Conductive two-dimensional polymer and method for preparing same

Abstract

The present invention relates to a conductive two-dimensional polymer and a method for preparing same. Specifically, a conductive two-dimensional polymer, according to one aspect, has a structure comprising a fused aromatic framework and bulky pendant groups, and can thus achieve excellent electrical conductivity and electron mobility. At the same time, the polymer exhibits improved solubility in organic solvents and can attain a high degree of polymerization, and is thus expected to be applicable to various industrial fields as a next-generation material capable of replacing inorganic semiconductors such as silicon.

Description

Conductive two-dimensional polymer and method for producing the same

[0001] The present invention relates to a conductive two-dimensional polymer, a method for producing the same, and an organic electronic device including the same.

[0002] Organic semiconductors offer a range of advantages, including flexibility, lightness, and ease of molecular structure control, making them a potential replacement for inorganic semiconductors like silicon. In particular, conducting two-dimensional polymers (C2Ps), with their two-dimensionally extended p-conjugation, are attracting attention as next-generation materials that can address the low electrical conductivity of existing organic semiconductors.

[0003] With recent technological advancements and the increasingly sophisticated properties required for organic semiconductors, research is continuing to optimize the electron transport pathways of conductive two-dimensional polymers. Most existing two-dimensional polymers contain rotatable single bonds within their backbones, which tends to reduce electrical conductivity. Therefore, two-dimensional polymers with fused aromatic backbones have been proposed as ideal structures. However, these polymers exhibit significantly reduced solubility due to their strong stacking behavior, making them difficult to manufacture and limiting their practical commercialization.

[0004] One aspect of the present invention provides a conductive two-dimensional polymer having excellent conductivity and improved solubility in an organic solvent, and a method for producing the same.

[0005] One aspect of the present invention provides a conductive two-dimensional polymer comprising a structural unit derived from a compound of the following chemical formula 1 and a structural unit derived from a compound of the following chemical formula 2.

[0006] [Chemical Formula 1]

[0007]

[0008] [Chemical Formula 2]

[0009]

[0010] (In the above chemical formula 1,

[0011] A 1 Inland A 3 Each ring is independently a C6-C20 aromatic ring;

[0012] R 1 Inland R 3 are each independently C1-C20 alkyl, halo(C1-C20)alkyl, halogen or nitrile;

[0013] a to c are each independently integers from 1 to 5.)

[0014] A above 1 Inland A 3 Each ring is independently a C6-C12 aromatic ring; R 1 Inland R 3 are each independently C1-C10 alkyl; a to c can each independently be an integer from 3 to 5.

[0015] The compound of the above chemical formula 1 may be represented by the following chemical formula 3.

[0016] [Chemical Formula 3]

[0017]

[0018] According to one aspect, the conductive two-dimensional polymer may include a diimine group formed by a reaction between a diketone group of a compound represented by the chemical formula 1 and a diamine group of a compound represented by the chemical formula 2.

[0019] According to one aspect, the conductive two-dimensional polymer may include a structural unit represented by the following chemical formula 4.

[0020] [Chemical Formula 4]

[0021]

[0022] (In the above chemical formula 4,

[0023] A 1 Inland A 3 , R 1Inland R 3 and a to c are the same as defined in the above chemical formula 1.)

[0024] According to one aspect, the conductive two-dimensional polymer may include a structural unit represented by the following chemical formula 5.

[0025] [Chemical Formula 5]

[0026]

[0027] The aspect ratio of the conductive two-dimensional polymer according to one aspect may be 20 to 1,000.

[0028] Another aspect of the present invention provides a p-type doped conductive two-dimensional polymer comprising the conductive two-dimensional polymer and a p-type dopant.

[0029] The above p-type dopant may be iodine (I2).

[0030] The dopant content of the p-type doped conductive two-dimensional polymer according to one aspect may be 10 to 30 wt%.

[0031] The above p-type doped conductive two-dimensional polymer according to one embodiment has an electrical conductivity of 1.0 x 10 as measured based on the van der Pauw method. -2 Scm -1 It could be strange.

[0032] Another aspect of the present invention provides a method for producing a conductive two-dimensional polymer, comprising the step of reacting compounds of chemical formula 1 and chemical formula 2 in the presence of an aldehyde compound, an acid catalyst, and an organic solvent.

[0033] [Chemical Formula 1]

[0034]

[0035] [Chemical Formula 2]

[0036]

[0037] (In the above chemical formula 1,

[0038] A 1Inland A 3 Each ring is independently a C6-C20 aromatic ring;

[0039] R 1 Inland R 3 are each independently C1-C20 alkyl;

[0040] a to c are each independently integers from 1 to 5.)

[0041] The above aldehyde compound may be represented by the following chemical formula 6.

[0042] [Chemical Formula 6]

[0043]

[0044] (In the above chemical formula 6,

[0045] R 4 are each independently C1-C20 alkyl;

[0046] d is an integer from 1 to 5.)

[0047] It may be possible to react 1 to 3 moles of the compound of chemical formula 2 with 1 mole of the compound of chemical formula 1.

[0048] For 1 mole of the compound of the above chemical formula 1, the aldehyde compound may be used in an amount of 10 to 30 moles.

[0049] The method for manufacturing the conductive two-dimensional polymer according to one aspect may include a step of exposing the polymer to supercritical CO2 after dialysis in distilled water after completion of the reaction and drying under reduced pressure.

[0050] Another aspect of the present invention provides an organic electronic device comprising the p-type doped conductive two-dimensional polymer.

[0051] The above organic electronic device may be an organic solar cell, an organic transistor, an organic memory, an organic photoreceptor, or an organic photosensor.

[0052] Another aspect of the present invention provides a compound represented by the following chemical formula 1.

[0053] [Chemical Formula 1]

[0054]

[0055] (In the above chemical formula 1,

[0056] A 1 Inland A 3 Each ring is independently a C6-C20 aromatic ring;

[0057] R 1 Inland R 3 are each independently C1-C20 alkyl, halo(C1-C20)alkyl, halogen or nitrile;

[0058] a to c are each independently integers from 1 to 5.)

[0059] A above 1 Inland A 3 Each ring is independently a C6-C12 aromatic ring; R 1 Inland R 3 are each independently C1-C10 alkyl; a to c can each independently be an integer from 3 to 5.

[0060] The compound of the above chemical formula 1 may be represented by the following chemical formula 3.

[0061] [Chemical Formula 3]

[0062]

[0063] A conductive two-dimensional polymer according to one embodiment has a structure comprising a fused aromatic backbone and bulky pendants, and can simultaneously satisfy excellent electrical conductivity and solubility properties. Specifically, the conductive two-dimensional polymer according to one embodiment has an in-plane crystal with a high aspect ratio, and can realize excellent electrical conductivity and electron transport properties. At the same time, the conductive two-dimensional polymer according to one embodiment effectively solves the problem of strong stacking behavior of conventional two-dimensional polymers, and can have improved solubility in organic solvents, thereby achieving a high degree of polymerization. Furthermore, the conductive two-dimensional polymer according to one embodiment can have a low intramolecular misbonding rate and higher stability.

[0064] In other words, it is expected that conductive two-dimensional polymers according to one aspect can be applied in various industrial fields as next-generation materials that can replace inorganic semiconductors such as silicon.

[0065] Figure 1 is an FT-IR spectrum of compound (1), TAP, and C2P-9.

[0066] Figure 2 is CP-MAS of C2P-9 13 This is a C-NMR spectrum.

[0067] Figure 3 is a TEM image of C2P-9.

[0068] Figure 4 is the UV-NIR spectrum of C2P-9.

[0069] Figure 5 is a graph of electron and electron mobility as a function of temperature for I2@C2P-9.

[0070] Unless otherwise defined herein, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0071] As used herein, the singular forms may be intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0072] Throughout this specification, the terms "comprises," "includes," "contains," or "has" a component, unless specifically stated to the contrary, do not exclude other components, but rather may include other components, and do not exclude additional unrecited elements, materials, or processes.

[0073] The numerical ranges used herein include the lower and upper limits and all values ​​within that range, increments logically derived from the shape and width of the defined range, all doubly defined values, and all possible combinations of the upper and lower limits of numerical ranges defined in different shapes. Unless otherwise specified herein, values ​​outside the defined range that may arise due to experimental error or rounding of values ​​are also included in the defined numerical range.

[0074] Unless otherwise specified herein, “about” may be considered a value within 30%, 25%, 20%, 15%, 10% or 5% of the stated value.

[0075] As used herein, “alkyl” means a monovalent straight-chain or branched saturated hydrocarbon radical composed solely of carbon and hydrogen atoms, including, but not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, and ethylhexyl.

[0076] As used herein, "aromatic ring" refers to an aromatic hydrocarbon compound, including a single or fused ring system, each ring suitably containing 4 to 7, preferably 5 or 6, ring atoms, and even including a form in which multiple aromatic rings are connected by single bonds. In addition, the aromatic ring may have a desired number of bonding sites by at least one hydrogen removal.

[0077] As used herein, “haloalkyl” means alkyl in which one or more hydrogen atoms are replaced with halogen atoms.

[0078] In this specification, “halogen” means fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).

[0079] As used herein, “nitrile” means -CN.

[0080] Below, the present disclosure will be described in detail. However, this is merely exemplary and the present disclosure is not limited to the specific embodiments described as examples.

[0081] Conducting two-dimensional polymers (C2Ps) possess two-dimensionally extended p-conjugation and are attracting attention as next-generation materials that can solve the low electrical conductivity problem of existing organic semiconductor materials. Recently, with technological advancements and the increasingly sophisticated physical properties required for organic semiconductors, efforts to further improve the electrical conductivity of conducting two-dimensional polymers are ongoing. However, attempts to improve the electrical conductivity of conducting two-dimensional polymers face challenges: their strong stacking behavior significantly reduces their solubility, leading to precipitation during the synthesis process, making their manufacturing difficult and limiting their commercialization.

[0082] One aspect of the present invention provides a conductive two-dimensional polymer having excellent conductivity and improved solubility in an organic solvent.

[0083] A conductive two-dimensional polymer according to one aspect may include a structural unit derived from a compound of the following chemical formula 1 and a structural unit derived from a compound of the following chemical formula 2.

[0084] [Chemical Formula 1]

[0085]

[0086] [Chemical Formula 2]

[0087]

[0088] (In the above chemical formula 1,

[0089] A 1 Inland A 3 Each ring is independently a C6-C20 aromatic ring;

[0090] R 1 Inland R 3 are each independently C1-C20 alkyl, halo(C1-C20)alkyl, halogen or nitrile;

[0091] a to c are each independently integers from 1 to 5.)

[0092] Specifically, the conductive two-dimensional polymer according to one embodiment can form a diimine group by a condensation reaction of a diketone group of a compound represented by Chemical Formula 1 and a diamine group of a compound represented by Chemical Formula 2 (see Chemical Formula 1 below), and thus can have a central skeleton of a structure in which aromatic rings are fused. At the same time, the conductive two-dimensional polymer according to one embodiment can have an alkyl substituent (R 1 Inland R 3 ) with A 1 Inland A 3 By including bulk pendants of the ring, the problem of reduced melting due to strong layering behavior can be effectively improved and a high degree of polymerization can be achieved.

[0093] [Formula 1]

[0094]

[0095] For example, the above A 1 Inland A 3 Each ring is independently a C6-C12 aromatic ring; R 1 Inland R 3 are each independently C1-C10 alkyl; a to c can each independently be an integer from 3 to 5.

[0096] For example, the above R 1 Inland R 3 may each independently be C1-C10 alkyl, C1-C7 alkyl, or C1-C4 alkyl, or C1-C3 alkyl, or methyl or ethyl.

[0097] For example, the above R 1 Inland R 3 may each independently be halo(C1-C10)alkyl, halo(C1-C7)alkyl, or fluoro(C1-C7)alkyl or perfluoro(C1-C7)alkyl, or -CF3 or -CF2CF3.

[0098] For example, the above A 1 Inland A 3 The rings can be identical to each other, R 1 Inland R 3 can be identical to each other, and a to c can be identical to each other.

[0099] For example, the compound of the above chemical formula 1 may be represented by the following chemical formula 1-1, and the pendant of the same structure ( ) are included in symmetrical positions, the lattice deformation of the conductive two-dimensional polymer can be more effectively suppressed and more precise lamination can be induced.

[0100] [Chemical Formula 1-1]

[0101]

[0102] (In the above chemical formula 11, R 11 is C1-C20 alkyl, halo(C1-C20)alkyl, halogen or nitrile.)

[0103] For example, the above R 11 may be C1-C10 alkyl, or C1-C7 alkyl, or C1-C4 alkyl, or C1-C3 alkyl, or methyl or ethyl.

[0104] For example, the above R 11may be halo(C1-C0)alkyl, halo(C1-C7)alkyl, or fluoro(C1-C7)alkyl or perfluoro(C1-C7)alkyl, or -CF3 or -CF2CF3.

[0105] For example, the compound of the above chemical formula 1 may be represented by the following chemical formula 3.

[0106] [Chemical Formula 3]

[0107]

[0108] The conductive two-dimensional polymer according to one aspect may be connected to each other by a diimine group formed by a condensation reaction of a diketone group of a compound represented by chemical formula 1 and a diamine group of a compound represented by chemical formula 2 to form a regular hexagonal repeating unit including a void on the inside, and may include a sheet in which the repeating unit is horizontally arranged in two dimensions.

[0109] Specifically, the conductive two-dimensional polymer according to one aspect may include a structural unit represented by the following chemical formula 4, and more specifically, by the following chemical formula 5, and may include a sheet in which the structural unit is horizontally arranged in two dimensions.

[0110] [Chemical Formula 4]

[0111]

[0112] (In the above chemical formula 4,

[0113] A 1 Inland A 3 , R 1 Inland R 3 and a to c are the same as defined in the above chemical formula 1.)

[0114] [Chemical Formula 5]

[0115]

[0116] The conductive two-dimensional polymer according to one embodiment may have a high aspect ratio, for example, the aspect ratio of the conductive two-dimensional polymer according to one embodiment may be from 20 to 1,000, or from 20 to 500, or from 20 to 100.

[0117] Another aspect of the present invention provides a method for producing the conductive two-dimensional polymer.

[0118] A method for producing a conductive two-dimensional polymer according to one aspect may include a step of reacting compounds of chemical formula 1 and chemical formula 2 in the presence of an aldehyde compound, an acid catalyst, and an organic solvent.

[0119] [Chemical Formula 1]

[0120]

[0121] [Chemical Formula 2]

[0122]

[0123] (In the above chemical formula 1,

[0124] A 1 Inland A 3 Each ring is independently a C6-C20 aromatic ring;

[0125] R 1 Inland R 3 are each independently C1-C20 alkyl, halo(C1-C20)alkyl, halogen or nitrile;

[0126] a to c are each independently integers from 1 to 5.)

[0127] Here, the aldehyde compound can act as a competitor, increasing the degree of polymerization, promoting in-plane growth, and suppressing defect formation. For example, if the reaction is performed without the aldehyde compound, the result may be amorphous or have poor crystallinity, making it difficult to obtain the conductive two-dimensional polymer desired in the present invention.

[0128] The above aldehyde compound may be represented by the following chemical formula 6.

[0129] [Chemical Formula 6]

[0130]

[0131] (In the above chemical formula 6,

[0132] R 4 are each independently C1-C20 alkyl;

[0133] d is an integer from 1 to 5.)

[0134] For example, the above R 4 may be C1-C10 alkyl, or C1-C7 alkyl, or C1-C3 alkyl, or ethyl or methyl.

[0135] For example, the above d may be an integer from 2 to 5, or an integer from 3 to 5.

[0136] For example, the above R 4 is R of the chemical formula 1 described above 1 Inland R 3 , and d may be the same as a to c of the chemical formula 1 described above.

[0137] For example, 10 to 30 moles, or 10 to 25 moles, or 15 to 25 moles of the compound of the chemical formula 2 may be reacted with 1 mole of the compound of the chemical formula 1.

[0138] For example, the aldehyde compound may be used in an amount of 1 to 5 moles, or 1 to 3 moles, or 1 to 2 moles per mole of the compound of the chemical formula 1.

[0139] For example, the acid catalyst may be an organic acid, and may be selected from lactic acid, acetic acid, formic acid, and citric acid.

[0140] For example, the reaction may be carried out under temperature conditions of 100 to 200°C, or 100 to 150°C, or 100 to 130°C for 10 to 30 hours, or 20 to 30 hours, or 20 to 25 hours.

[0141] The organic solvent is not particularly limited as long as it can dissolve the chemical formula 1, chemical formula 2 and the aldehyde compound, but non-limiting examples thereof include hydrocarbon solvents such as butane, isobutane, pentane, hexane, heptane, octane, isooctane, nonane, decane, dodecane, cyclohexane, methylcyclohexane, benzene, toluene and xylene; halogenated hydrocarbon solvents such as dichloromethane, trichloromethane, chloroethane, dichloroethane and trichloroethane; ether solvents such as tetrahydrofuran, 2-methyl tetrahydrofuran, dimethyl ether, diethyl ether, dipropyl ether, methyl ethyl ether, methyl propyl ether and ethyl propyl ether; Alcohol solvents such as methanol, ethanol, isopropanol, 1-butanol, isobutanol, 2-butanol, propylene glycol, ethylene glycol, etc.; but are not limited thereto.

[0142] In addition, the method for manufacturing a conductive two-dimensional polymer according to one aspect may include a step of purifying after completion of the reaction, and the purification may be a mild purification performed under mild conditions, and specifically, may include a step of removing residual organic matter by dialysis against distilled water, drying under reduced pressure, and then treating with supercritical CO2.

[0143] Another aspect of the present invention provides a p-type doped conductive two-dimensional polymer comprising the conductive two-dimensional polymer and a p-type dopant.

[0144] The above p-type dopant is not particularly limited as long as it is commonly used in the relevant technical field, but for example, iodine (I2), FeCl3, F4TCNQ, F6TCNNQ, NOBF4, It may be selected from NOPF6, etc.

[0145] The dopant content of the above p-type doped conductive two-dimensional polymer may be, but is not limited to, 5 to 40 wt%, or 5 to 30 wt%, or 10 to 30 wt%, or 10 to 20 wt%, or 10 to 15 wt%.

[0146] The above p-type doped conductive two-dimensional polymer according to one embodiment has an electrical conductivity of 1.0 x 10 as measured based on the van der Pauw method. -2 Scm -1 Ideal, or 5.0 x 10 -2 Scm -1 Ideal, or 1.0 x 10 -1 Scm -1 Ideal, or 2.0 x 10 -1 Scm -1 It may be ideal, 9.0 x 10 -1 Scm -1 or less, or 8.0 x 10 -1 Scm -1 or less, or 6.0 x 10 -1 Scm -1 or less, or 5.0 x 10 -1 Scm -1 It could be as follows:

[0147] Another aspect of the present invention provides an organic electronic device comprising the conductive two-dimensional polymer or the p-type doped conductive two-dimensional polymer.

[0148] The organic electronic device is not particularly limited as long as it can use a conductive two-dimensional polymer according to one aspect, and non-limiting examples thereof include an organic solar cell, an organic transistor, an organic memory, an organic photoconductor, or an organic light sensor, and can be used as an electrode or active layer material of the organic electronic device.

[0149] Another aspect of the present invention provides a compound represented by the following chemical formula 1.

[0150] [Chemical Formula 1]

[0151]

[0152] (In the above chemical formula 1,

[0153] A 1 Inland A 3 Each ring is independently a C6-C20 aromatic ring;

[0154] R 1 Inland R 3 are each independently C1-C20 alkyl, halo(C1-C20)alkyl, halogen or nitrile;

[0155] a to c are each independently integers from 1 to 5.)

[0156] The compound represented by the above chemical formula 1 can be usefully used as a monomer for manufacturing a conductive two-dimensional polymer due to its structural characteristics described above.

[0157] For example, the above A 1 Inland A 3 Each ring is independently a C6-C12 aromatic ring; R 1 Inland R 3 are each independently C1-C10 alkyl; a to c can each independently be an integer from 3 to 5.

[0158] For example, the above R 1 Inland R 3 may each independently be C1-C10 alkyl, C1-C7 alkyl, or C1-C4 alkyl, or C1-C3 alkyl, or methyl or ethyl.

[0159] For example, the above R 1 Inland R 3 may each independently be halo(C1-C10)alkyl, halo(C1-C7)alkyl, or fluoro(C1-C7)alkyl or perfluoro(C1-C7)alkyl, or -CF3 or -CF2CF3.

[0160] For example, the above A 1 Inland A 3The rings can be identical to each other, R 1 Inland R 3 can be identical to each other, and a to c can be identical to each other.

[0161] For example, the compound of the above chemical formula 1 may be represented by the following chemical formula 1-1, and the pendant of the same structure ( ) are included in symmetrical positions, the lattice deformation of the conductive two-dimensional polymer can be more effectively suppressed and more precise lamination can be induced.

[0162] [Chemical Formula 1-1]

[0163]

[0164] (In the above chemical formula 1-1, R 11 is C1-C20 alkyl, halo(C1-C20)alkyl, halogen or nitrile.)

[0165] For example, the above R 11 may be C1-C10 alkyl, or C1-C7 alkyl, or C1-C4 alkyl, or C1-C3 alkyl, or methyl or ethyl.

[0166] For example, the above R 11 may be halo(C1-C0)alkyl, halo(C1-C7)alkyl, or fluoro(C1-C7)alkyl or perfluoro(C1-C7)alkyl, or -CF3 or -CF2CF3.

[0167] For example, the compound of the above chemical formula 1 may be represented by the following chemical formula 3.

[0168] [Chemical Formula 3]

[0169]

[0170] Hereinafter, the above-described implementation examples will be described in more detail through examples. However, the following examples are for illustrative purposes only and do not limit the scope of the rights.

[0171] [Example 1] Synthesis of a conductive two-dimensional polymer (C2P-9)

[0172]

[0173] Step 1: Synthesis of compound (1)-A

[0174] A mixture of 1,5,9-triamino-2,3,6,7,10,11-hexamethoxytrimethylene (1.01 g (2.23 mmol), mesitaldehyde (2.00 mL (13.38 mmol), and acetic acid (30 mL)) was refluxed for 12 hours. The temperature of the reaction mixture was lowered to room temperature, and 1.26 g (5.58 mmol) of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) was added. The mixture was stirred for 1 hour, filtered, washed with distilled water, and dried under vacuum. The obtained powder was purified by column chromatography (volume ratio of ethyl acetate / hexane = 1 / 9) to obtain compound (1)-A (82%).

[0175] 1 H NMR (850 MHz, CDCl3): δ 7.59 (s, 3H), 3.99 (s, 9H), 4.06 (s, 9H).

[0176] 13 C NMR (214 MHz, CDCl3): δ 55.81, 62.09, 107.34, 114.05, 122.89, 141.64, 143.35, 152.03.

[0177]

[0178] Step 2: Synthesis of compound (1)

[0179] Compound (1)-A (1.0 g, 1.19 mmol) obtained above was dissolved in 20 mL of acetic acid, and then 1.6 mL of HBr (48% w / w aq.) was added and refluxed for 12 hours. The mixture was cooled to room temperature, extracted with ethyl acetate, washed with brine, dried over Na2SO4, and concentrated to obtain a black solid. The solid obtained above and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (810 mg, 3.57 mmol) were dissolved in 20 mL of methanol and stirred at room temperature for 2 hours. The reaction mixture was then concentrated in vacuo and purified by column chromatography (volume ratio of dichloromethane / methanol=97 / 3) to obtain compound (1) (92%).

[0180] 1 H NMR (850 MHz, MeOD): δ 7.05 (s, 2H), 7.02 (s, 2H), 6.97 (d, J = 3.9 Hz, 4H), 6.94 (d, J = 2.9 Hz, 9H), 3.36 (s, 9H), 2.14 (d, J = 6.8 Hz, 6H), 2.03 (t, J = 15.8 Hz, 9H), 1.95 (d, J = 7.6 Hz, 6H).

[0181] 13 C NMR (214 MHz, MeOD): δ 190.8, 190.7, 190.6, 160.9, 160.8, 160.5, 159.7, 159.6, 159.1, 158.9, 137.7, 136.8, 136.5, 136.0, 135.9, 135.8, 135.7, 135.6, 133.8, 127.6, 127.5, 123.1, 122.9, 122.7, 122.6, 116.1, 116.0, 115.9, 115.8, 94.0, 93.6, 19.9, 19.1, 18.9, 18.8, 18.7, 18.6.

[0182]

[0183]

[0184] Step 3: C2P-9 Synthesis

[0185] 16 mg (18.5 μmol) of the compound (1) obtained above was mixed with 0.5 mL of ethanol and 0.5 ml of mesitylene, and 13.5 μL (370 μmol, 15 equiv.) of 2,4,5-trimethylbenzaldehyde was added.

[0186] The above mixed solution was transferred to a 15 mL pressure tube containing 6.7 mg (27.8 μmol, 1.5 equiv.) of 2,3,6,7-tetraaminophenazine (TAP), and 0.1 mL of 6 M acetic acid was added. After sonication for 1 minute, the mixture was stirred at room temperature for 30 minutes and then stirred at 120 °C for 24 hours. After cooling to room temperature, it was filtered, washed with methanol, and Soxhlet extracted with methanol and tetrahydrofuran for 12 hours to obtain a black solid. Afterwards, the obtained powder was dialyzed with distilled water (Thermo Fisher scientific, MWCO: 10,000) and dried under reduced pressure, and then purified through supercritical CO2 treatment to obtain C2P-9, a conductive two-dimensional polymer (yield ~100%, quantitative).

[0187] [Example 2]

[0188] A 1.5 mL vial containing 14.4 mg of the conductive two-dimensional polymer (C2P-9) obtained in Example 1 was placed in a 30 mL vial filled with 10 g of iodine (I-2). The 30 mL vial was then capped, wrapped with aluminum foil, and stored in a sand bath at 40 °C in the dark for 48 h, followed by vacuum drying at 50 °C for 4 h to obtain I2-doped C2P-9 (I2@C2P-9) containing 14.3 wt% of iodine.

[0189] Iodine content was calculated by comparing the weight before and after doping, and it was confirmed that the iodine increase was saturated after 48 hours.

[0190] <Evaluation example>

[0191] Evaluation 1. Structural Analysis

[0192] FT-IR (Fourier transform infrared spectroscopy, Agilent Technologies Cary 600 series) and CP-MAS (cross-polarization magic angle spinning) of the conductive two-dimensional polymer (C2P-9) obtained in Example 1 above 13 C-NMR was analyzed, and the results are shown in Figures 1 and 2.

[0193] Referring to the FT-IR graph of C2P-9 in Fig. 1, the mesityl CH (2,931 cm) of compound (1) -1 ), C=C and C=N (1,496 and 1,623 cm -1 ) peak is maintained, and the C=O peak (1,718 cm) of compound (1) -1 ) and NH peak of TAP (3000 ~ 3400 cm -1 ) can be confirmed to disappear. Through this, it can be seen that a condensation reaction occurred between the diketone group of compound (1) and the diamine group of TAP.

[0194] Referring to Figure 2, it can be confirmed that peaks for aromatic carbons located next to pyridine nitrogen, sp2 quaternary aromatic carbons, and aliphatic carbons of the mesityl group appear at 162, 140, 130, and 22 ppm, respectively.

[0195] In addition, the results of analyzing the conductive two-dimensional polymer (C2P-9) of the above example using transmission electron microscopy (TEM) are shown in Fig. 3. Referring to Fig. 3, it was confirmed that C2P-9 has a hexagonal structure and has in-plane periodicity with long-range order.

[0196] Evaluation 2. Optical properties

[0197] C2P-9 of Example 1 was dissolved in dimethylformamide (DMF) and the UV-NIR spectrum (Agilent Cary 5000 UV-Vis-NIR Spectrophotometer) was analyzed and shown in Fig. 4. Referring to Fig. 4, the maximum absorption wavelength of C2P-9 was observed in the near-infrared region, indicating that it has an extended p-conjugated structure. In addition, the optical band gap of C2P-9, calculated by analyzing the Tauc plot in the UV-NIR spectrum of Fig. 4, was confirmed to be 1.71 eV, which corresponds to the semiconductor band gap range.

[0198] Evaluation 3. Electrical Characteristics

[0199] The electrical conductivity of C2P-9 of Example 1 and I2@C2P-9 of Example 2 was measured through 4-probe measurement based on the van der Pauw method. Specifically, each sample was subjected to a pressure of about 1 GPa in a vacuum at 80°C to produce pellets with a thickness of about 0.05 mm and a length of 5.6 mm, and then the electrical conductivity at room temperature (25°C) was measured using a Keithley 4200 SCS parameter analyzer. As a result, the electrical conductivity of C2P-9 was 1.1 x 10 -9 Scm -1 , I2@C2P-9 is 2.5 x 10 -1 Scm -1 It was confirmed that C2P-9 has a very high electrical conductivity value after I2 doping.

[0200] In addition, the electron mobility (μ) of the I2@C2P-9 as a function of temperature e ) and hole mobility (μ h ) was analyzed and shown in Fig. 5. Specifically, 5 mg of I2@C2P-9 sample was made into a pellet using a pellet press (10 ton, 10 s), and contact was formed using graphite ink (dispersed in toluene), and electron and hole mobilities were analyzed using van der Pauw geometry. As shown in Fig. 5, the electron mobility at 10 K of I2@C2P-9 according to the present invention was 3,200 cm 2 V ―1 s ―1 It was confirmed that it has an ultra-high electron mobility similar to that of graphene.

[0201] As described above, the present invention has been described by limited embodiments, but these are provided only to help a more general understanding of the present invention, and the present invention is not limited to the above embodiments, and those skilled in the art to which the present invention pertains can make various modifications and variations based on this description.

[0202] Therefore, the idea of ​​the present invention should not be limited to the described embodiments, and all things that are equivalent or equivalent to the claims described below as well as the claims are considered to fall within the scope of the idea of ​​the present invention.

Claims

1. A conductive two-dimensional polymer comprising a structural unit derived from a compound of the following chemical formula 1 and a structural unit derived from a compound of the following chemical formula 2: [Chemical Formula 1] [Chemical formula 2] In the above chemical formula 1, A 1 Inland A 3 Each ring is independently a C6-C20 aromatic ring; R 1 Inland R 3 are each independently C1-C20 alkyl, halo(C1-C20)alkyl, halogen or nitrile; a to c are each independently an integer from 1 to 5.

2. In paragraph 1, A above 1 Inland A 3 Each ring is independently a C6-C12 aromatic ring; R 1 Inland R 3 are each independently C1-C10 alkyl; A conductive two-dimensional polymer, wherein a to c are each independently an integer from 3 to 5.

3. In paragraph 1, The compound of the above chemical formula 1 is a conductive two-dimensional polymer represented by the following chemical formula 3. [Chemical Formula 3] 4. In paragraph 1, The conductive two-dimensional polymer is a conductive two-dimensional polymer including a diimine group formed by a reaction between a diketone group of a compound represented by the chemical formula 1 and a diamine group of a compound represented by the chemical formula 2.

5. In paragraph 1, A conductive two-dimensional polymer comprising a structural unit represented by the following chemical formula 4. [Chemical Formula 4] In the above chemical formula 4, A 1 Inland A 3 , R 1 Inland R 3 and a to c are the same as defined in paragraph 1.

6. In paragraph 1, A conductive two-dimensional polymer comprising a structural unit represented by the following chemical formula 5. [Chemical Formula 5] 7. In paragraph 1, A conductive two-dimensional polymer having an aspect ratio of 20 to 1,000.

8. A p-type doped conductive two-dimensional polymer comprising the conductive two-dimensional polymer of any one of claims 1 to 7 and a p-type dopant.

9. In paragraph 8, A p-type doped conductive two-dimensional polymer, wherein the p-type dopant is iodine (I2).

10. In paragraph 8, A p-type doped conductive two-dimensional polymer, wherein the dopant content of the p-type doped conductive two-dimensional polymer is 10 to 30 wt%.

11. In paragraph 8, Electrical conductivity measured based on the van der Poe method was 1.0 x 10 -2 Scm -1 Ideal, p-type doped conductive two-dimensional polymer.

12. A method for producing a conductive two-dimensional polymer, comprising the step of reacting compounds of chemical formulae 1 and 2 in the presence of an aldehyde compound, an acid catalyst, and an organic solvent. [Chemical Formula 1] [Chemical formula 2] In the above chemical formula 1, A 1 Inland A 3 Each ring is independently a C6-C20 aromatic ring; R 1 Inland R 3 are each independently C1-C20 alkyl; a to c are each independently an integer from 1 to 5.

13. In paragraph 12, A method for producing a conductive two-dimensional polymer, wherein the above aldehyde compound is represented by the following chemical formula 6. [Chemical formula 6] In the above chemical formula 6, R 4 are each independently C1-C20 alkyl; d is an integer from 1 to 5.

14. In paragraph 12, A method for producing a conductive two-dimensional polymer, comprising reacting 1 to 3 moles of a compound of chemical formula 2 with 1 mole of a compound of chemical formula 1.

15. In paragraph 12, A method for producing a conductive two-dimensional polymer, wherein 10 to 30 moles of an aldehyde compound are used per 1 mole of the compound of the above chemical formula 1.

16. In paragraph 12, A method for producing a conductive two-dimensional polymer, comprising the steps of: dialyzing the polymer against distilled water after completion of the reaction, drying under reduced pressure, and exposing the polymer to supercritical CO2.

17. An organic electronic device comprising a p-type doped conductive two-dimensional polymer according to claim 8.

18. In paragraph 17, The above organic electronic device is an organic solar cell, an organic transistor, an organic memory, an organic photoconductor or an organic light sensor.

19. A compound represented by the following chemical formula 1. [Chemical Formula 1] In the above chemical formula 1, A 1 Inland A 3 Each ring is independently a C6-C20 aromatic ring; R 1 Inland R 3 are each independently C1-C20 alkyl, halo(C1-C20)alkyl, halogen or nitrile; a to c are each independently an integer from 1 to 5.

20. In paragraph 19, A above 1 Inland A 3 Each ring is independently a C6-C12 aromatic ring; R 1 Inland R 3 are each independently C1-C10 alkyl; A compound wherein a to c are each independently an integer from 3 to 5.

21. In paragraph 19, The compound of the above chemical formula 1 is a compound represented by the following chemical formula 3. [Chemical Formula 3]

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