Diketopyrrolopyrrole and thiophene-based conductive polymer with siloxane and methoxy side chains and manufacturing method thereof

Abstract

The present invention relates to a conductive polymer and a method for manufacturing it, and more specifically, to a conductive polymer having siloxane and methoxy side chains, using diketopyrrolopyrrole (DPP) and thiophene as the main structure of the conductive polymer.

Description

Technology Field

[0001] The present invention relates to a conductive polymer and a method for manufacturing the same. Background Technology

[0003] In general, solution-processable conjugated polymers are widely used in organic semiconductors due to their advantages, such as flexibility, optoelectronic properties, and very low cost.

[0004] Organic semiconductors can be utilized in flexible displays, RFID (radio frequency identification), and sensors in the ubiquitous era. Conductive polymers can be broadly divided into side chains and the polymer main backbone. To date, most research on conductive polymers has focused on polymer structure rather than side chains. This is because it was believed that molecular structure determines energy levels, crystal structure, and molecular orientation. Consequently, while research on side chains has not been extensive, the side chains of conductive polymers significantly influence intermolecular interactions and molecular packing.

[0005] Conventional technologies have had disadvantages such as poor flexibility, poor optoelectronic properties, and high manufacturing costs. To address this, there is a need to develop conductive polymers with good flexibility and excellent optoelectronic properties. Prior art literature

[0007] Republic of Korea Registered Patent No. 10-2461135 The problem to be solved

[0008] The present invention has been devised to solve the above-mentioned problems, and the objective of the present invention is to provide a conductive polymer with good flexibility and excellent photoelectric properties.

[0009] The technical problems that the present invention aims to solve are not limited to those mentioned above, and other unmentioned technical problems will be clearly understood by those skilled in the art from the description below. means of solving the problem

[0011] To achieve the above objective, the present invention provides a conductive polymer comprising a repeating unit represented by the following chemical formula 1.

[0012] [Chemical Formula 1]

[0013]

[0014] In the above chemical formula 1,

[0015] n is an integer from 1 to 30, and

[0016] X is H or OCH3, and

[0017] R is one selected from R1 or R2 of the following structure.

[0018]

[0019] In addition, the present invention provides a method for manufacturing a conductive polymer by polymerizing a compound (A) represented by the following chemical formula 2 and a compound (B) represented by the following chemical formula 3 to produce a polymer compound represented by the following chemical formula 1.

[0020] [Chemical Formula 1]

[0021]

[0022] In the above chemical formula 1, n is an integer from 1 to 30, X is H or OCH3, and R may be one selected from R1 or R2 of the following structure.

[0023]

[0024] [Chemical Formula 2]

[0025]

[0026] In the above chemical formula 2, X can be H or OCH3.

[0028] [Chemical Formula 3]

[0029]

[0030] In the above chemical formula 3, R may be one selected from R1 or R2 of the following structure.

[0031]

[0033] The above compound (A) and the above compound (B) can be polymerized in a molar ratio of 1:0.5 to 1.5.

[0034] The polymerization reaction of the above compound (A) and the above compound (B) can be carried out at 100 to 200 ℃ for 1 to 5 hours.

[0035] In addition, the present invention provides an organic semiconductor device comprising the conductive polymer described above. Effects of the invention

[0037] By means of solving the above problem, the present invention can provide a conductive polymer having DPP, a thiophene-based siloxane, and a methoxy side chain.

[0038] In addition, the present invention can provide a conductive polymer with excellent flexibility and photoelectric properties.

[0039] The effects of the present invention are not limited to those mentioned above, and other unmentioned effects will be clearly understood by those skilled in the art from the description in the claims. Brief explanation of the drawing

[0041] Figure 1 shows a design and synthesis mechanism for a conductive polymer having a diketopyrrolopyrrole (DPP), a thiophene-based siloxane, and a methoxy side chain according to the present invention. Figure 2 is the result of Fourier-transform infrared spectroscopy (FT-IR) measurements of conductive polymers (PTDPPod-Th, PTDPPod-Meth, PTDPPsi-Th and PTDPPsi-Meth) according to an embodiment of the present invention. FIG. 3 is an absorption spectrum in (a) a solution state and (b) a film state analyzed by UV-Visible molecular absorption spectroscopy of a conductive polymer according to an embodiment of the present invention, and a Tauc plot of (c) PTDPPod-Th, (d) PTDPPod-Meth, (e) PTDPPsi-Th, and (f) PTDPPsi-Meth. Figure 4 is the result of measuring the potential difference analyzed by cyclic voltammetry (electrochemical workstation) of a conductive polymer according to one embodiment of the present invention. Figure 5 is the result of thermogravimetric analysis (TGA) of a conductive polymer according to one embodiment of the present invention. Figure 6 is the result of measuring the gel permeability of a conductive polymer according to one embodiment of the present invention. Specific details for implementing the invention

[0042] The terms used in this invention have been selected based on currently widely used general terms, taking into account their functions within the invention; however, these terms may vary depending on the intent of those skilled in the art, case law, the emergence of new technologies, etc. Additionally, in specific cases, terms have been arbitrarily selected by the applicant, and in such cases, their meanings will be described in detail in the relevant description of the invention. Therefore, the terms used in this invention should be defined not merely by their names, but based on their meanings and the overall content of the invention.

[0043] Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as generally understood by those skilled in the art to which the present invention pertains. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with their meaning in the context of the relevant technology, and should not be interpreted in an ideal or overly formal sense unless explicitly defined in this application.

[0044] When a part of a specification is described as “comprising” a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but may include additional components.

[0045] Embodiments of the present invention are described below with reference to the attached drawings so that those skilled in the art can easily implement them. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.

[0047] The present invention will be described in detail below.

[0049] The present invention provides a conductive polymer comprising a repeating unit represented by the following chemical formula 1.

[0050] [Chemical Formula 1]

[0051]

[0052] In the above chemical formula 1,

[0053] n is an integer from 1 to 30, and

[0054] X is H or OCH3, and

[0055] R is one selected from R1 or R2 of the following structure.

[0056]

[0057] In addition, the present invention provides a method for manufacturing a conductive polymer by polymerizing a compound (A) represented by the following chemical formula 2 and a compound (B) represented by the following chemical formula 3 to produce a polymer compound represented by the following chemical formula 1.

[0058] [Chemical Formula 1]

[0059]

[0060] In the above chemical formula 1, n is an integer from 1 to 30, X is H or OCH3, and R may be one selected from R1 or R2 of the following structure.

[0061]

[0063] [Chemical Formula 2]

[0064]

[0065] In the above chemical formula 2, X can be H or OCH3.

[0067] [Chemical Formula 3]

[0068]

[0069] In the above chemical formula 1, R may be one selected from R1 or R2 of the following structure.

[0070]

[0071] The above compound (A) and the above compound (B) can be polymerized in a molar ratio of 1:0.5 to 1.5. Preferably, they can be polymerized in a molar ratio of 1:1, but are not limited thereto.

[0072] In the step of polymerizing the above compound (A) and the above compound (B), the catalyst may be a complex catalyst or a co-catalyst. The complex catalyst may be one or more selected from the group consisting of Pd2(dba)3, Pd2(dba)3CHCl3, PdCl2, Pd(OAc)2, Pd(CH3CN)2Cl2, Pd(PhCN)2Cl2, and Pd(PPh3)4. More preferably, it may be Pd2(dba)3, and when Pd2(dba)3 is used, the high reactivity may lead to a higher yield of high molecular weight polymers. The co-catalyst may be one selected from the group consisting of tris(o-tolyl)phosphine, triphenylphosphine, and tricyclohexylphosphine tetrafluoroborate, and more preferably, it may be tris(o-tolyl)phosphine, but is not limited thereto.

[0073] The above compound (A) and the above compound (B) may be mixed with a solvent, and the solvent may be one or more selected from the group consisting of toluene, water, xylene, ethanol, methanol, chlorobenzene, dichlorobenzene, dimethylformamide, N-methylpyrrolidone, and dimethyl sulfoxide. More preferably, it may be toluene, but is not limited thereto.

[0074] The polymerization reaction of the above compound (A) and the above compound (B) can be carried out at 100 to 200 ℃ for 1 to 5 hours. Preferably, it can be carried out at 110 to 150 ℃ for 2 to 4 hours, and more preferably at 130 ℃ for 3 hours, but is not limited thereto.

[0075] The polymerization reaction of the above compound (A) and the above compound (B) can be carried out under an inert gas atmosphere, and more preferably, nitrogen gas may be used, but is not limited thereto.

[0076] The above manufacturing method may additionally perform the step of precipitating and filtering the polymerized conductive polymer. The precipitation solution may be one or more selected from the group consisting of methanol, acetone, hexane, dichloromethane, chloroform, and chlorobenzene, and more preferably may be methanol, but is not limited thereto.

[0077] The step of removing impurities and unreacted materials from the precipitated conductive polymer and purifying it can be performed using a Soxhlet extractor. More specifically, Soxhlet extraction can be performed by removing impurities in the order of methanol, acetone, and hexane, followed by extraction with chloroform.

[0078] The extracted conductive polymer may additionally undergo the steps of precipitation and vacuum drying using a precipitation solvent. The precipitation solution may be one or more selected from the group consisting of methanol, acetone, hexane, dichloromethane, chloroform, and chlorobenzene, and more preferably may be methanol, but is not limited thereto.

[0079] In addition, the present invention provides an organic semiconductor device comprising the conductive polymer described above.

[0080] The above organic semiconductor device may include an organic solar cell, a dye-sensitized solar cell, a perovskite solar cell, an organic field-effect transistor, or an organic light-emitting diode.

[0082] Hereinafter, the present invention will be described in detail with reference to examples to specifically explain the invention. However, the embodiments according to the present invention may be modified in various different forms, and the scope of the present invention is not to be interpreted as being limited to the embodiments described below. The embodiments of this specification are provided to more completely explain the present invention to those with average knowledge in the art.

[0084] <Example 1> Synthesis of PTDPPod-Th

[0085] 3,6-bis(5-bromothiophen-2-yl)-2,5-bis(2-octyldodecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (M3) (300 mg, 0.294 mmol), 2,5-bis(trimethylstannyl)thiophene (M1) (120 mg, 0.294 mmol), tetrakis(triphenylphosphine)palladium (10 mg, 8.82 μmol), and anhydrous toluene (10 mL) were added to a 30 mL microwave reaction vessel under nitrogen gas conditions. The reaction mixture was reacted using an Anton-Paar microwave at 130 °C for 3 hours, cooled to room temperature, precipitated in methanol, and filtered. The precipitate was sequentially purified of impurities in methanol, acetone, and hexane for 24 hours each using a Soxhlet extractor, and then extracted with chloroform. The product was obtained by precipitation in methanol and vacuum drying.

[0087] <Example 2> PTDPPod-Meth Synthesis

[0088] 3,6-bis(5-bromothiophen-2-yl)-2,5-bis(2-octyldodecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (M3) (300 mg, 0.294 mmol), (3-methoxythiophene-2,5-diyl)bis(trimethylstannane) (M2) (130 mg, 0.294 mmol), tetrakis(triphenylphosphine)palladium (10 mg, 8.82 μmol), and anhydrous toluene (10 mL) were added to a 30 mL microwave reaction vessel under nitrogen gas conditions. The reaction mixture was reacted using an Anton-Paar microwave at 130 °C for 3 hours, cooled to room temperature, precipitated in methanol, and filtered. The precipitate was sequentially purified of impurities in methanol, acetone, and hexane for 24 hours each using a Soxhlet extractor, and then extracted with chloroform. The product was obtained by precipitation in methanol and vacuum drying.

[0090] <Example 3> Synthesis of PTDPPsi-Th

[0091] 3,6-bis(5-bromothiophen-2-yl)-2,5-bis(5-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)pentyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (M4) (300 mg, 0.289 mmol), 2,5-bis(trimethylstannyl)thiophene (M1) (118 mg, 0.289 mmol), tetrakis(triphenylphosphine)palladium (10 mg, 8.67 μmol), and anhydrous toluene (10 mL) were added to a 30 mL microwave reaction vessel under nitrogen gas conditions. The reaction mixture was reacted using an Anton-Paar microwave at 130 °C for 3 hours, cooled to room temperature, precipitated in methanol, and filtered. The precipitate was sequentially purified of impurities in methanol, acetone, and hexane for 24 hours each using a Soxhlet extractor, and then extracted with chloroform. The product was obtained by precipitation in methanol and vacuum drying.

[0093] <Example 4> PTDPPod-Meth Synthesis

[0094] 3,6-bis(5-bromothiophen-2-yl)-2,5-bis(2-octyldodecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (M4) (300 mg, 0.289 mmol), (3-methoxythiophene-2,5-diyl)bis(trimethylstannane) (M2) (130 mg, 0.289 mmol), tetrakis(triphenylphosphine)palladium (10 mg, 8.67 μmol), and anhydrous toluene (10 mL) were added to a 30 mL microwave reaction vessel under nitrogen gas conditions. The reaction mixture was reacted using an Anton-Paar microwave at 130 °C for 3 hours, cooled to room temperature, precipitated in methanol, and filtered. The precipitate was sequentially purified of impurities in methanol, acetone, and hexane for 24 hours each using a Soxhlet extractor, and then extracted with chloroform. The product was obtained by precipitation in methanol and vacuum drying.

[0096] <Experimental Example 1> Fourier-transform infrared spectroscopy (FT-IR) measurement

[0097] As shown in Fig. 2, measurements were performed in the solid state in reflection mode (ATR mode) using a Fourier transform infrared spectroscopic analyzer (IRAffinity-1, SHIADZU), and the results are shown in Fig. 2. PTDPPod-Th, PTDPPod-Meth, PTDPPsi-Th, and PTDPPsi-Meth are sp 2 / sp 3 CH stretching vibration peaks of hybrid hydrocarbons at 3074 / 2920, 3065 / 2920, 3066 / 2955, and 3074 / 2955 cm⁻¹ -1 They were observed in each region, and the C=O stretching vibration peak corresponding to the imide of DPP was found at 1663, 1660, 1663, and 1660 cm⁻¹.-1 They were confirmed in each region. In addition, the CN stretching vibration peaks corresponding to the aromatic amine of DPP were found at 1227, 1227, 1249, and 1249 cm⁻¹. -1 The structural characteristics of the polymers could be confirmed as they were observed in the region. PTDPPsi-Th and PTDPPsi-Meth, being siloxane side chains, exhibited identical Si-O-Si and Si-C stretching vibration peaks at 1034 cm⁻¹. -1 and 834 cm -1 This was confirmed in the region, and for PTDPPod-Meth and PTDPPsi-Meth, CO stretching vibration peaks corresponding to alkyl aryl ethers due to methoxy were observed at 1320 and 1330 cm⁻¹. -1 Successful substitution of the side chain was observed in each region.

[0099] <Experimental Example 2> Ultraviolet / Visible Molecular Absorption Spectroscopy (UV-Visible Spectrophotometer) Measurement

[0100] The solution state was measured by diluting the polymer in chloroform to 25 μg / mL and using a UV-Vis spectrophotometer (OPTIZEN POP, Mecasys) at a wavelength of 300-1100 nm with a scan interval of 1 nm / s, and the thin film state was measured by dissolving the polymer in chloroform to 8 mg / mL, dropping it onto a quartz plate, coating it with a spin coater at 700 rpm for 30 seconds, and using a UV-Vis spectrophotometer (OPTIZEN POP, Mecasys) at a wavelength of 300-1100 nm with a scan interval of 1 nm / s, and the results are shown in Figure 3.

[0101] As shown in Figure 3, it was observed that the absorbance of all four polymers broadened in the intramolecular charge transfer (ICT) peak (500-1100 nm) in the thin film state compared to the solution state. In particular, it was confirmed that the methoxy-substituted polymers (PTDPPod-Meth and PTDPPsi-Meth) showed a significantly wider absorption range than the non-methoxy polymers (PTDPPod-Th and PTDPPsi-Th). The optical band gaps of PTDPPod-Th, PTDPPod-Meth, PTDPPsi-Th, and PTDPPsi-Meth were calculated using a Tauc plot in the thin film state and were found to be 1.36, 1.22, 1.30, and 1.20 eV, respectively.

[0103] <Experimental Example 3> Cyclic Volammetry (Electrochemical Workstation) Measurement

[0104] The reference electrode, working electrode, and counter electrode were Ag / Ag+, carbon disk (GC), and platinum (Pt) wire, respectively, and measurements were taken at a rate of 200 mV / s. The electrolyte was prepared by dissolving tetra-n-butylammonium hexafluorophosphate (n-Bu4NPF6) in acetonitrile (ACN) to a concentration of 0.1 M, and the reference electrode (Ag / Ag+) was calibrated using a ferrocene / ferrocenium oxidation / reduction reaction, with the oxidation potential set to -4.8 eV at vacuum level.

[0105] As shown in Figure 4, the HOMO / LUMO energy level values ​​of PTDPPod-Th, PTDPPod-Meth, PTDPPsi-Th, and PTDPPsi-Meth were confirmed to be -5.21 / -3.48, -4.79 / -3.64, -4.79 / -3.55, and -4.94 / -3.67 eV, respectively, and the energy band gaps were found to be 1.73, 1.15, 1.53, and 1.27 eV, respectively.

[0107] <Experimental Example 4> Thermogravimetric Analysis (TGA) Measurement

[0108] Using a thermal analyzer (TGA N-1000, Shinko), the mass loss rate according to temperature was measured when the temperature was increased at a rate of 10 °C / min from room temperature (about 16 °C) to 900 °C in a nitrogen atmosphere, and the results are shown in Figure 5.

[0109] As shown in Fig. 5, to verify the thermal stability of PTDPPod-Th, PTDPPod-Meth, PTDPPsi-Th, and PTDPPsi-Meth, the decomposition temperature (T d ) was measured. T d The value was measured at the point showing a 5% weight reduction rate, and the T of PTDPPod-Th, PTDPPod-Meth, PTDPPsi-Th, and PTDPPsi-Meth d With values ​​of 410 ℃, 383 ℃, 441 ℃, and 383 ℃, it was confirmed that the methoxy-substituted polymers (PTDPPod-Meth and PTDPPsi-Meth) had lower thermal stability than the non-methoxy polymers (PTDPPod-Th and PTDPPsi-Th).

[0111] <Experimental Example 5> Gel Permeation Chromatography (GPC) Measurement

[0112] The results were measured using gel permeation chromatography (Agilent 1200S / miniDAWN TREOS, Agilent / Wyatt) with polystyrene as the base and tetrahydrofuran (THF) as the mobile phase, and the results are shown in Figure 6.

[0113] As shown in Fig. 6, the number average molecular weights of TDPPod-Th, PTDPPod-Meth, PTDPPsi-Th, and PTDPPsi-Meth ( M n The values ​​were 66.3 kg / mol, 14.2 kg / mol, 173.6 kg / mol, and 16.7 kg / mol, respectively, and the PDI values ​​were confirmed to be 1.85, 1.44, 6.22, and 1.37, respectively.

[0115] Specific embodiments of the present invention have been examined so far. Those skilled in the art will understand that the present invention may be embodied in modified forms without departing from the essential characteristics of the invention. Therefore, the disclosed embodiments should be considered in an illustrative rather than a restrictive sense. The scope of the present invention is defined by the claims, not by the foregoing description, and all variations within the scope of equivalents should be interpreted as being included in the present invention.

Claims

Claim 1 Conductive polymer comprising repeating units represented by the following chemical formula 1; [Chemical Formula 1] In the above chemical formula 1, n is an integer from 1 to 30, X is OCH3, and R is am. Claim 2 A method for preparing a conductive polymer by adding a compound (A) represented by the following chemical formula 2 and a compound (B) represented by the following chemical formula 3 to a microwave reaction vessel and polymerizing them at 130°C for 3 hours to prepare a polymer compound represented by the following chemical formula 1. [Chemical Formula 1] In the above chemical formula 1, n is an integer from 1 to 30, X is OCH3, and R is It is.[Chemical Formula 2] In the above Chemical Formula 2, X is OCH3.[Chemical Formula 3] In the above chemical formula 3, R is am Claim 3 A method for manufacturing a conductive polymer according to claim 2, characterized in that the compound (A) and the compound (B) are polymerized in a molar ratio of 1:0.5 to 1.

5. Claim 4 delete Claim 5 An organic semiconductor device comprising a conductive polymer according to claim 1.

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