: the molar ratio of 3-phenothiazinylpropene and 3-bromopropene was 3: 1.
Table 1 shows the raw material components and performance parameters of the phenothiazine derivatives prepared in the present invention:
Claims (10)
1. the polythiophene derivative is characterized in that the structural formula of the polythiophene derivative is as follows:
2. A polythiophene derivative according to claim 1, wherein a molecular weight of said polythiophene derivative is Mn 7000 to 9000 and Mw 12000 to 16000.
3. A polythiophene derivative according to claim 1 or 2, wherein a fluorescence emission peak of the polythiophene derivative is 445-450 nm, CIE coordinates are (a, b), wherein a is 0.17-0.22, and b is 0.14-0.17; the quantum yield of the polythiophene ramification is 6.12-9.23%, and the luminous life is 4-6 ns.
4. The preparation method of the polythiophene derivative according to any one of claims 1 to 3, wherein 3-bromopropene is added into a 3-phenothiazinylpropene solution under a protective atmosphere, then the temperature is reduced to-60 ℃ to-80 ℃, then an initiator is added and the reaction is carried out for 1 to 1.5 hours, then the temperature is increased to room temperature and the reaction is continued for 3 to 4 hours, and finally the polythiophene derivative is obtained through inactivation, washing and extraction.
5. The method according to claim 4, wherein the solvent of the 3-phenothiazinylpropene solution is tetrahydrofuran THF or CH2Cl2And CHCl3At least one of; the molar ratio of the 3-phenothiazinylpropene to the 3-bromopropene is 0.4-2.8.
6. The production method according to claim 4 or 5, wherein the initiator is selected from at least one of butyl lithium and potassium tert-butoxide; the addition amount of the initiator is 0.2-1.5 wt% of the mass of the 3-phenothiazinylpropene.
7. The production method according to any one of claims 4 to 6, characterized in that the production method of 3-phenothiazinylpropene includes:
(1) adding 3-bromopropylene and an alkali solution into a phenothiazine solution under a protective atmosphere, stirring and reacting for 10-12 hours at 18-28 ℃, and then washing, extracting, drying and filtering to obtain a filtrate;
(2) and mixing the obtained filtrate with silica gel, adsorbing the 3-phenothiazinylpropene on the silica gel by using a rotary evaporator, and performing column chromatography by using n-hexane/ethyl acetate as an eluent to obtain the 3-phenothiazinylpropene.
8. The preparation method of claim 7, wherein the alkali solution is a sodium hydroxide or potassium hydroxide solution with a concentration of 1-1.5 moL/L; the mass ratio of the phenothiazine to the 3-bromopropylene is (5-7): (6-10).
9. The production method according to claim 7 or 8, wherein the solvent of the phenothiazine solution is at least one selected from the group consisting of N, N-dimethylformamide and toluene.
10. Use of a polythiophene derivative according to any one of claims 1 to 3 in an electroluminescent device.
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