Preparation method of polythiophene conjugated polymer

Abstract

The invention relates to a preparation method of a polythiophene conjugated polymer, which comprises the following steps: in the presence of a palladium catalyst, a nitrogen-containing heterocyclic ligand, an oxidant, a deprotonated ligand and a solvent, carrying out oxidation direct arylation polymerization reaction on aromatic hydrocarbon to be activated to synthesize a polythiophene conductive polymer in one step; the aromatic hydrocarbon to be activated is one or more of thiophene and derivatives thereof; the coordination number of the nitrogen-containing heterocyclic ring ligand and palladium is 1, and the coordination number of the deprotonated ligand and palladium is 2; or, the coordination number of the nitrogen-containing heterocyclic ring ligand and palladium is 2, and the coordination number of the deprotonated ligand and palladium is 1; the sum of WPd-C and WC-H obtained through calculation according to a reaction transition state of a metal synergistic deprotonation step in which a ligand and a deprotonated ligand participate, which is calculated according to a density functional theory, is not less than 0.75; the method provided by the invention is simple and rapid in steps, does not need to pre-activate the monomer, and solves the problems of low yield and polymerization degree of polythiophene polymers prepared by direct arylation polymerization through oxidation in the prior art.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials and relates to a method for preparing a polythiophene conjugated polymer. Background Art

[0002] Conjugated polymers have been widely used in organic electronic devices. Since the sulfur atoms in polythiophene polymers have a certain positive charge, the polymers are easily doped with negative ions, which promotes the transmission of holes on the polymer chain, thus giving the polymer materials properties such as high capacitance and high conductivity.

[0003] At present, the polymerization methods for synthesizing polythiophene conjugated polymers are usually electrochemical polymerization, oxidative polymerization and transition metal catalyzed polymerization.

[0004] The polymers prepared by electrochemical polymerization and oxidative polymerization have low yields, poor monomer utilization, low molecular weight, large dispersion coefficient, and the obtained polymers are easily cross-linked, resulting in poor solubility and limiting their machinability.

[0005] Document 1 (Chemical Review, 2016, 116, 14225) and Document 2 (Acta Polymerica Sinica, 2019, 50, (6), 109.) record that the transition metal catalyzed polymerization method has a high monomer utilization rate, and the controllability and high catalytic efficiency of the polymerization reaction can be achieved by controlling the reaction conditions and additives. However, the polymerized monomers are usually preactivated, such as Document 3 (ACS Catalysis, 2015, 5, 3040-3053) records the introduction of organic selenium groups and halogen groups (Still polymerization) at the reaction site of the polymerization unit, Document 4 (ACS Sensors, 2020, 5, 191-198) records the introduction of boric acid groups and halogen groups (Suzuki) at the reaction site of the polymerization unit, and Document 5 (Progress in Polymer Science, 2018, 83, 135-201) records the introduction of halogen groups at the reaction site of the polymerization unit. This type of method makes the polymerization process complicated and costly, and the by-products are environmentally unfriendly, which greatly limits the industrial development of functionalized conductive polymer materials.

[0006] As the direct arylation reaction is further derived into the oxidative direct arylation polymerization system, the steps are more concise and environmentally friendly, and it is expected to achieve technical upgrades. However, according to the technical conditions of the existing oxidative direct arylation system, the catalytic efficiency of the polymerization monomer is poor, and it is impossible to prepare high-performance polythiophene polymers, which makes the application of this technology fall into a bottleneck. Document 6 (Polymer Journal, 2013, 45, 281-286) synthesized poly 3-hexylthiophene by oxidative direct arylation polymerization under the catalytic action of palladium catalyst for the first time, but the yield was only 20% and the degree of polymerization was 23. Among them, the document uses oxygen atmosphere as an oxidant to achieve the regeneration of the palladium catalyst. The catalytic efficiency of this condition is low and the reaction time is long, which is difficult to be applied to industrial production on a large scale. Reference 7 (Polymer Chemistry, 2016, 7, 1623-1631) used silver carbonate and copper acetate as oxidants for oxidative polymerization when synthesizing ester-functionalized polythiophene, and explored the experimental conditions of different oxidants. It was found that the oxidation efficiency of silver carbonate (yield 68%, degree of polymerization 49) was higher than that of copper acetate (yield 33%, degree of polymerization 31), but both were much lower than the polymer prepared by the Stille method (yield 78%, degree of polymerization 202), and industrial upgrading could not be achieved. At the same time, when we tried to prepare poly 3,4-ethylenedioxythiophene derivatives with 3,4-ethylenedioxythiophene derivatives under the same reaction conditions, no product was obtained. Reference 8 (ACS Marcro Letters, 2019, 8, 931-936) selected different phosphine ligands for oxidative arylation polymerization under the oxidation of the oxidant silver carbonate when synthesizing alkyl-functionalized poly 3,4-propylenedioxythiophene. Among them, under the conditions of palladium catalyst, ligand and silver acetate, the reaction was carried out for 48 hours to obtain a yield of 92%, but the degree of polymerization was only 26; Reference 9 (European Polymer Journal, 2022, 178, 111436) used an oxygen atmosphere as an oxidation catalyst (yield 72%, degree of polymerization only 17). The ligand-free reaction conditions are environmentally friendly, but the temperature needs to be controlled to rise slowly, which makes the process too complicated and the degree of polymerization is not high. Its catalytic efficiency is still far behind the traditional direct arylation polymerization method.

[0007] Generally speaking, the greater the degree of polymerization of the conjugated polymer, the higher its conductivity, and at the same time has a stronger resistance to deformation. Conjugated polymers with high polymerization degrees have excellent electrochemical and mechanical properties, and have broad prospects in electrochemical application scenarios with different requirements. In order to solve the problem of low degree of polymerization of polythiophene derivatives prepared by oxidative direct arylation reaction method, improving the catalytic efficiency of the reaction system for the reaction site of the polymerization unit is the key to solving this problem. Document 10 (Journal of the American Chemical Society, 2022, 144, 6123-6135) records that according to the Carothers equation, when the conversion rate of the monomer decreases slightly, it affects the growth of the polymer chain exponentially. Therefore, it is particularly important to improve the catalytic efficiency of the polymerization unit under palladium catalysis. Compared with the existing direct arylation polymerization method, the oxidative direct arylation polymerization method continues to apply the modification of the monodentate phosphine ligand to improve the reaction efficiency, which obviously can no longer meet the preparation of high-performance polythiophene conjugated polymer materials.

[0008] Therefore, it is still challenging to efficiently synthesize high-performance polythiophene conjugated polymers via oxidative direct arylation polymerization. Summary of the invention

[0009] In order to solve the problem of low yield and polymerization degree of polythiophene polymers prepared by direct oxidative arylation polymerization in the prior art, the present invention provides a method for preparing polythiophene conjugated polymers;

[0010] To achieve the above object, the scheme adopted by the present invention is as follows:

[0011] A method for preparing a polythiophene conjugated polymer, wherein the polythiophene conductive polymer is synthesized in one step by directly oxidizing and arylating the aromatic hydrocarbon to be activated in the presence of a palladium catalyst, a nitrogen-containing heterocyclic ligand, an oxidant, a deprotonated ligand and a solvent;

[0012] The aromatic hydrocarbon to be activated is one or more of thiophene and its derivatives;

[0013] The coordination number of the nitrogen-containing heterocyclic ligand with palladium is 1, and the coordination number of the deprotonated ligand with palladium is 2; or, the coordination number of the nitrogen-containing heterocyclic ligand with palladium is 2, and the coordination number of the deprotonated ligand with palladium is 1;

[0014] The W calculated by density functional theory is the reaction transition state of the metal-coordinated deprotonation step involving the ligand and the deprotonated ligand. Pd-C With W C-H The sum is not less than 0.75, where W Pd-C is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and palladium, W C-HIt is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom connected to it.

[0015] As the preferred technical solution:

[0016] In the method for preparing a polythiophene conjugated polymer as described above, the molar ratio of the aromatic hydrocarbon to be activated, the palladium catalyst, the nitrogen-containing heterocyclic ligand, the oxidant and the deprotonated ligand is 1:0.01-0.2:0.02-0.5:2-10:2-10, and the ratio of the volume of the solvent to the molar number of the aromatic hydrocarbon to be activated is 0.001-1 L / mol.

[0017] The method for preparing the polythiophene conjugated polymer as described above is carried out under an inert atmosphere, the reaction temperature is 100 to 160° C., and the reaction time is 0.2 to 36 hours.

[0018] In the method for preparing a polythiophene conjugated polymer as described above, the inert atmosphere is helium, nitrogen or argon atmosphere.

[0019] The preparation method of a polythiophene conjugated polymer as described above, wherein the nitrogen-containing heterocyclic ligand is The deprotonated ligand is acetylglycine;

[0020] Wherein, R1 to R5 are each independently selected from one of an alkyl group, an alkoxy group, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a dimethylamino group and a trifluoromethyl group.

[0021] The preparation method of a polythiophene conjugated polymer as described above, wherein the nitrogen-containing heterocyclic ligand is The deprotonated ligand is a carboxylate or carbonate;

[0022] Among them, R6~R 13 Each is independently selected from a fluorine atom, a chlorine atom, a cyano group, a nitro group and a trifluoromethyl group.

[0023] In the method for preparing a polythiophene conjugated polymer as described above, the carboxylate is potassium pivalate or cesium pivalate; and the carbonate is potassium carbonate or cesium carbonate.

[0024] In the method for preparing a polythiophene conjugated polymer as described above, the palladium catalyst is palladium acetate, palladium pivalate or palladium chloride, the oxidant is copper acetate, copper valerate, copper sulfate or copper chloride, and the solvent is N,N-dimethylformamide or N,N-dimethylacetamide.

[0025] The preparation method of the polythiophene conjugated polymer described above, the thiophene derivatives are specifically 3,4-ethylenedioxythiophene and 3,4-propylenedioxythiophene, and the structural formula of thiophene and its derivatives is

[0026] Where R is a hydrogen atom,

[0027] is a hydrogen atom, a methyl group, a hydroxyl group, a hexafluoroisopropanol group, a carboxyl group, x and y are integers, and 0≤x≤20, 0≤y≤20.

[0028] Principle of the invention:

[0029] The maximum coordination number of palladium is 4. If the four-coordination number of the palladium atom is filled, the reaction intermediate has higher stability and thus higher reactivity. Based on this, we attribute the low efficiency of the prior art oxidative direct arylation polymerization method to the fact that the intermediate cannot be guaranteed to be a tetraligand under the action of monodentate ligands and carboxylates, that is, the reaction intermediate is unstable, so it is difficult to activate the α site of thiophene derivatives; in addition, the compatibility of ligands / deprotonated ligands and polythiophene monomers should be qualitatively characterized. Based on this, bidentate ligands can provide better stability to stabilize and activate the α site of thiophene derivatives, and at the same time, density functional theory is used to characterize the compatibility of ligands / deprotonated ligands and polythiophene monomers.

[0030] The method provided by the present invention can be generally used to prepare polythiophene conjugated polymers, and is not limited to polythiophene and poly-3,4-propylenedioxythiophene. Based on the exploration of the oxidative direct arylation polymerization method of the polythiophene system, the present invention proposes two ligand selection modes, one is a combination of nitrogen-nitrogen bidentate ligand / pivalate; the other is a combination of monodentate nitrogen ligand / acetylglycine. The two groups of combinations and thiophene polymerization units are more beneficial to catalyze the α position of its polymerization unit under the palladium catalytic system, and can prepare polythiophene polymers with higher polymerization degree. One thing they have in common is that the coordination site jointly occupied by the nitrogen-containing heterocyclic ligand and the deprotonated ligand is 3, which is helpful for the activation of the thiophene derivative polymerization unit. At the same time, each polymerization unit has two α-active sites. After activating the first polymerization site, a Pd-C bond is formed, and an empty coordination bond formed by the existing ligand needs to be destroyed to make room for the reaction for the activation of the second α-position.

[0031] The combination of nitrogen-nitrogen bidentate ligand / pivalate means that the coordination number of the nitrogen-containing heterocyclic ligand is 2, and the coordination number of the deprotonated ligand is 1; taking pyridine as the ligand / acetylglycine as the deprotonated ligand as an example, the reaction mechanism diagram is as follows Figure 2 As shown;

[0032] The combination of monodentate nitrogen ligand / acetylglycine means that the coordination number of the nitrogen-containing heterocyclic ligand is 1, and the coordination number of the deprotonated ligand is 2; taking 2,2-bipyridine as the ligand / acetate as the deprotonated ligand as an example, the reaction mechanism diagram is as follows Figure 1 As shown;

[0033] In addition, by extending the quantitative calculation results of the direct arylation reaction mechanism (ACS catalysis, 2019, 9, 6921-6836), the reaction transition states of the metal-coordinated deprotonation step involving the ligand and the deprotonated ligand calculated by density functional theory were calculated, and the W Pd-C With W C-H When the sum is not less than 0.75, the polythiophene polymerization monomer has a catalytic efficiency higher than that of the prior art under the oxidative direct arylation polymerization system, that is, within the specified reaction time, the prepared polythiophene derivative has a higher yield and degree of polymerization.

[0034] Beneficial Effects

[0035] (1) The preparation method of the present invention has simple and rapid steps, does not require pre-activation of the monomer, and is suitable for industrial production;

[0036] (2) The preparation method of the present invention solves the problem of low yield and polymerization degree of polythiophene polymers prepared by direct oxidative arylation polymerization in the prior art. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 This is a reaction mechanism diagram of Example 8 of the present invention using 2,2-bipyridine as a ligand and acetate as a deprotonated ligand;

[0038] Figure 2 This is a reaction mechanism diagram of Example 1 of the present invention using pyridine as a ligand and acetylglycine as a deprotonated ligand.

[0039] Figure 3 This is a UV-visible spectrum of a conductive polymer prepared in Example 1.

[0040] Figure 4 This is a hydrogen nuclear magnetic resonance spectrum of a conductive polymer prepared in Example 1. DETAILED DESCRIPTION

[0041] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

[0042] The test or calculation method involved in the embodiment is as follows:

[0043] W Pd-C With W C-HCalculation method of the sum: calculated by Gaussian 09 software, using M06L functional theory for structure optimization, where Pd atoms are calculated using the SDD basis set, and other atoms are calculated using the 6-31G (d) basis set, and Gaussian09 is used to calculate the atomic charge and Weber bond order of the reaction state (the input keywords are POP = NBORead, BNDIDX).

[0044] Degree of polymerization: The hydrogen spectrum signal of the polymer is tested by hydrogen spectrum nuclear magnetic resonance, and the ratio of the integrated area of ​​the cycloalkyl number of the dioxane part on the PEDOT skeleton to the integrated area of ​​the hydrogen spectrum signal of the terminal CH bond is divided by the average number of hydrogen atoms in the cycloalkyl group of a single polymerization unit. The obtained value is the degree of polymerization of the polymer;

[0045] Taking Example 1 as an example, the terminal peak (CH) position of the polymer is 6.45 ppm, the chemical shift of the cycloalkyl of the dioxane part connected to thiophene in the polymer is 3.92-4.80, and the integrated area ratio of the two is 298.6: 1. The number of carbon-hydrogen bonds of the cycloalkyl of every two polymer units is 7, so the degree of polymerization n = integrated area of ​​cycloalkyl * 2 / (7 * integrated area of ​​terminal hydrogen), and n is calculated to be 85.

[0046] Yield: the amount of polymer product obtained / the amount of aromatic hydrocarbon to be activated*100%.

[0047] Example 1

[0048] A method for preparing a polythiophene conjugated polymer, the specific steps are as follows:

[0049] (1) Preparation of raw materials;

[0050] Palladium catalyst: palladium acetate;

[0051] Nitrogen-containing heterocyclic ligands:

[0052] Oxidant: copper acetate;

[0053] Deprotonated ligand: acetylglycine;

[0054] Solvent: N,N-dimethylformamide;

[0055] Aromatic hydrocarbons to be activated:

[0056] The W calculated by density functional theory is the reaction transition state of the metal-coordinated deprotonation step involving the ligand and the deprotonated ligand. Pd-C With W C-H The sum is 1.059, where W Pd-C is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and palladium, WC-H It is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom connected to it.

[0057] (2) In the presence of a palladium catalyst, a nitrogen-containing heterocyclic ligand, an oxidant, a deprotonated ligand and a solvent, the activated aromatic hydrocarbon is subjected to an oxidative direct arylation polymerization reaction at 100°C for 6 h in a helium atmosphere to synthesize a polythiophene-based conductive polymer in one step. The reaction mechanism is as follows: Figure 2 As shown; wherein the molar ratio of the aromatic hydrocarbon to be activated, the palladium catalyst, the nitrogen-containing heterocyclic ligand, the oxidant and the deprotonated ligand is 1:0.1:0.2:2:2, and the ratio of the volume of the solvent to the molar number of the aromatic hydrocarbon to be activated is 0.01 L / mol.

[0058] like Figure 3 , 4 As shown, the structural formula of the prepared polythiophene conjugated polymer is: The yield was 58% and the degree of polymerization was 85.

[0059] like Figure 3 The ultraviolet spectrum shows that the maximum absorption wavelength of the polymer is 588nm.

[0060] like Figure 4 As shown in the nuclear magnetic hydrogen spectrum, 2.7-3.4ppm is the hydrogen spectrum signal of the O-CH2-CH2-N bond, 3.95-4.65ppm is the hydrogen spectrum signal of the cycloalkyl group of the dioxane part on the dioxane PEDOT skeleton, and 6.45ppm is the hydrogen spectrum signal of the CH bond of the polymer end group.

[0061] Example 2

[0062] A method for preparing a polythiophene conjugated polymer, the specific steps are as follows:

[0063] (1) Preparation of raw materials;

[0064] Palladium catalyst: palladium acetate;

[0065] Nitrogen-containing heterocyclic ligands:

[0066] Oxidant: copper acetate;

[0067] Deprotonated ligand: acetylglycine;

[0068] Solvent: N,N-dimethylformamide;

[0069] Aromatic hydrocarbons to be activated:

[0070] The W calculated by density functional theory is the reaction transition state of the metal-coordinated deprotonation step involving the ligand and the deprotonated ligand.Pd-C With W C-H The sum is 1.065, where W Pd-C is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and palladium, W C-H It is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom connected to it.

[0071] (2) In the presence of a palladium catalyst, a nitrogen-containing heterocyclic ligand, an oxidant, a deprotonated ligand and a solvent, the aromatic hydrocarbon to be activated is subjected to an oxidative direct arylation polymerization reaction at 120° C. for 1 h in a helium atmosphere to synthesize a polythiophene-based conductive polymer in one step; wherein the molar ratio of the aromatic hydrocarbon to be activated, the palladium catalyst, the nitrogen-containing heterocyclic ligand, the oxidant and the deprotonated ligand is 1:0.01:0.02:2:2, and the ratio of the volume of the solvent to the molar number of the aromatic hydrocarbon to be activated is 0.01 L / mol.

[0072] The structural formula of the obtained polythiophene conjugated polymer is: The yield was 78% and the degree of polymerization was 45.

[0073] Example 3

[0074] A method for preparing a polythiophene conjugated polymer, the specific steps are as follows:

[0075] (1) Preparation of raw materials;

[0076] Palladium catalyst: palladium acetate;

[0077] Nitrogen-containing heterocyclic ligands:

[0078] Oxidant: copper valerate;

[0079] Deprotonated ligand: acetylglycine;

[0080] Solvent: N,N-dimethylacetamide;

[0081] Aromatic hydrocarbons to be activated:

[0082] The W calculated by density functional theory is the reaction transition state of the metal-coordinated deprotonation step involving the ligand and the deprotonated ligand. Pd-C With W C-H The sum is 1.062, where W Pd-C is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and palladium, W C-H It is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom connected to it.

[0083] (2) In the presence of a palladium catalyst, a nitrogen-containing heterocyclic ligand, an oxidant, a deprotonated ligand and a solvent, the aromatic hydrocarbon to be activated is subjected to an oxidative direct arylation polymerization reaction at 140° C. for 3 h in a nitrogen atmosphere to synthesize a polythiophene-based conductive polymer in one step; wherein the molar ratio of the aromatic hydrocarbon to be activated, the palladium catalyst, the nitrogen-containing heterocyclic ligand, the oxidant and the deprotonated ligand is 1:0.01:0.02:2:2, and the ratio of the volume of the solvent to the molar number of the aromatic hydrocarbon to be activated is 0.1 L / mol.

[0084] The structural formula of the obtained polythiophene conjugated polymer is: The yield was 88% and the degree of polymerization was 35.

[0085] Example 4

[0086] A method for preparing a polythiophene conjugated polymer, the specific steps are as follows:

[0087] (1) Preparation of raw materials;

[0088] Palladium catalyst: palladium pivalate;

[0089] Nitrogen-containing heterocyclic ligands:

[0090] Oxidant: copper valerate;

[0091] Deprotonated ligand: acetylglycine;

[0092] Solvent: N,N-dimethylformamide;

[0093] Aromatic hydrocarbons to be activated:

[0094] The W calculated by density functional theory is the reaction transition state of the metal-coordinated deprotonation step involving the ligand and the deprotonated ligand. Pd-C With W C-H The sum is 1.098, where W Pd-C is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and palladium, W C-H It is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom connected to it.

[0095] (2) In the presence of a palladium catalyst, a nitrogen-containing heterocyclic ligand, an oxidant, a deprotonated ligand and a solvent, the aromatic hydrocarbon to be activated is subjected to an oxidative direct arylation polymerization reaction at 160° C. for 6 hours in a nitrogen atmosphere to synthesize a polythiophene-based conductive polymer in one step; wherein the molar ratio of the aromatic hydrocarbon to be activated, the palladium catalyst, the nitrogen-containing heterocyclic ligand, the oxidant and the deprotonated ligand is 1:0.01:0.05:2:2, and the ratio of the volume of the solvent to the molar number of the aromatic hydrocarbon to be activated is 0.05 L / mol.

[0096] The structural formula of the obtained polythiophene conjugated polymer is: The yield was 93% and the degree of polymerization was 41.

[0097] Example 5

[0098] A method for preparing a polythiophene conjugated polymer, the specific steps are as follows:

[0099] (1) Preparation of raw materials;

[0100] Palladium catalyst: Palladium pivalate

[0101] Nitrogen-containing heterocyclic ligands:

[0102] Oxidant: copper sulfate;

[0103] Deprotonated ligand: acetylglycine;

[0104] Solvent: N,N-dimethylformamide;

[0105] Aromatic hydrocarbons to be activated:

[0106] The W calculated by density functional theory is the reaction transition state of the metal-coordinated deprotonation step involving the ligand and the deprotonated ligand. Pd-C With W C-H The sum is 1.064, where W Pd-C is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and palladium, W C-H It is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom connected to it.

[0107] (2) In the presence of a palladium catalyst, a nitrogen-containing heterocyclic ligand, an oxidant, a deprotonated ligand and a solvent, the aromatic hydrocarbon to be activated is subjected to an oxidative direct arylation polymerization reaction at 100° C. for 12 hours under an argon atmosphere to synthesize a polythiophene-based conductive polymer in one step; wherein the molar ratio of the aromatic hydrocarbon to be activated, the palladium catalyst, the nitrogen-containing heterocyclic ligand, the oxidant and the deprotonated ligand is 1:0.01:0.02:10:10, and the ratio of the volume of the solvent to the molar number of the aromatic hydrocarbon to be activated is 0.1 L / mol.

[0108] The structural formula of the obtained polythiophene conjugated polymer is: The yield was 98% and the degree of polymerization was 55.

[0109] Example 6

[0110] A method for preparing a polythiophene conjugated polymer, the specific steps are as follows:

[0111] (1) Preparation of raw materials;

[0112] Palladium catalyst: palladium chloride;

[0113] Nitrogen-containing heterocyclic ligands:

[0114] Oxidant: copper chloride;

[0115] Deprotonated ligand: acetylglycine;

[0116] Solvent: N,N-dimethylacetamide;

[0117] Aromatic hydrocarbons to be activated:

[0118] The W calculated by density functional theory is the reaction transition state of the metal-coordinated deprotonation step involving the ligand and the deprotonated ligand. Pd-C With W C-H The sum is 0.991, where W Pd-C is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and palladium, W C-H It is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom connected to it.

[0119] (2) In the presence of a palladium catalyst, a nitrogen-containing heterocyclic ligand, an oxidant, a deprotonated ligand and a solvent, under an argon atmosphere, the aromatic hydrocarbon to be activated is subjected to an oxidative direct arylation polymerization reaction at 120° C. for 24 hours to synthesize a polythiophene-based conductive polymer in one step; wherein the molar ratio of the aromatic hydrocarbon to be activated, the palladium catalyst, the nitrogen-containing heterocyclic ligand, the oxidant and the deprotonated ligand is 1:0.1:0.2:2:2, and the ratio of the volume of the solvent to the molar number of the aromatic hydrocarbon to be activated is 1 L / mol.

[0120] The structural formula of the obtained polythiophene conjugated polymer is: The yield was 100%.

[0121] Example 7

[0122] A method for preparing a polythiophene conjugated polymer, the specific steps are as follows:

[0123] (1) Preparation of raw materials;

[0124] Palladium catalyst: palladium chloride;

[0125] Nitrogen-containing heterocyclic ligands:

[0126] Oxidant: copper chloride;

[0127] Deprotonated ligand: acetylglycine;

[0128] Solvent: N,N-dimethylacetamide;

[0129] Aromatic hydrocarbons to be activated:

[0130] The W calculated by density functional theory is the reaction transition state of the metal-coordinated deprotonation step involving the ligand and the deprotonated ligand. Pd-C With W C-H The sum is 0.879, where W Pd-C is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and palladium, W C-H It is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom connected to it.

[0131] (2) In the presence of a palladium catalyst, a nitrogen-containing heterocyclic ligand, an oxidant, a deprotonated ligand and a solvent, under an argon atmosphere, the aromatic hydrocarbon to be activated is subjected to an oxidative direct arylation polymerization reaction at 140° C. for 36 hours to synthesize a polythiophene-based conductive polymer in one step; wherein the molar ratio of the aromatic hydrocarbon to be activated, the palladium catalyst, the nitrogen-containing heterocyclic ligand, the oxidant and the deprotonated ligand is 1:0.01:0.02:2:2, and the ratio of the volume of the solvent to the molar number of the aromatic hydrocarbon to be activated is 0.125 L / mol.

[0132] The structural formula of the obtained polythiophene conjugated polymer is: The yield was 91% and the degree of polymerization was 210.

[0133] Example 8

[0134] A method for preparing a polythiophene conjugated polymer, the specific steps are as follows:

[0135] (1) Preparation of raw materials;

[0136] Palladium catalyst: palladium acetate;

[0137] Nitrogen-containing heterocyclic ligands:

[0138] Oxidant: copper acetate;

[0139] Deprotonated ligand: potassium pivalate;

[0140] Solvent: N,N-dimethylformamide;

[0141] Aromatic hydrocarbons to be activated:

[0142] The W calculated by density functional theory is the reaction transition state of the metal-coordinated deprotonation step involving the ligand and the deprotonated ligand. Pd-C With W C-H The sum is 0.751, where WPd-C is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and palladium, W C-H It is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom connected to it.

[0143] (2) In the presence of a palladium catalyst, a nitrogen-containing heterocyclic ligand, an oxidant, a deprotonated ligand and a solvent, the activated aromatic hydrocarbon is directly oxidized and arylated in a helium atmosphere at 100°C for 0.2 h to synthesize a polythiophene conductive polymer in one step. Figure 1 As shown; wherein, the molar ratio of the aromatic hydrocarbon to be activated, the palladium catalyst, the nitrogen-containing heterocyclic ligand, the oxidant and the deprotonated ligand is 1:0.01:0.02:2:2, and the ratio of the volume of the solvent to the molar number of the aromatic hydrocarbon to be activated is 0.125 L / mol.

[0144] The structural formula of the obtained polythiophene conjugated polymer is: The yield was 58% and the degree of polymerization was 45.

[0145] Example 9

[0146] A method for preparing a polythiophene conjugated polymer, the specific steps are as follows:

[0147] (1) Preparation of raw materials;

[0148] Palladium catalyst: palladium acetate;

[0149] Nitrogen-containing heterocyclic ligands:

[0150] Oxidant: copper acetate;

[0151] Deprotonated ligand: cesium pivalate;

[0152] Solvent: N,N-dimethylformamide;

[0153] Aromatic hydrocarbons to be activated:

[0154] The W calculated by density functional theory is the reaction transition state of the metal-coordinated deprotonation step involving the ligand and the deprotonated ligand. Pd-C With W C-H The sum is 0.78, where W Pd-C is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and palladium, W C-H It is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom connected to it.

[0155] (2) In the presence of a palladium catalyst, a nitrogen-containing heterocyclic ligand, an oxidant, a deprotonated ligand and a solvent, the aromatic hydrocarbon to be activated is subjected to an oxidative direct arylation polymerization reaction at 120° C. for 1 h in a helium atmosphere to synthesize a polythiophene-based conductive polymer in one step; wherein the molar ratio of the aromatic hydrocarbon to be activated, the palladium catalyst, the nitrogen-containing heterocyclic ligand, the oxidant and the deprotonated ligand is 1:0.01:0.02:2:2, and the ratio of the volume of the solvent to the molar number of the aromatic hydrocarbon to be activated is 0.125 L / mol.

[0156] The structural formula of the obtained polythiophene conjugated polymer is: The yield was 71% and the degree of polymerization was 88.

[0157] Example 10

[0158] A method for preparing a polythiophene conjugated polymer, the specific steps are as follows:

[0159] (1) Preparation of raw materials;

[0160] Palladium catalyst: palladium acetate;

[0161] Nitrogen-containing heterocyclic ligands:

[0162] Oxidant: copper acetate;

[0163] Deprotonated ligand: acetylglycine;

[0164] Solvent: N,N-dimethylformamide;

[0165] Aromatic hydrocarbons to be activated:

[0166] The W calculated by density functional theory is the reaction transition state of the metal-coordinated deprotonation step involving the ligand and the deprotonated ligand. Pd-C With W C-H The sum is 1.059, where W Pd-C is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and palladium, W C-H It is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom connected to it.

[0167] (2) In the presence of a palladium catalyst, a nitrogen-containing heterocyclic ligand, an oxidant, a deprotonated ligand and a solvent, the aromatic hydrocarbon to be activated is subjected to an oxidative direct arylation polymerization reaction at 100° C. for 0.2 h in a helium atmosphere to synthesize a polythiophene-based conductive polymer in one step; wherein the molar ratio of the aromatic hydrocarbon to be activated, the palladium catalyst, the nitrogen-containing heterocyclic ligand, the oxidant and the deprotonated ligand is 1:0.01:0.02:2:2, and the ratio of the volume of the solvent to the molar number of the aromatic hydrocarbon to be activated is 0.125 L / mol.

[0168] The structural formula of the obtained polythiophene conjugated polymer is: The yield was 45% and the degree of polymerization was 21.

[0169] Embodiment 11

[0170] A method for preparing a polythiophene conjugated polymer, the specific steps are as follows:

[0171] (1) Preparation of raw materials;

[0172] Palladium catalyst: palladium acetate;

[0173] Nitrogen-containing heterocyclic ligands:

[0174] Oxidant: copper acetate;

[0175] Deprotonated ligand: acetylglycine;

[0176] Solvent: N,N-dimethylformamide;

[0177] Aromatic hydrocarbons to be activated:

[0178] The W calculated by density functional theory is the reaction transition state of the metal-coordinated deprotonation step involving the ligand and the deprotonated ligand. Pd-C With W C-H The sum is 1.065, where W Pd-C is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and palladium, W C-H It is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom connected to it.

[0179] (2) In the presence of a palladium catalyst, a nitrogen-containing heterocyclic ligand, an oxidant, a deprotonated ligand and a solvent, the aromatic hydrocarbon to be activated is subjected to an oxidative direct arylation polymerization reaction at 120° C. for 1 h in a helium atmosphere to synthesize a polythiophene-based conductive polymer in one step; wherein the molar ratio of the aromatic hydrocarbon to be activated, the palladium catalyst, the nitrogen-containing heterocyclic ligand, the oxidant and the deprotonated ligand is 1:0.01:0.02:2:2, and the ratio of the volume of the solvent to the molar number of the aromatic hydrocarbon to be activated is 0.125 L / mol.

[0180] The structural formula of the obtained polythiophene conjugated polymer is: The yield was 68% and the degree of polymerization was 38.

[0181] Example 12

[0182] A method for preparing a polythiophene conjugated polymer, the specific steps are as follows:

[0183] (1) Preparation of raw materials;

[0184] Palladium catalyst: palladium acetate;

[0185] Nitrogen-containing heterocyclic ligands:

[0186] Oxidant: copper valerate;

[0187] Deprotonated ligand: acetylglycine;

[0188] Solvent: N,N-dimethylacetamide;

[0189] Aromatic hydrocarbons to be activated:

[0190] The W calculated by density functional theory is the reaction transition state of the metal-coordinated deprotonation step involving the ligand and the deprotonated ligand. Pd-C With W C-H The sum is 1.062, where W Pd-C is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and palladium, W C-H It is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom connected to it.

[0191] (2) In the presence of a palladium catalyst, a nitrogen-containing heterocyclic ligand, an oxidant, a deprotonated ligand and a solvent, the aromatic hydrocarbon to be activated is subjected to an oxidative direct arylation polymerization reaction at 140° C. for 3 h in a nitrogen atmosphere to synthesize a polythiophene-based conductive polymer in one step; wherein the molar ratio of the aromatic hydrocarbon to be activated, the palladium catalyst, the nitrogen-containing heterocyclic ligand, the oxidant and the deprotonated ligand is 1:0.01:0.02:2:2, and the ratio of the volume of the solvent to the molar number of the aromatic hydrocarbon to be activated is 0.125 L / mol.

[0192] The structural formula of the obtained polythiophene conjugated polymer is: The yield was 74% and the degree of polymerization was 49.

[0193] Example 13

[0194] A method for preparing a polythiophene conjugated polymer, the specific steps are as follows:

[0195] (1) Preparation of raw materials;

[0196] Palladium catalyst: palladium chloride;

[0197] Nitrogen-containing heterocyclic ligands:

[0198] Oxidant: copper chloride;

[0199] Deprotonated ligand: acetylglycine;

[0200] Solvent: N,N-dimethylacetamide;

[0201] Aromatic hydrocarbons to be activated:

[0202] The W calculated by density functional theory is the reaction transition state of the metal-coordinated deprotonation step involving the ligand and the deprotonated ligand. Pd-C With W C-H The sum is 0.991, where W Pd-C is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and palladium, W C-H It is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom connected to it.

[0203] (2) In the presence of a palladium catalyst, a nitrogen-containing heterocyclic ligand, an oxidant, a deprotonated ligand and a solvent, under an argon atmosphere, the aromatic hydrocarbon to be activated is subjected to an oxidative direct arylation polymerization reaction at 120° C. for 24 hours to synthesize a polythiophene-based conductive polymer in one step; wherein the molar ratio of the aromatic hydrocarbon to be activated, the palladium catalyst, the nitrogen-containing heterocyclic ligand, the oxidant and the deprotonated ligand is 1:0.01:0.02:2:2, and the ratio of the volume of the solvent to the molar number of the aromatic hydrocarbon to be activated is 0.125 L / mol.

[0204] The structural formula of the obtained polythiophene conjugated polymer is: The yield was 90% and the degree of polymerization was 98.

[0205] Embodiment 14

[0206] A method for preparing a polythiophene conjugated polymer, the specific steps are as follows:

[0207] (1) Preparation of raw materials;

[0208] Palladium catalyst: palladium chloride;

[0209] Nitrogen-containing heterocyclic ligands:

[0210] Oxidant: copper chloride;

[0211] Deprotonated ligand: acetylglycine;

[0212] Solvent: N,N-dimethylacetamide;

[0213] Aromatic hydrocarbons to be activated:

[0214] The W calculated by density functional theory is the reaction transition state of the metal-coordinated deprotonation step involving the ligand and the deprotonated ligand. Pd-C With W C-HThe sum is 0.997, where W Pd-C is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and palladium, W C-H It is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom connected to it.

[0215] (2) In the presence of a palladium catalyst, a nitrogen-containing heterocyclic ligand, an oxidant, a deprotonated ligand and a solvent, under an argon atmosphere, the aromatic hydrocarbon to be activated is subjected to an oxidative direct arylation polymerization reaction at 140° C. for 36 hours to synthesize a polythiophene-based conductive polymer in one step; wherein the molar ratio of the aromatic hydrocarbon to be activated, the palladium catalyst, the nitrogen-containing heterocyclic ligand, the oxidant and the deprotonated ligand is 1:0.01:0.02:2:2, and the ratio of the volume of the solvent to the molar number of the aromatic hydrocarbon to be activated is 0.125 L / mol.

[0216] The structural formula of the obtained polythiophene conjugated polymer is: The yield was 91% and the degree of polymerization was 78.

[0217] Embodiment 15

[0218] A method for preparing a polythiophene conjugated polymer, the specific steps are as follows:

[0219] (1) Preparation of raw materials;

[0220] Palladium catalyst: palladium acetate;

[0221] Nitrogen-containing heterocyclic ligands:

[0222] Oxidant: copper acetate;

[0223] Deprotonated ligand: acetylglycine;

[0224] Solvent: N,N-dimethylformamide;

[0225] Aromatic hydrocarbons to be activated:

[0226] The W calculated by density functional theory is the reaction transition state of the metal-coordinated deprotonation step involving the ligand and the deprotonated ligand. Pd-C With W C-H The sum is 0.979, where W Pd-C is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and palladium, W C-H It is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom connected to it.

[0227] (2) In the presence of a palladium catalyst, a nitrogen-containing heterocyclic ligand, an oxidant, a deprotonated ligand and a solvent, the aromatic hydrocarbon to be activated is subjected to an oxidative direct arylation polymerization reaction at 100° C. for 12 hours in a helium atmosphere to synthesize a polythiophene-based conductive polymer in one step; wherein the molar ratio of the aromatic hydrocarbon to be activated, the palladium catalyst, the nitrogen-containing heterocyclic ligand, the oxidant and the deprotonated ligand is 1:0.01:0.02:2:2, and the ratio of the volume of the solvent to the molar number of the aromatic hydrocarbon to be activated is 0.125 L / mol.

[0228] The structural formula of the obtained polythiophene conjugated polymer is: The yield was 91% and the degree of polymerization was 49.

[0229] Example 16

[0230] A method for preparing a polythiophene conjugated polymer, the specific steps are as follows:

[0231] (1) Preparation of raw materials;

[0232] Palladium catalyst: palladium acetate;

[0233] Nitrogen-containing heterocyclic ligands:

[0234] Oxidant: copper acetate;

[0235] Deprotonated ligand: acetylglycine;

[0236] Solvent: N,N-dimethylformamide;

[0237] Aromatic hydrocarbons to be activated:

[0238] The W calculated by density functional theory is the reaction transition state of the metal-coordinated deprotonation step involving the ligand and the deprotonated ligand. Pd-C With W C-H The sum is 0.919, where W Pd-C is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and palladium, W C-H It is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom connected to it.

[0239] (2) In the presence of a palladium catalyst, a nitrogen-containing heterocyclic ligand, an oxidant, a deprotonated ligand and a solvent, the aromatic hydrocarbon to be activated is subjected to an oxidative direct arylation polymerization reaction at 120° C. for 12 hours in a helium atmosphere to synthesize a polythiophene-based conductive polymer in one step; wherein the molar ratio of the aromatic hydrocarbon to be activated, the palladium catalyst, the nitrogen-containing heterocyclic ligand, the oxidant and the deprotonated ligand is 1:0.01:0.02:2:2, and the ratio of the volume of the solvent to the molar number of the aromatic hydrocarbon to be activated is 0.125 L / mol.

[0240] The structural formula of the obtained polythiophene conjugated polymer is: The yield was 87% and the degree of polymerization was 44.

[0241] Embodiment 17

[0242] A method for preparing a polythiophene conjugated polymer, the specific steps are as follows:

[0243] (1) Preparation of raw materials;

[0244] Palladium catalyst: palladium acetate;

[0245] Nitrogen-containing heterocyclic ligands:

[0246] Oxidant: copper valerate;

[0247] Deprotonated ligand: acetylglycine;

[0248] Solvent: N,N-dimethylacetamide;

[0249] Aromatic hydrocarbons to be activated: mass ratio of 1:99 mixture of

[0250] The W calculated by density functional theory is the reaction transition state of the metal-coordinated deprotonation step involving the ligand and the deprotonated ligand. Pd-C With W C-H The sum is 0.874, where W Pd -C is The Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site and palladium, W C-H for The Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site and the hydrogen atom connected to it;

[0251] The W calculated by density functional theory is the reaction transition state of the metal-coordinated deprotonation step involving the ligand and the deprotonated ligand. Pd-C With W C-H The sum is 1.059, where W Pd-C for The Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site and palladium, W C-H for The Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site and the hydrogen atom connected to it.

[0252] (2) In the presence of a palladium catalyst, a nitrogen-containing heterocyclic ligand, an oxidant, a deprotonated ligand and a solvent, the aromatic hydrocarbon to be activated is subjected to an oxidative direct arylation polymerization reaction at 120° C. for 12 hours under a nitrogen atmosphere to synthesize a polythiophene-based conductive polymer in one step; wherein the molar ratio of the aromatic hydrocarbon to be activated, the palladium catalyst, the nitrogen-containing heterocyclic ligand, the oxidant and the deprotonated ligand is 1:0.01:0.02:2:2, and the ratio of the volume of the solvent to the molar number of the aromatic hydrocarbon to be activated is 0.125 L / mol.

[0253] The structural formula of the obtained polythiophene conjugated polymer is: The yield was 96% and the degree of polymerization was 121.

[0254] Embodiment 18

[0255] A method for preparing a polythiophene conjugated polymer, the specific steps are as follows:

[0256] (1) Preparation of raw materials;

[0257] Palladium catalyst: palladium acetate;

[0258] Nitrogen-containing heterocyclic ligands:

[0259] Oxidant: copper acetate;

[0260] Deprotonated ligand: acetylglycine;

[0261] Solvent: N,N-dimethylformamide;

[0262] Aromatic hydrocarbons to be activated: mass ratio of 50:50 mixture of

[0263] The W calculated by density functional theory is the reaction transition state of the metal-coordinated deprotonation step involving the ligand and the deprotonated ligand. Pd-C With W C-H The sum is 1.059, where W Pd-C is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and palladium, W C-H It is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom connected to it.

[0264] (2) In the presence of a palladium catalyst, a nitrogen-containing heterocyclic ligand, an oxidant, a deprotonated ligand and a solvent, the aromatic hydrocarbon to be activated is subjected to an oxidative direct arylation polymerization reaction at 120° C. for 12 hours in a helium atmosphere to synthesize a polythiophene-based conductive polymer in one step; wherein the molar ratio of the aromatic hydrocarbon to be activated, the palladium catalyst, the nitrogen-containing heterocyclic ligand, the oxidant and the deprotonated ligand is 1:0.01:0.02:2:2, and the ratio of the volume of the solvent to the molar number of the aromatic hydrocarbon to be activated is 0.125 L / mol.

[0265] The structural formula of the obtained polythiophene conjugated polymer is The yield was 87% and the degree of polymerization was 55.

[0266] Embodiment 19

[0267] A method for preparing a polythiophene conjugated polymer, the specific steps are as follows:

[0268] (1) Preparation of raw materials;

[0269] Palladium catalyst: palladium acetate;

[0270] Nitrogen-containing heterocyclic ligands:

[0271] Oxidant: copper acetate;

[0272] Deprotonated ligand: acetylglycine;

[0273] Solvent: N,N-dimethylformamide;

[0274] Aromatic hydrocarbons to be activated: mass ratio of 25:75 mixture of

[0275] The W calculated by density functional theory is the reaction transition state of the metal-coordinated deprotonation step involving the ligand and the deprotonated ligand. Pd-C With W C-H The sum is 0.979, where W Pd-C for The Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site and palladium, W C-H for The Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site and the hydrogen atom connected to it;

[0276] The W calculated by density functional theory is the reaction transition state of the metal-coordinated deprotonation step involving the ligand and the deprotonated ligand. Pd-C With W C-H The sum is 1.059, where W Pd-C for The Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site and palladium, WC-H for The Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site and the hydrogen atom connected to it.

[0277] (2) In the presence of a palladium catalyst, a nitrogen-containing heterocyclic ligand, an oxidant, a deprotonated ligand and a solvent, the aromatic hydrocarbon to be activated is subjected to an oxidative direct arylation polymerization reaction at 120° C. for 12 hours in a helium atmosphere to synthesize a polythiophene-based conductive polymer in one step; wherein the molar ratio of the aromatic hydrocarbon to be activated, the palladium catalyst, the nitrogen-containing heterocyclic ligand, the oxidant and the deprotonated ligand is 1:0.01:0.02:2:2, and the ratio of the volume of the solvent to the molar number of the aromatic hydrocarbon to be activated is 0.125 L / mol.

[0278] The structural formula of the obtained polythiophene conjugated polymer is: The yield was 89% and the degree of polymerization was 61.

[0279] Embodiment 20

[0280] A method for preparing a polythiophene conjugated polymer, the specific steps are as follows:

[0281] (1) Preparation of raw materials;

[0282] Palladium catalyst: palladium acetate;

[0283] Nitrogen-containing heterocyclic ligands:

[0284] Oxidant: copper valerate;

[0285] Deprotonated ligand: acetylglycine;

[0286] Solvent: N,N-dimethylacetamide;

[0287] Aromatic hydrocarbons to be activated: mass ratio of 99:1 mixture of

[0288] The W calculated by density functional theory is the reaction transition state of the metal-coordinated deprotonation step involving the ligand and the deprotonated ligand. Pd-C With W C-H The sum is 0.979, where W Pd-C is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and palladium, W C-H It is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom connected to it.

[0289] (2) In the presence of a palladium catalyst, a nitrogen-containing heterocyclic ligand, an oxidant, a deprotonated ligand and a solvent, the aromatic hydrocarbon to be activated is subjected to an oxidative direct arylation polymerization reaction at 120° C. for 12 hours under a nitrogen atmosphere to synthesize a polythiophene-based conductive polymer in one step; wherein the molar ratio of the aromatic hydrocarbon to be activated, the palladium catalyst, the nitrogen-containing heterocyclic ligand, the oxidant and the deprotonated ligand is 1:0.01:0.02:2:2, and the ratio of the volume of the solvent to the molar number of the aromatic hydrocarbon to be activated is 0.125 L / mol.

[0290] The structural formula of the obtained polythiophene conjugated polymer is: The yield was 96% and the degree of polymerization was 89.

Claims

1. A method for preparing a polythiophene conjugated polymer, characterized in that: In the presence of a palladium catalyst, a nitrogen-containing heterocyclic ligand, an oxidant, a deprotonated ligand and a solvent, the aromatic hydrocarbon to be activated is directly oxidized and arylated to synthesize a polythiophene conductive polymer in one step; The aromatic hydrocarbon to be activated is one or more of thiophene and its derivatives; The coordination number of the nitrogen-containing heterocyclic ligand with palladium is 1, and the coordination number of the deprotonated ligand with palladium is 2; or, the coordination number of the nitrogen-containing heterocyclic ligand with palladium is 2, and the coordination number of the deprotonated ligand with palladium is 1; The W calculated by density functional theory is the reaction transition state of the metal-coordinated deprotonation step involving the ligand and the deprotonated ligand. Pd-C With W C-H The sum is not less than 0.75, where W Pd-C is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and palladium, W C-H It is the Weber bond order of the transition state chemical bond formed by the carbon atom at the activation site of the aromatic hydrocarbon to be activated and the hydrogen atom connected to it.

2. The method for preparing a polythiophene conjugated polymer according to claim 1, characterized in that: The molar ratio of the aromatic hydrocarbon to be activated, the palladium catalyst, the nitrogen-containing heterocyclic ligand, the oxidant and the deprotonated ligand is 1:0.01-0.2:0.02-0.5:2-10:2-10, and the ratio of the volume of the solvent to the molar number of the aromatic hydrocarbon to be activated is 0.001-1 L / mol.

3. The method for preparing a polythiophene conjugated polymer according to claim 1, characterized in that: The reaction is carried out under an inert atmosphere, the reaction temperature is 100-160° C., and the reaction time is 0.2-36 h.

4. The method for preparing a polythiophene conjugated polymer according to claim 3, characterized in that: The inert atmosphere is helium, nitrogen or argon atmosphere.

5. The method for preparing a polythiophene conjugated polymer according to claim 1, characterized in that: The nitrogen-containing heterocyclic ligand is The deprotonated ligand is acetylglycine; Wherein, R1 to R5 are each independently selected from one of an alkyl group, an alkoxy group, a fluorine atom, a chlorine atom, a cyano group, a nitro group, a dimethylamino group and a trifluoromethyl group.

6. The method for preparing a polythiophene conjugated polymer according to claim 1, characterized in that: The nitrogen-containing heterocyclic ligand is The deprotonated ligand is a carboxylate or carbonate; Among them, R6~R 13 Each is independently selected from a fluorine atom, a chlorine atom, a cyano group, a nitro group and a trifluoromethyl group.

7. The method for preparing a polythiophene conjugated polymer according to claim 6, characterized in that: The carboxylate is potassium pivalate or cesium pivalate; the carbonate is potassium carbonate or cesium carbonate.

8. The method for preparing a polythiophene conjugated polymer according to claim 1, characterized in that: The palladium catalyst is palladium acetate, palladium pivalate or palladium chloride, the oxidant is copper acetate, copper valerate, copper sulfate or copper chloride, and the solvent is N,N-dimethylformamide or N,N-dimethylacetamide.

9. The method for preparing a polythiophene conjugated polymer according to claim 1, characterized in that: The structural formula of thiophene and its derivatives is Where R is a hydrogen atom, Y is a hydrogen atom, a methyl group, a hydroxyl group, a hexafluoroisopropanol group, a carboxyl group, x and y are integers, and 0≤x≤20, 0≤y≤20.

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