Polythiophene compound as well as preparation method and application thereof

Abstract

The invention discloses a polythiophene compound as well as a preparation method and application thereof. The preparation method comprises the following steps: adding carbon disulfide and a dicarbonyl compound into an organic solvent, and stirring for reaction; adding polybromide into the reacted solution, and stirring to react; and adding the polymethylene activated bromide into the reacted solution, stirring to react, diluting, precipitating and drying to obtain the polythiophene compound. The preparation method has the advantages of easily available reaction raw materials, mild polymerization conditions, simple process and high polymerization efficiency. The polythiophene compound can be used for preparing a high refractive index film or an optical device, and can also be used for coating a carbon nanotube to prepare a composite material.

Description

Technical Field

[0001] The present invention belongs to the fields of polymer chemistry and materials science, and particularly relates to a polythiophene compound, a preparation method thereof, and an application thereof. Background Art

[0002] Sulfur-containing heterocyclic compounds are an indispensable class of compounds in daily life and have important applications from natural products and bioactive substances to functional materials. Traditional sulfur-containing heterocyclic compounds are mainly constructed directly using heterocyclic monomers. The synthesis methods used have many complicated steps and often use metal catalysts, which will cause environmental pollution problems. The synthesis of sulfur-containing heterocyclic compounds (such as thiophene, thiazole, etc.) based on non-heterocyclic monomers has been widely concerned, but the reported synthesis methods of related sulfur-containing polymers are very limited (Macromol. Rapid Commun, 2021, 42, 2000695.; J. Am. Chem. Soc. 2023, 145, 28204-28215.; Polymer Chemistry, 2024, 15, 2408-2415.; Macromolecules, 1998, 31(21): 7570-7571.). Therefore, it will be of great innovative and industrial significance to develop or explore the efficient construction of sulfur-containing heterocycles or the synthesis of polymers from non-heterocyclic monomers under mild conditions. Summary of the Invention

[0003] Aiming at the deficiencies of the existing technology, the purpose of the present invention is to provide a polythiophene compound, a preparation method thereof, and an application thereof.

[0004] In order to achieve the above invention purpose, the present invention provides the following technical solutions:

[0005] The present invention provides a preparation method of a polythiophene compound, comprising the following steps:

[0006] (1) Carbon disulfide and a dicarbonyl compound are added to an organic solvent and stirred for reaction;

[0007] (2) A polybromide is added to the solution obtained in step (1) and stirred for reaction;

[0008] (3) A poly(methylene-activated) bromide is added to the solution obtained in step (2), stirred for reaction, diluted, precipitated, and dried to obtain a polythiophene compound.

[0009] Preferably, the molar ratio of carbon disulfide, the dicarbonyl compound, the bromo-functional group of the polybromide, and the methylene bromo-functional group of the poly(methylene-activated) bromide is 1-3:1:0.5-1.0:1-2.

[0010] Preferably, the polybromide includes dibromide, tribromide, and tetrabromide. The reaction formula is shown in Figure 8 .

[0011] More preferably, when the polybromide is dibromide, the molar ratio of dibromide: carbon disulfide: dicarbonyl compound: methylene bromo-functional group of polymethylene-activated bromide is 0.25 - 0.5: 1 - 3: 1: 1 - 2.

[0012] Preferably, steps (1)-(3) are carried out under air conditions;

[0013] Preferably, the temperature of the stirring reaction in steps (1)-(3) is room temperature (20 - 30 °C);

[0014] Preferably, the stirring reaction time in step (1) is 1 - 2 hours;

[0015] More preferably, the stirring reaction time is 0.5 - 1.5 hours.

[0016] Preferably, the stirring speed of the stirring reaction in step (1) is 200 - 600 rpm;

[0017] More preferably, the stirring speed of the stirring reaction is 300 - 500 rpm.

[0018] Preferably, the stirring reaction time in step (2) is 4 - 8 hours;

[0019] More preferably, the stirring reaction time is 5 - 7 hours.

[0020] Preferably, the stirring speed of the stirring reaction in step (2) is 200 - 600 rpm;

[0021] More preferably, the stirring speed of the stirring reaction is 300 - 500 rpm.

[0022] Preferably, the stirring reaction time in step (3) is 2 - 4 hours;

[0023] More preferably, the stirring reaction time is 2.5 - 3.5 hours.

[0024] Preferably, the stirring speed of the stirring reaction in step (3) is 200 - 600 rpm;

[0025] More preferably, the stirring speed of the stirring reaction is 300 - 500 rpm.

[0026] Preferably, the dilution solvent used for dilution in step (3) is an organic solvent;

[0027] Further preferably, the organic solvent is one or a mixture of more than one of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and tetrahydrofuran.

[0028] Preferably, the precipitation solvent used in step (3) for precipitation is methanol.

[0029] Preferably, step (3) of drying is drying to constant weight at room temperature.

[0030] Preferably, the concentration of the dicarbonyl compound in the organic solvent in step (1) is 0.25 - 2 mol / L;

[0031] Preferably, the organic solvent in step (1) is one or a mixture of more than one of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and tetrahydrofuran;

[0032] Preferably, an organic solvent is further added in step (2), and the concentration of the polybromide in the organic solvent is 0.125 - 1 mol / L;

[0033] Further preferably, the organic solvent is one or a mixture of more than one of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and tetrahydrofuran;

[0034] Preferably, the concentration of the poly(methylene-activated) bromide in the organic solvent in step (3) is 0.125 - 1 mol / L.

[0035] Preferably, the carbon disulfide is a purified sample.

[0036] Preferably, the structural formula of the dicarbonyl compound is as follows:

[0037]

[0038] The structural formula of the polybromide is as follows:

[0039]

[0040] The structural formula of the poly(methylene-activated) bromide is as follows:

[0041]

[0042] Among them, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are each independently an aliphatic group or an aromatic group, and x is each independently an integer from 0 to 5, and y is each independently an integer from 0 to 3.

[0043] Further preferably, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are each independently selected from one or more combinations of a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C1-C10 alkoxy group, a substituted or unsubstituted C2-C10 ether group, a substituted or unsubstituted C2-C10 ester group, a substituted or unsubstituted C6-C15 aryl group, and a substituted or unsubstituted C3-C15 heteroaryl group, and the substituents are halogen (fluorine, chlorine, bromine, iodine), amino group, and hydroxyl group.

[0044] Preferably, the dicarbonyl compound is selected from any one of the following structural formulas:

[0045]

[0046] The polybromide is selected from any one of the following structural formulas:

[0047]

[0048] The poly(methylene-activated) bromide is selected from any one of the following structural formulas:

[0049]

[0050] The present invention also provides a polythiophene compound prepared by the above preparation method.

[0051] Preferably, the structural formula of the polythiophene compound is as follows:

[0052]

[0053] wherein, n is an integer from 2 to 800, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are each independently an aliphatic group or an aromatic group, and x are each independently an integer from 0 to 5, and y are each independently an integer from 0 to 3.

[0054] The present invention also provides the application of the above polythiophene compound in preparing a high refractive index film, preparing an optical device, or wrapping carbon nanotubes to prepare a composite material.

[0055] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0056] (1) The reaction raw materials of the preparation method of the present invention are easily available, can be directly commercially purchased and are inexpensive; the polymerization conditions are mild, the process is simple, and the polymerization efficiency is high.

[0057] (2) No catalyst is required under the preparation method of the present invention.

[0058] (3) The preparation method of the present invention has strong group universality, and various functional groups can be introduced into the monomers.

[0059] (4) The refractive index of the film prepared from the polythiophene compound obtained by the present invention reaches 1.7542 at 633 nm, and has particularly outstanding optical properties.

[0060] (5) The polythiophene compound obtained by the present invention can wrap carbon nanotubes, and the obtained composite material has good photothermal properties. Description of the Drawings

[0061] Figure 1 It is a comparison diagram of the proton nuclear magnetic resonance spectra of the polythiophene compound prepared in Example 1 of the present invention, its corresponding monomer and the model compound in deuterated chloroform.

[0062] Figure 2 It is a comparison diagram of the carbon nuclear magnetic resonance spectra of the polythiophene compound prepared in Example 1 of the present invention, its corresponding monomer and the model compound in deuterated chloroform.

[0063] Figure 3 It is an infrared absorption spectrum diagram of the polythiophene compound prepared in Example 1 of the present invention, its corresponding monomer and the model compound.

[0064] Figure 4 It is a relationship spectrum diagram of the refractive index and wavelength of the polymer film prepared from the polythiophene compound P1 in Example 1 of the present invention.

[0065] Figure 5 It is a transmission electron microscope spectrum diagram before and after the polythiophene compound P2 in Example 2 of the present invention is wrapped with carbon nanotubes.

[0066] Figure 6 It is a scanning electron microscope spectrum diagram before and after the polythiophene compound P2 in Example 2 of the present invention is wrapped with carbon nanotubes.

[0067] Figure 7 It is a photothermal temperature change diagram of the composite material prepared by wrapping the polythiophene compound P2 in Example 2 of the present invention with carbon nanotubes.

[0068] Figure 8 It is a reaction formula of dibromide, tribromide and tetrabromide. Detailed Embodiments

[0069] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0070] Embodiment 1

[0071] A polythiophene compound, the structural formula of which is shown in P1:

[0072]

[0073] The polythiophene compound is prepared by a two-step method using carbon disulfide, a dicarbonyl compound, a bromide, and a methylene-activated bromide. The reaction formula is as shown in formula (I):

[0074]

[0075] Among them, monomer M1 is 1,6-dibromohexane, and M1' is 4,4'-bis(2-bromoacetyl)biphenyl, both of which can be purchased from the market. In this example, they are purchased from Anyuji Company; M is carbon disulfide, which can be purchased from the market. In this example, it is purchased from Anyuji Company; M0 is ethyl acetoacetate, which can be purchased from the market. In this example, it is purchased from Anyuji Company.

[0076] The synthesis steps of the polythiophene are as follows: Under air conditions, monomers M and M0 are sequentially added to a polymerization tube according to a molar ratio of 3:1, and N,N-dimethylformamide is injected until the concentration of monomer M0 is 1 mol / L. Stir at a rate of 450 rpm at room temperature for 1 hour; then monomer M1 is added to the polymerization tube according to half of the feeding ratio of monomer M0, and N,N-dimethylformamide is injected until the concentration of monomer M1 is 0.2 mol / L. Stir at a rate of 450 rpm at room temperature for 4 hours; then monomer M1' is added to the polymerization tube according to half of the feeding ratio of monomer M0, and stir at a rate of 450 rpm at room temperature for 4 hours. After the reaction is completed, the reaction mother liquor is dissolved in N,N-dimethylformamide, and then it is dropped into methanol, allowed to stand, filtered, and dried to obtain the polythiophene compound P1.

[0077] After determination and analysis, the yield of the final product polythiophene compound P1 is 88%, the weight-average molecular weight is 17700 g / mol, and the molecular weight distribution is 1.94.

[0078] The comparison chart of the nuclear magnetic resonance hydrogen spectrum of the polythiophene compound and its corresponding monomer (* represents the solvent peak) is shown in Figure 1 , compared with monomer M0 ( Figure 1In A) of , in the 1H NMR spectrum of the polythiophene compound P1, the chemical shift value of the hydrogen in the ester group [-C(=O)O-CH2-] is located at 4.38 ppm, which is consistent with that of the model molecule ( Figure 1 In D) of , the chemical shift value of the hydrogen in the ester group [-C(=O)O-CH2-] is consistent. Compared with the monomer M1 ( Figure 1 In B) of , in the 1H NMR spectrum of the polythiophene compound P1, the chemical shift value of the hydrogen in the methylene [-CH2-Br] is located at 3.02 ppm, which is consistent with that of the model molecule ( Figure 1 In D) of , the chemical shift value of the hydrogen in the methylene [-CH2-Br] is consistent. In the 1H NMR spectrum of the polythiophene compound P1, the chemical shift value of the hydrogen in the methyl [Ph-CH3] on the thiophene moiety is located at 2.51 ppm, which is consistent with that of the model molecule ( Figure 1 In D) of , the chemical shift value of the hydrogen in the methyl [Ph-CH3] on the thiophene moiety is consistent. There are two sets of aromatic hydrogens on the benzene ring, and their chemical shift values are doublets at 7.86 ppm and 7.73 ppm.

[0079] The comparative diagram of the 13C NMR spectrum is shown in Figure 2 , compared with the monomer M0 ( Figure 2 In A) of and the model molecule ( Figure 2 In D) of , in the carbon spectrum of the polythiophene compound P1, the chemical shift value of C=O is at 163.78 ppm. Compared with the monomer M1' ( Figure 2 In C) of and the model molecule ( Figure 2 In D) of , in the carbon spectrum of the polythiophene compound P1, the chemical shift value of C=O is at 188.24 ppm. The infrared absorption spectrum is shown in Figure 3 , in the spectrum of polythiophene P1, near 1719 cm -1 is the characteristic peak of C=O on the ester group of the monomer M0. In the spectrum of polythiophene P1, near 1690 cm -1 is the characteristic peak of C=O on the carbonyl group of the monomer M1'. The stretching vibration peak of C-S in the thiophene moiety is located near 1233 cm -1 .

[0080] Example 2

[0081] A polythiophene compound, the structural formula of which is shown as P2:

[0082]

[0083] The described polythiophene compound is prepared by a two-step method using carbon disulfide, dicarbonyl compound, bromide and methylene-activated bromide, and the reaction formula is as formula (two):

[0084]

[0085] Among them, monomer M2 is 1,4-bis(bromomethyl)benzene, and M2' is 4,4'-bis(2-bromoacetyl)biphenyl, both of which can be purchased from the market. In this example, they are purchased from Energy Chemical; M is carbon disulfide, which can be purchased from the market. In this example, it is purchased from Energy Chemical; M0 is ethyl acetoacetate, which can be purchased from the market. In this example, it is purchased from Energy Chemical.

[0086] The synthesis steps of the poly(thiophene) are as follows: Under air conditions, monomers M and M0 are sequentially added to a polymerization tube in a molar ratio of 3:1, and N,N-dimethylformamide is injected until the concentration of monomer M0 is 1 mol / L. While maintaining the room temperature constant, it is stirred at a rate of 450 rpm for 1 hour; subsequently, monomer M2 is added to the polymerization tube at half of the feeding ratio of monomer M0, and N,N-dimethylformamide is injected until the concentration of monomer M2 is 0.2 mol / L. While maintaining the room temperature constant, it is stirred at a rate of 450 rpm for 4 hours; subsequently, monomer M2' is added to the polymerization tube at half of the feeding ratio of monomer M0, and it is stirred at a rate of 450 rpm for 4 hours while maintaining the room temperature constant. After the reaction is completed, the reaction mother liquor is dissolved in N,N-dimethylformamide, and then it is dropped into methanol, allowed to stand, filtered, and dried to obtain the poly(thiophene) compound P2.

[0087] After measurement and analysis, the yield of the final product poly(thiophene) compound P2 is 88%, the weight-average molecular weight is 29400 g / mol, and the molecular weight distribution is 2.48.

[0088] Example 3

[0089] A poly(thiophene) compound, the structural formula of which is shown as P3:

[0090]

[0091] The described poly(thiophene) compound is prepared by a two-step method using carbon disulfide, a dicarbonyl compound, a bromide, and a methylene-activated bromide. The reaction formula is as shown in Formula (III):

[0092]

[0093] Among them, monomer M3 is 1,6-dibromohexane, which can be purchased from the market. In this example, it is purchased from Energy Chemical; M3' is α,α'-dibromo-1,3-diacetylbenzene, which needs to be synthesized by referring to the literature (Beilstein journal of organic chemistry, 2010, 6, 50); M is carbon disulfide, which can be purchased from the market. In this example, it is purchased from Energy Chemical; M0 is ethyl acetoacetate, which can be purchased from the market. In this example, it is purchased from Energy Chemical.

[0094] The synthesis steps of the poly(thiophene) are as follows: Under air conditions, monomers M and M0 are sequentially added to a polymerization tube at a molar ratio of 3:1. N,N-dimethylformamide is injected until the concentration of monomer M0 is 1 mol / L. Stir at a rate of 450 rpm for 1 hour while keeping the room temperature constant; Subsequently, monomer M3 is added to the polymerization tube at half of the feeding ratio of monomer M0. N,N-dimethylformamide is injected until the concentration of monomer M3 is 0.2 mol / L. Stir at a rate of 450 rpm for 4 hours while keeping the room temperature constant; Subsequently, monomer M3’ is added to the polymerization tube at half of the feeding ratio of monomer M0. Stir at a rate of 450 rpm for 4 hours while keeping the room temperature constant. After the reaction is completed, the reaction mother liquor is dissolved in N,N-dimethylformamide, and then it is dropped into methanol, allowed to stand, filtered, and dried to obtain the poly(thiophene) compound P3.

[0095] After determination and analysis, the yield of the final product poly(thiophene) compound P3 is 71%, the weight-average molecular weight is 14200 g / mol, and the molecular weight distribution is 1.67.

[0096] Example 4

[0097] A poly(thiophene) compound, whose structural formula is shown as P4:

[0098]

[0099] The poly(thiophene) compound is prepared by a two-step method using carbon disulfide, a dicarbonyl compound, a bromide, and a methylene-activated bromide. The reaction formula is as shown in Formula (IV):

[0100]

[0101]

[0102] Among them, monomer M4 is 1,4-bis(bromomethyl)benzene, which can be purchased from the market. In this example, it is purchased from Energy Chemical; M4’ is α,α’-dibromo-1,3-diacetylbenzene, which needs to be synthesized according to the literature (Beilstein journal of organic chemistry, 2010, 6, 50); M is carbon disulfide, which can be purchased from the market. In this example, it is purchased from Energy Chemical; M0 is ethyl acetoacetate, which can be purchased from the market. In this example, it is purchased from Energy Chemical.

[0103] The synthesis steps of the poly(thiophene) are as follows: Under air conditions, monomer M and monomer M0 are successively added to a polymerization tube in a molar ratio of 3:1. N,N-dimethylformamide is injected until the concentration of monomer M0 is 1 mol / L, and the mixture is stirred at a rate of 450 rpm for 1 hour while keeping the room temperature constant; subsequently, monomer M4 is added to the polymerization tube at half of the feeding ratio of monomer M0, and N,N-dimethylformamide is injected until the concentration of monomer M4 is 0.2 mol / L, and the mixture is stirred at a rate of 450 rpm for 4 hours while keeping the room temperature constant; subsequently, monomer M4' is added to the polymerization tube at half of the feeding ratio of monomer M0, and the mixture is stirred at a rate of 450 rpm for 4 hours while keeping the room temperature constant. After the reaction is completed, the reaction mother liquor is dissolved in N,N-dimethylformamide, and then it is dropped into methanol, allowed to stand, filtered, and dried to obtain the poly(thiophene) compound P4.

[0104] Through measurement and analysis, the yield of the final product poly(thiophene) compound P4 is 82%, the weight-average molecular weight is 12300 g / mol, and the molecular weight distribution is 1.58.

[0105] Application Example 1

[0106] The polymer P1 in Example 1 was made into a film and tested. 15 mg of the polymer P1 was weighed and dissolved in 1 mL of N,N-dimethylacetamide, and then 15 μL of dichlorobenzene was added and mixed well. Then it was filtered through a 200-μm nylon filter membrane, and 30 μL of the filtrate was dropped onto a 1.5 cm * 1.5 cm silicon wafer for spin coating. The selected spin coater model was KW-41, and the rotation speed was 2500 rpm. The prepared film was dried in vacuum for 8 h, and then its refractive index was tested by a variable-angle spectroscopic ellipsometer. The selected instrument model was V-VASE. The wavelength range was 400 - 1700 nm, and the relationship spectrum of its refractive index with the wavelength was as Figure 4 shown. The results showed that the refractive index of the polymer P1 film at a wavelength of 590 nm was 1.7324, at 633 nm was 1.7195, at 550 nm was 1.7494, and at a wavelength of 1700 nm, it still maintained a high refractive index of 1.6616, far exceeding most traditional polymers. The above data indicate that poly(thiophene) P1 has excellent optical properties.

[0107] The polymers P2 - P4 synthesized in Examples 2 to 4 were used to prepare polymer thin films according to the film - making method of polymer P1. The refractive index of the P2 polymer thin film at a wavelength of 590 nm is 1.7210, at 633 nm is 1.7111, and at 550 nm is 1.7339; the refractive index of the P3 polymer thin film at a wavelength of 590 nm is 1.6946, at 633 nm is 1.6862, and at 550 nm is 1.7065; the refractive index of the P4 polymer thin film at a wavelength of 590 nm is 1.7645, at 633 nm is 1.7542, and at 550 nm is 1.7783.

[0108] Application Example 2

[0109] A certain amount of polymer P2 was weighed and fully dissolved in an organic solvent to prepare a mixed solution with a concentration of 1.0 mg / mL. The organic solvent is N,N - dimethylformamide, N,N - dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran (in this example, N,N - dimethylacetamide is used). Then, 0.5 mL of the mixed solution was weighed and 1 mg of carbon nanotubes (outer diameter <10 nm, length: 5 - 30 μm) was added. The mixture was ultrasonically treated at room temperature for about 1 h and then continuously stirred for 12 h. Finally, the mixture was centrifuged at a speed of 15000 rpm for 40 min to obtain the encapsulated mixed solution. When a certain amount of the supernatant was dropped into a methanol solution, a large amount of black solid precipitated. The black solid was filtered with a filter paper, washed with methanol, and then placed in an oven at 60 °C for drying for 12 h to obtain the encapsulated composite material CNT@P2. The microscopic morphologies of the polymer before and after encapsulation were characterized by transmission electron microscopy and scanning electron microscopy. As Figure 5 and Figure 6 shown, it can be found that CNTs with tubular structures appear on the surface and inside of the polymer after encapsulation, which proves the successful encapsulation of carbon nanotubes. Then, its photothermal properties were characterized by a solar simulator, and the selected instrument model is CEL - S500. The test condition is one - sun intensity. The relationship spectrum of the temperature and time after illumination is as Figure 7 shown. The results show that the composite material CNT@P2 has more excellent photothermal properties than P2. After 300 s of illumination, the temperature of P2 stabilizes at about 40 °C, and the temperature of CNT@P2 stabilizes at about 48 °C.

[0110] The above embodiments and application examples show that the polythiophene compound film prepared by the present invention has excellent refractive index (reaching 1.7542 at 633 nm), demonstrating outstanding optical properties. At the same time, the polythiophene compound prepared by the present invention can also be used to wrap carbon nanotubes to prepare a composite material, and the photothermal properties of the composite material have been significantly improved. In addition, the preparation method of the present invention has the following advantages: the reaction raw materials are easy to obtain and inexpensive, and can be directly purchased from commercial channels; the polymerization conditions are mild, the process is simple, and the polymerization efficiency is high. These characteristics make this method have broad application potential in the field of optical materials.

[0111] The above content is only the preferred embodiment of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and modifications can be made to the present invention. These improvements and modifications should also be regarded as the protection scope of the present invention.

Claims

1. A method for preparing a polythiophene compound, characterized in that, It includes the following steps: (1) Carbon disulfide and a dicarbonyl compound are added to an organic solvent and stirred for reaction; (2) A polybromide is added to the solution obtained after the reaction in step (1), and stirred for reaction; (3) A polymethylene-activated bromide is added to the solution obtained after the reaction in step (2), stirred for reaction, diluted, precipitated, and dried to obtain a polythiophene compound.

2. The preparation method of the polythiophene compound according to claim 1, characterized in that, The molar ratio of carbon disulfide, the dicarbonyl compound, the bromo-functional group of the polybromide, and the methylene bromo-functional group of the polymethylene-activated bromide is 1-3:1:0.5-1.0:1-2.

3. The preparation method of the polythiophene compound according to claim 1, characterized in that, Steps (1)-(3) are carried out under air conditions; The temperature for the stirring reaction in steps (1)-(3) is room temperature; The stirring reaction time in step (1) is 1-2 hours; The stirring reaction time in step (2) is 4-8 hours; The stirring reaction time in step (3) is 2-4 hours; The precipitation solvent used for precipitation in step (3) is methanol.

4. The preparation method of the polythiophene compound according to claim 1, characterized in that, The concentration of the dicarbonyl compound in the organic solvent in step (1) is 0.25-2 mol / L; An organic solvent is further added in step (2), and the concentration of the polybromide in the organic solvent is 0.125-1 mol / L; The concentration of the polymethylene-activated bromide in the organic solvent in step (3) is 0.125-1 mol / L.

5. The preparation method of the polythiophene compound according to claim 1 or 4, characterized in that, The organic solvent is one or a mixture of more of N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and tetrahydrofuran; the carbon disulfide is a purified sample.

6. The method for preparing a polythiophene compound according to claim 1, wherein The structural formula of the dicarbonyl compound is as follows: The structural formula of the polybromide is as follows: The structural formula of the polymethylene-activated bromide is as follows: Among them, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are each independently an aliphatic group or an aromatic group, x is each independently an integer from 0 to 5, and y is each independently an integer from 0 to 3.

7. The preparation method of the polythiophene compound according to claim 1, characterized in that, The dicarbonyl compound is selected from any one of the following structural formulas: The polybromide is selected from any one of the following structural formulas: The polymethylene-activated bromide is selected from any one of the following structural formulas:

8. A polythiophene compound prepared by the preparation method according to any one of claims 1-7.

9. The polythiophene compound according to claim 8, wherein The structural formula is as follows: Wherein, n is an integer from 2 to 800, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are each independently a fatty group or an aromatic group, x are each independently an integer from 0 to 5, and y are each independently an integer from 0 to 3.

10. The application of the polythiophene compound according to claim 8 or 9 in preparing a high refractive index film, preparing an optical device, or wrapping carbon nanotubes to prepare a composite material.

Images