Intrinsic conductive cross-linked polyimide as well as preparation method and application thereof

Abstract

The invention discloses intrinsic conductive cross-linked polyimide as well as a preparation method and application thereof. Starting from a pyrrole or pyrrole derivative structure, the novel diamine monomer containing the pyrrole ring side group is prepared through a series of chemical reactions. The synthesized novel diamine monomer and tetracid dianhydride monomer are used as raw materials, and polyamic acid containing pyrrole ring side groups is obtained through polymerization. Carrying out imidization on the polyamide acid to obtain polyimide containing a pyrrole ring side group, or ionizing the polyamide acid by using triethylamine to obtain ionized polyamide acid containing the pyrrole ring side group; on the basis, a chemical oxidative polymerization method or an electrochemical oxidative polymerization method is adopted, and a pyrrole ring in the side group and pyrrole or a pyrrole derivative monomer are subjected to oxidative polymerization; and then respectively carrying out doping or doping and imidization to obtain the conductive cross-linked polyimide. The intrinsic conductive cross-linked polyimide prepared by the invention has excellent conductivity and heat resistance, and can be widely applied to the fields of microelectronics, photoelectricity, military industry, aerospace and the like.

Description

Technical Field

[0001] The present invention relates to the field of materials science and technology, and more specifically, to an intrinsic conductive crosslinked polyimide and its preparation method and application. Background Art

[0002] Polyimide (PI) has excellent heat resistance and mechanical properties, and conductive PI materials have broad application prospects in the fields of optics, electronics, aerospace, etc. For example, as a high-temperature electromagnetic shielding material, it is used for anti-static coating magnetic storage devices, electromagnetic shielding filter plates, electromagnetic shielding films for electronic devices such as aerospace and national defense, etc.; as a new type of special coating to solve the problem of static electricity accumulation and avoid combustion and explosion caused by charge accumulation; as an electrolyte membrane applied in fuel cells, it is expected to develop high-efficiency and high-energy density batteries; it can also be applied in flexible display materials and is expected to develop flexible integrated circuit boards.

[0003] Currently, the most common method for making conductive PI is to add conductive fillers (such as conductive carbon black, graphene, metal particles, and carbon nanotubes, etc.) to polyamic acid (PAA), and then form a film through casting drying, chemical or high-temperature thermal imidization treatment, such as CN202010288148.5, CN201610692333.4, CN201710582792.1, CN201410341743.5, CN201610156760.0, etc. However, the surface energy of the conductive filler is large, and it is easy to agglomerate, which easily causes a decrease in the mechanical properties of the PI composite material, thus limiting its application. In addition, surface metallization treatment of PI to achieve high surface conductivity is also one of the main methods for preparing conductive PI, such as CN202310769728.X, CN202211112091.9, CN202110716806.0, CN202110338844.7, CN202110716806.0, etc. However, the force between the metal and PI is weak, and the metal layer is prone to peeling off, thus limiting its application. Intrinsic conductive PI has excellent heat resistance. Compared with conductive filler-added and surface metallization-treated conductive PI, its chemical and thermal stability is good. Therefore, developing intrinsic conductive PI is an effective way to solve these problems existing in current conductive PI.

[0004] Through reasonable molecular structure design, the present invention designs and synthesizes a new diamine monomer containing pyrrole ring side groups, introduces it into the PI structure, and then oxidatively polymerizes and dopes the side group pyrrole ring with pyrrole or pyrrole derivative monomers to obtain an intrinsic conductive crosslinked PI with excellent comprehensive properties. This research is of great significance for promoting the application of conductive PI. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide an intrinsic conductive crosslinked PI in view of the problems existing in traditional additive and surface metallization treated conductive PIs.

[0006] Another technical problem to be solved by the present invention is to provide a preparation method of the intrinsic conductive PI.

[0007] The object of the present invention is achieved by the following technical solutions:

[0008] An intrinsic conductive crosslinked polyimide, characterized in that the conductive polyimide is formed by polymerizing a diamine monomer containing a pyrrole ring side group and a dianhydride monomer to form a polyamic acid containing a pyrrole ring side group, and then undergoing imidization and oxidative polymerization, and its molecular structure general formula is one of the following general formulas:

[0009]

[0010] Wherein: m is 5 to 10000, n is 0 to 10000, a is 0 to 200, b is 4 to 200, c is 0 to 200, s is 1 to 10000;

[0011] When the molecular structure general formula is (Ⅰ), X is selected from one of the following general formulas:

[0012]

[0013] * represents the connection position;

[0014] Wherein M is any one of the following structural formulas:

[0015]

[0016] * represents the connection position, wherein the ether bond is connected to R2, and the other bonds are connected to the imide ring;

[0017] Wherein Q is any one of the following structural formulas:

[0018]

[0019] * represents the connection position, wherein the ether bond is connected to R2, and the other bonds are connected to R1, and R1 is connected to the imide ring;

[0020] Wherein R1 is any one of the following structural formulas:

[0021]

[0022] * represents the connection position;

[0023] When the molecular structure general formula is (Ⅱ), X is selected from one of the following general formulas:

[0024]

[0025] * represents the connection position;

[0026] Among them, A is any one of the following structural formulas:

[0027]

[0028] * represents the connection position, where the ether bond is connected to R2, and the other bonds are connected to the imide ring;

[0029] Among them, E is any one of the following structural formulas:

[0030]

[0031] * represents the connection position, where the ether bond is connected to R2, the other bonds are connected to R1, and R1 is connected to the imide ring;

[0032] Among them, R1 is any one of the following structural formulas:

[0033]

[0034] * represents the connection position;

[0035] Among them, R2 is any one of the following structural formulas:

[0036]

[0037] * represents the connection position, where: q is 1 to 7;

[0038] Among them, R3 is one or more of the following structural formulas:

[0039]

[0040] * represents the connection position;

[0041] Among them, Y is selected from one or more of the following structures:

[0042]

[0043] * represents the connection position;

[0044] Among them, Z is selected from one or more of the following structural formulas:

[0045]

[0046] * represents the connection position.

[0047] A preparation method of an intrinsic conductive cross-linked polyimide, and the synthesis steps of the diamine monomer containing a pyrrole ring side group are as follows:

[0048] When the general formula of the X structure is (Ⅲ) or (Ⅴ), the preparation steps are as follows:

[0049] (A1) Add the R2 monomer with two bromine group substitutions to a solvent, add a base, dropwise add a solution containing the R3 monomer with a hydrogen substitution, perform an ice bath, stir and introduce an inert protective gas. After the reaction, purify and dry to obtain monomer 1, and the monomer structure is as follows:

[0050]

[0051] (A2) Add monomer 1 in step (A1) to a solvent, add a base, and then add the M monomer with one hydrogen and two amino substitutions or the A monomer with two hydrogens and two amino substitutions, stir and introduce an inert protective gas. After the reaction, purify and dry to obtain the diamine monomer 2 or diamine monomer 3 with pyrrole ring side groups respectively, and they have the following structural characteristics:

[0052]

[0053] When the general formula of the X structure is (Ⅳ) or (Ⅵ), the preparation steps are as follows:

[0054] (B1) Add monomer 1 in step (A1) to a solvent, add a base, and then add the Q monomer with one hydrogen and two bromine substitutions or the E monomer with two hydrogens and two bromine substitutions, stir and introduce an inert protective gas. After the reaction, purify and dry to obtain monomer 4 or monomer 5 respectively, and they have the following structural characteristics:

[0055]

[0056] (B2) Add monomer 4 or monomer 5 in step (B1) and the R1 monomer with one amino and one boric acid substitution to a solvent, add a base, stir and introduce an inert protective gas, heat, add a catalyst and reflux. After the reaction, purify and dry to obtain the diamine monomer 6 or diamine monomer 7 with pyrrole ring side groups, and they have the following structural characteristics:

[0057]

[0058] Furthermore, the inert protective gas in steps (A1), (A2), (B1), and (B2) is one or more of nitrogen, helium, neon, argon, krypton, xenon, and radon;

[0059] Furthermore, the solvent in steps (A1), (A2), (B1), and (B2) is one or more of tetrahydrofuran, ethanol, dichloromethane, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylacetamide, and N,N-dimethylformamide;

[0060] Further, the base in step (A1), step (A2), step (B1) and step (B2) is one or more of sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium fluoride, n-butyllithium, potassium tert-butoxide, sodium tert-butoxide, lithium hexamethyldisilazide;

[0061] Further, the R2 monomer containing two bromo substituents in step (A1) is one of dibromomethane, 1,2-dibromoethane, 1,3-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane, 1,6-dibromohexane, 1,7-dibromoheptane, 2,4-dibromopentane, 2,3-dibromobutane, 2,3-dibromo-2,3-dimethylbutane, 1-bromo-2-(2-bromoethoxy)ethane, 1,5-dibromopentan-3-one, 1,3-dibromo-2-methylpropane, 1-bromo-3-(3-bromopropoxy)propane, 1,3-dibromo-2-methoxypropane;

[0062] Further, the R3 monomer substituted by hydrogen in step (A1) is one of 1H-pyrrole, 2-methyl-1H-pyrrole, 2-acetyl-1H-pyrrole, 3-ethyl-1H-pyrrole, 3-cyano-1H-pyrrole, 3-nitro-1H-pyrrole, 3-acetyl-1H-pyrrole, 3,4-diethyl-1H-pyrrole, 3,4-difluoro-1H-pyrrole, 3-nonyl-1H-pyrrole, methyl 1H-pyrrole-3-carboxylate, 3,4-dimethyl-1H-pyrrole, 3-octyl-1H-pyrrole, 1H-pyrrole-3-carbaldehyde, 3-methyl-1H-pyrrole;

[0063] Further, when the general formula of the X structure is (III) or (V), the M monomer containing one hydrogen and two amino substituents in step (A2) is one of 2,6-diaminopyridin-4-ol, 2,5-diaminophenol, 3,4-diaminophenol and 2-(aminomethyl)-4-aminophenol; the A monomer containing two hydrogens and two amino substituents is one of 4,6-diaminobenzene-1,3-diol, 2,5-diaminobenzene-1,4-diol, 4,4'-sulfonylbis(2-aminophenol), 5,5'-diamino-[1,1'-biphenyl]-2,2'-diol, 4,4'-diamino-[1,1'-biphenyl]-3,3'-diol, 1,5-diamino-4,8-dihydroxy-9,10-anthraquinone, 1,8-diamino-4,5-dihydroxy-9,10-anthraquinone, 4,4'-(perfluoropropane-2,2-diyl)bis(2-aminophenol);

[0064] Further, when the general formula of the X structure is (IV) or (VI), the Q monomer containing one hydrogen and two bromo substituents described in step (B1) is one of 3,5-dibromophenol, 2,5-dibromophenol, 4,6-dibromonaphthalen-2-ol, 1,6-dibromonaphthalen-2-ol, 2',5'-dibromo-[1,1'-biphenyl]-4-ol, 3',5'-dibromo-[1,1'-biphenyl]-4-ol; the E monomer containing two hydrogens and two bromo substituents is one of 4,5-dibromobenzene-1,2-diol, 3,6-dibromonaphthalene-2,7-diol, 2,5-dibromobenzene-1,4-diol, 6,6'-dibromo-[1,1'-binaphthalene]-2,2'-diol, 3,6-dibromophenanthrene-9,10-diol, 3,3'-dibromo-[1,1'-biphenyl]-4,4'-diol;

[0065] Further, when the general formula of the X structure is (IV) or (VI), the R1 monomer containing one amino group and one boric acid substituent described in step (B2) is one of 4-aminophenylboronic acid, 3-aminophenylboronic acid, 2-aminophenylboronic acid, 6-aminopyridineboronic acid, 2-aminopyrimidine-5-boronic acid, [4-(4-aminophenoxy)phenyl]boronic acid, 4'-aminobiphenyl-4-boronic acid, 3'-aminobiphenyl-4-boronic acid, 4-aminonaphthalen-1-boronic acid, 5-aminonaphthalen-1-boronic acid, 6-aminonaphthalen-2-boronic acid;

[0066] Further, the dosage of the base described in step (A1) is 1 to 1.5 times the amount of the substance of the R2 monomer containing two bromo substituents, and the dosage of the R2 monomer containing two bromo substituents is 3 to 4 times the amount of the substance of the R3 monomer substituted by hydrogen;

[0067] Further, when the general formula of the X structure is (III) or (V), the dosage of the base described in step (A2) is 2 to 4 times the amount of the substance of monomer 1, the M monomer containing one hydrogen and two amino substituents is 1.2 to 1.6 times the amount of the substance of monomer 1, and the A monomer containing two hydrogens and two amino substituents is 0.6 to 0.8 times the amount of the substance of monomer 1;

[0068] Further, when the general formula of the X structure is (IV) or (VI), the dosage of the base described in step (B1) is 2 to 4 times the amount of the substance of monomer 1, the amount of the substance of the Q monomer containing one hydrogen and two bromo substituents is 1.2 to 1.6 times the amount of the substance of monomer 1, and the amount of the substance of the E monomer containing two hydrogens and two bromo substituents is 0.6 to 0.8 times the amount of the substance of monomer 1;

[0069] Further, when the general formula of the X structure is (IV) or (VI), the molar ratio of the monomer 4 or monomer 5 described in step (B2) to the R1 monomer containing one amino group and one boric acid-substituted group is 1:2 to 1:3, and the amount of the base used is 1.5 to 4 times the molar amount of the R1 monomer containing one amino group and one boric acid-substituted group;

[0070] Further, the temperature of the reaction described in step (A1) is -5 to 0 °C, the time is 4 to 8 h, the drying temperature is 40 to 120 °C, and the drying time is 6 to 30 h;

[0071] Further, when the general formula of the X structure is (III) or (V), the temperature of the reaction described in step (A2) is 50 to 100 °C, the time is 12 to 24 h, the drying temperature is 40 to 120 °C, and the drying time is 6 to 30 h;

[0072] Further, when the general formula of the X structure is (IV) or (VI), the temperature of the reaction described in step (B1) is 50 to 100 °C, the time is 12 to 24 h, the drying temperature is 40 to 120 °C, and the drying time is 6 to 30 h;

[0073] Further, when the general formula of the X structure is (IV) or (VI), the temperature of the reaction described in step (B2) is 50 to 120 °C, the time is 10 to 48 h, the drying temperature is 40 to 120 °C, and the drying time is 6 to 30 h;

[0074] An intrinsic conductive cross-linked polyimide, and the synthesis of the above-mentioned intrinsic conductive cross-linked polyimide is any one of the following methods:

[0075] (1) Dissolve the diamine monomer in one or more of the following strongly polar aprotic organic solvents: N-methylpyrrolidone, dimethyl sulfoxide, dimethyl sulfone, sulfolane, 1,4-dioxane, N,N-dimethylacetamide, N,N-dimethylformamide, m-cresol; after the diamine monomer is completely dissolved, add the dianhydride monomer, and the molar ratio of the diamine monomer to the dianhydride monomer is 1:0.9 - 1:1.1. Stir and react at -20 - 50 °C for 0.5 - 72 h to obtain a homogeneous and viscous polyamic acid precursor colloidal solution; then perform thermal imidization or chemical imidization on the polyamic acid precursor to dehydrate and obtain PI containing pyrrole ring side groups, and the total mass of the diamine and the dianhydride accounts for 2 - 50% of the mass of the polyamic acid colloidal solution; dissolve the obtained PI containing pyrrole ring side groups and the hydrogen-substituted R3 monomer (one or several of 1H-pyrrole, 2-methyl-1H-pyrrole, 2-acetyl-1H-pyrrole, 3-ethyl-1H-pyrrole, 3-cyano-1H-pyrrole, 3-nitro-1H-pyrrole, 3-acetyl-1H-pyrrole, 3,4-diethyl-1H-pyrrole, 3,4-difluoro-1H-pyrrole, 3-nonyl-1H-pyrrole, methyl 1H-pyrrole-3-carboxylate, 3,4-dimethyl-1H-pyrrole, 3-octyl-1H-pyrrole, 1H-pyrrole-3-carbaldehyde, 3-methyl-1H-pyrrole) in one or more of the following strongly polar aprotic solvents: N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylacetamide, N,N-dimethylformamide. The molar ratio of the hydrogen-substituted R3 monomer to the diamine monomer containing pyrrole ring side groups is 4:1 - 200:1. Stir at 0 - 50 °C, add an oxidant (one of iron oxide, copper chloride, ferric chloride, ferric perchlorate, ammonium persulfate, hydrogen peroxide) and a dopant (p-toluenesulfonic acid, dodecylbenzenesulfonic acid, hydrochloric acid, nitric acid, sulfuric acid, acetic acid, citric acid, sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, cetyltrimethylammonium bromide, sodium p-toluenesulfonate). The molar ratio of the hydrogen-substituted R3 monomer to the dopant is 1:0.8 - 1:1.2, and the molar ratio of the oxidant to the dopant is 1:0.8 - 1:1.2. Continue to stir and react for 0.5 - 4 h to obtain the intrinsic conductive crosslinked PI;

[0076] (2) Dissolve the diamine monomer in one or more of the following strongly polar aprotic organic solvents: N-methylpyrrolidone, dimethyl sulfoxide, dimethyl sulfone, sulfolane, 1,4-dioxane, N,N-dimethylacetamide, N,N-dimethylformamide, m-cresol; after the diamine monomer is completely dissolved, add the dianhydride monomer, and the molar ratio of the diamine monomer to the dianhydride monomer is 1:0.9 - 1:1.1. Stir and react at -20 to 50 °C for 0.5 - 72 h to obtain a homogeneous and viscous polyamic acid precursor colloidal solution; then add triethylamine to the polyamic acid precursor, where the molar ratio of triethylamine to the diamine monomer is 1:1 - 2:1, and ionize to obtain an ionized polyamic acid containing pyrrole ring side groups. The total mass of the diamine and the dianhydride accounts for 2 - 50% of the mass of the polyamic acid colloidal solution; then dissolve the obtained ionized polyamic acid containing pyrrole ring side groups and the hydrogen-substituted R3 monomer (one or several of 1H-pyrrole, 2-methyl-1H-pyrrole, 2-acetyl-1H-pyrrole, 3-ethyl-1H-pyrrole, 3-cyano-1H-pyrrole, 3-nitro-1H-pyrrole, 3-acetyl-1H-pyrrole, 3,4-diethyl-1H-pyrrole, 3,4-difluoro-1H-pyrrole, 3-nonyl-1H-pyrrole, methyl 1H-pyrrole-3-carboxylate, 3,4-dimethyl-1H-pyrrole, 3-octyl-1H-pyrrole, 1H-pyrrole-3-carbaldehyde, 3-methyl-1H-pyrrole) in one or more of the following mixed strongly polar aprotic solvents: N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylacetamide, N,N-dimethylformamide. The molar ratio of the hydrogen-substituted R3 monomer to the diamine monomer containing pyrrole ring side groups is 4:1 - 200:1. Add a dopant (p-toluenesulfonic acid, dodecylbenzenesulfonic acid, hydrochloric acid, nitric acid, sulfuric acid, acetic acid, citric acid, sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, cetyltrimethylammonium bromide, sodium p-toluenesulfonate), where the molar ratio of the hydrogen-substituted R3 monomer to the dopant is 1:0.8 - 1:1.2. Add the mixed solution to an electrophoresis device and perform electrophoresis for 0.5 - 24 h to oxidatively polymerize to obtain an intrinsic conductive crosslinked polyamic acid; perform thermal imidization or chemical imidization on the crosslinked polyamic acid to obtain an intrinsic conductive crosslinked PI;

[0077] Further, the specific operation of the thermal imidization in method (1) is as follows: First, add methanol or ethanol to the polyamic acid colloidal solution to precipitate polyamic acid powder, and then place the polyamic acid powder in a vacuum oven for heating. The temperature rising program is: raise the temperature from room temperature to 100 °C and keep it constant for 0.2 - 1.5 h, raise the temperature from 100 °C to 200 °C and keep it constant for 0.2 - 1.5 h, raise the temperature from 200 °C to 300 °C and keep it constant for 0.2 - 1.5 h, raise the temperature from 300 °C to 350 - 500 °C and keep it constant for 0.1 - 1 h, and then take it out after cooling to obtain PI;

[0078] Further, the specific operation of the thermal imidization in method (2) is as follows: Place the crosslinked polyamic acid in a vacuum oven and heat it. The temperature rising program is as follows: Raise the temperature from room temperature to 100 °C and keep it constant for 0.2 - 1.5 h, then raise the temperature from 100 °C to 200 °C and keep it constant for 0.2 - 1.5 h, then raise the temperature from 200 °C to 300 °C and keep it constant for 0.2 - 1.5 h, then raise the temperature from 300 °C to 350 - 500 °C and keep it constant for 0.1 - 1 h. After cooling, it can be taken out to obtain the intrinsic conductive crosslinked PI.

[0079] Further, the specific operation of the chemical imidization in method (1) is as follows: Add a dehydrating agent (acetic anhydride) and a catalyst (pyridine, triethylamine, sodium acetate or isoquinoline) to the polyamic acid solution. Stir and react at 0 - 100 °C for 0.5 - 2 h, then pour it into a solvent (methanol, ethanol) to precipitate a solid. Put the obtained solid in an oven and dry it at 80 - 100 °C. After cooling, PI is obtained.

[0080] Further, the specific operation of the chemical imidization in method (2) is as follows: Immerse the crosslinked polyamic acid in a mixed solution of a dehydrating agent (acetic anhydride) and a catalyst (pyridine, triethylamine, sodium acetate or isoquinoline), and carry out an imidization reaction at 0 - 100 °C for 0.5 - 2 h. Put the imidized crosslinked polyimide in an oven and dry it at 80 - 100 °C to obtain the intrinsic conductive crosslinked PI.

[0081] Compared with the prior art, the beneficial effects are as follows:

[0082] The conductive crosslinked PI containing a long-range conjugated structure proposed by the present invention has excellent conductive performance. Such PI endows its intrinsic conductive performance through molecular structure design, and does not need to add conductive fillers or coat a conductive layer on the surface to achieve conductivity. Moreover, its thermal performance is excellent, which is of great significance for expanding the application fields of PI materials for electromagnetic shielding.

[0083] The present invention prepares a novel type of intrinsic conductive crosslinked PI material by introducing a pyrrole ring structure into the PI molecular chain. The long-range conjugated structure of polypyrrole formed by crosslinking can effectively improve the electron transition ability on the molecular chain and make the polymer conductive through doping. In addition, the rigid aromatic structure of the main chain and the formed crosslinked structure can maintain the excellent thermal performance of PI, which can be used in high-tech fields such as microelectronics, optoelectronics, military and aerospace. At present, there is no report on diamine monomers containing side-chain pyrrole structures and their conductive crosslinked PI. Description of the Drawings

[0084] Figure 1 For the product 1 in Example 1 1 1H NMR (a) and 13 13C NMR (b) diagrams;

[0085] Figure 2For the product 2 in Example 1 1 1H NMR (c) and 13 13C NMR (d) spectra;

[0086] Figure 3 For the diamine monomer in Example 1 1 1H NMR (e) and 13 13C NMR (f) spectra;

[0087] Figure 4 For the MS spectrum of the diamine monomer in Example 1;

[0088] Figure 5 For the product 1 in Example 2 1 1H NMR (g) and 13 13C NMR (h) spectra;

[0089] Figure 6 For the product 2 in Example 2 1 1H NMR (i) and 13 13C NMR (j) spectra;

[0090] Figure 7 For the diamine monomer in Example 2 1 1H NMR (k) and 13 13C NMR (l) spectra;

[0091] Figure 8 For the MS spectrum of the diamine monomer in Example 2;

[0092] Figure 9 For the product 1 in Example 3 1 1H NMR (m) and 13 13C NMR (n) spectra;

[0093] Figure 10 For the product 2 in Example 3 1 1H NMR (o) and 13 13C NMR (p) spectra;

[0094] Figure 11 For the diamine monomer in Example 3 1 1H NMR (q) and 13 13C NMR (r) spectra;

[0095] Figure 12 For the MS spectrum of the diamine monomer in Example 3;

[0096] Figure 13 For the FT-IR spectra of the intermediate and its diamine monomer in Example 1, Example 15 and Comparative Example 1;

[0097] Figure 14FT-IR spectra of the intermediate and its diamine monomer of Example 2, and those of Example 16 and Comparative Example 3;

[0098] Figure 15 FT-IR spectra of the intermediate and its diamine monomer of Example 3, and those of Example 17 and Comparative Example 5;

[0099] Figure 16 TGA(s) and DMA(t) curves of Example 15, polypyrrole, Comparative Example 1, and Comparative Example 2;

[0100] Figure 17 TGA curves of the intrinsic conductive crosslinked PI in Examples 15 - 24. Detailed implementation manners

[0101] The present invention will be further elaborated below in conjunction with specific embodiments. It is necessary to point out that the following embodiments cannot be construed as limiting the protection scope of the invention. Some non-essential improvements and adjustments made by those skilled in the art to the present invention based on the above-mentioned invention content still fall within the protection scope of the present invention.

[0102] Example 1:

[0103] This example provides a synthesis method of 4-(4-(1H-pyrrol-1-yl)butoxy)-3-(aminomethyl)aniline:

[0104]

[0105] (1) Add 12.955 g (60 mmol) of 1,4-dibromobutane and 150 mL of dry tetrahydrofuran into a dry three-necked flask, cool down to 0 °C, add 1.440 g (60 mmol) of sodium hydride, stir at a constant temperature and purge with argon for protection, slowly dropwise add 1.342 g (20 mmol) of 1H-pyrrole. After the dropping is completed, react for 4 h, and concentrate the reaction solution by a rotary evaporator to obtain a crude product. Purify it by silica gel column chromatography, select n-hexane and dichloromethane as eluents, and elute successively with n-hexane:dichloromethane = 6:1, 4:1, 2:1 to obtain a solid. Dry it in vacuo at 80 °C for 12 h to obtain Product 1, whose structure is as follows:

[0106]

[0107] (2) Weigh 2.021 g (10 mmol) of product 1, 3.023 g (12 mmol) of 3,5-dibromophenol, 4.146 g (30 mmol) of anhydrous potassium carbonate, and 80 mL of dehydrated tetrahydrofuran and add them to a dry three-necked flask. Stir and purge with argon, heat to 75 °C and reflux for 12 h. After the reaction is completed, filter off the inorganic salts by suction filtration, collect the crude product by vacuum filtration, purify the crude product by column chromatography using dichloromethane:n-hexane = 1:1 (volume ratio) as the mobile phase and silica gel as the stationary phase, collect the product and evaporate to dryness, and dry it in vacuo at 50 °C for 10 h to obtain product 2, whose structure is as follows:

[0108]

[0109] (3) Weigh 3.731 g (10 mmol) of product 2 and 3.013 g (22 mmol) of 4-aminophenylboronic acid and add them to a three-necked flask. Add 50 mL of tetrahydrofuran, then add 30 mL of an aqueous solution of potassium carbonate (2 mol / L) and an appropriate amount of Aliquat 336. Stir and purge with argon, heat to 80 °C, add 0.1 g of tetrakis(triphenylphosphine)palladium, and reflux for 20 h. Take the organic phase of the reaction solution, evaporate the solvent by rotary evaporation, purify it by column chromatography using ethyl acetate as the mobile phase and silica gel as the stationary phase, collect the product and evaporate to dryness to obtain a solid, and dry it in vacuo at 80 °C for 12 h to obtain the target product.

[0110] Example 2:

[0111] This example provides a synthesis method for 5'-((5-(1H-pyrrol-1-yl)pentyl)oxy)-[1,1':3',1”-terphenyl]-4,4”-diamine:

[0112]

[0113] (1) Add 13.796 g (60 mmol) of 1,5-dibromopentane and 80 mL of N-methylpyrrolidone to a dry three-necked flask, cool to 0 °C, add 1.440 g (60 mmol) of sodium hydride, stir at a constant temperature and purge with argon, slowly add dropwise 1.007 g (15 mmol) of 1H-pyrrole, and react for 6 h after the addition is completed. Concentrate the reaction solution by a rotary evaporator to obtain a crude product. Purify it by silica gel column chromatography, select n-hexane and dichloromethane as the eluents, elute with n-hexane:dichloromethane = 2:1 to obtain a solid, and dry it in vacuo at 70 °C for 10 h to obtain product 1, whose structure is as follows:

[0114]

[0115] (2) Weigh 2.161 g (10 mmol) of product 1, 3.527 g (14 mmol) of 3,5-dibromophenol, 1.200 g (30 mmol) of sodium hydroxide and 100 mL of dehydrated tetrahydrofuran, add them to a dry three-necked flask, stir and introduce argon for protection, heat up to 75 °C and reflux for 12 h. After the reaction is completed, filter off the inorganic salts by suction filtration, collect the crude product by vacuum filtration, purify the crude product by column chromatography using dichloromethane:n-hexane = 1:1 (volume ratio) as the mobile phase and silica gel as the stationary phase, collect the product and evaporate to dryness, and dry it in vacuo at 70 °C for 6 h to obtain product 2, whose structure is as follows:

[0116]

[0117] (3) Weigh 3.871 g (10 mmol) of product 2 and 3.013 g (22 mmol) of 4-aminophenylboronic acid and add them to a three-necked flask, add 60 mL of tetrahydrofuran, then add 30 mL of an aqueous solution of anhydrous potassium carbonate (2 mol / L) and an appropriate amount of Aliquat 336, stir and introduce argon for protection, heat up to 80 °C and then add 0.1 g of tetrakis(triphenylphosphine)palladium, and reflux and react for 20 h. Take the organic phase of the reaction solution, evaporate the solvent by rotary evaporation, purify it by column chromatography using ethyl acetate as the mobile phase and silica gel as the stationary phase, collect the product and evaporate to dryness to obtain a solid, and dry it in vacuo at 80 °C for 12 h to obtain the target product.

[0118] Example 3:

[0119] This example provides a synthesis method of 5'-((6-(1H-pyrrol-1-yl)hexyl)oxy)-[1,1':3',1”-terphenyl]-4,4”-diamine:

[0120]

[0121] (1) Add 14.638 g (60 mmol) of 1,6-dibromohexane and 120 mL of dry tetrahydrofuran to a dry three-necked flask, cool down to 0 °C, add 1.440 g (60 mmol) of sodium hydride, stir at a constant temperature and introduce argon for protection, slowly dropwise add 1.342 g (20 mmol) of 1H-pyrrole, and react for 5 h after the addition is completed. Concentrate the reaction solution by a rotary evaporator to obtain a crude product. Purify it by silica gel column chromatography, select n-hexane and dichloromethane as the eluents, and elute successively with n-hexane:dichloromethane = 6:1, 4:1, 2:1 to obtain a solid, and dry it in vacuo at 80 °C for 12 h to obtain product 1, whose structure is as follows:

[0122]

[0123] (2) Weigh 2.302 g (10 mmol) of product 1, 3.023 g (12 mmol) of 3,5-dibromophenol, 4.146 g (30 mmol) of anhydrous potassium carbonate, and 80 mL of dehydrated tetrahydrofuran and add them to a dry three-necked flask. Stir and purge with argon, heat to 75 °C and reflux for 12 h. After the reaction is completed, filter off the inorganic salts by suction filtration, collect the crude product by vacuum filtration, purify the crude product by column chromatography using dichloromethane:n-hexane = 1:1 (volume ratio) as the mobile phase and silica gel as the stationary phase, collect the product and evaporate to dryness, and dry it in vacuo at 50 °C for 10 h to obtain product 2, whose structure is as follows:

[0124]

[0125] (3) Weigh 4.011 g (10 mmol) of product 2 and 3.013 g (22 mmol) of 4-aminophenylboronic acid and add them to a three-necked flask. Add 50 mL of tetrahydrofuran, then add 30 mL of an aqueous solution of potassium carbonate (2 mol / L) and an appropriate amount of Aliquat 336. Stir and purge with argon, heat to 80 °C, add 0.1 g of tetrakis(triphenylphosphine)palladium, and reflux for 20 h. Take the organic phase of the reaction solution, evaporate the solvent by rotary evaporation, purify it by column chromatography using ethyl acetate as the mobile phase and silica gel as the stationary phase, collect the product and evaporate to dryness to obtain a solid, and dry it in vacuo at 80 °C for 12 h to obtain the target product.

[0126] Example 4:

[0127] This example provides a synthesis method of 2'-(4-(1H-pyrrol-1-yl)butoxy)-[1,1':4',1”-terphenyl]-4,4”-diamine, and the synthesis steps are as follows:

[0128]

[0129] (1) Add 12.955 g (60 mmol) of 1,4-dibromobutane and 50 mL of dry tetrahydrofuran to a dry three-necked flask, cool to 0 °C, add 1.44 g (60 mmol) of sodium hydride, stir at a constant temperature and purge with argon. Mix 1.342 g (20 mmol) of 1H-pyrrole and 10 mL of tetrahydrofuran to form a solution and slowly add it dropwise. After the addition is complete, react for 4 h, and concentrate the reaction solution by rotary evaporator to obtain a crude product. Purify it by silica gel column chromatography, select n-hexane and dichloromethane as the eluent, collect the product and evaporate to dryness to obtain a solid, and dry it in vacuo at 80 °C for 10 h to obtain product 1. Its structure is as follows:

[0130]

[0131] (2) Weigh 2.021 g (10 mmol) of product 1, 1.796 g (13 mmol) of 2-aminomethyl-4-aminophenol, 3.366 g (30 mmol) of potassium tert-butoxide, and 90 mL of dehydrated ethanol, add them to a dry three-necked flask, stir, and introduce argon for protection. Heat up to 90 °C and reflux for 12 hours. After the reaction is completed, filter off the inorganic salts by suction filtration, collect the crude product by vacuum filtration, purify the crude product by column chromatography with dichloromethane as the mobile phase and silica gel as the stationary phase, collect the product and evaporate to dryness to obtain a solid, and dry it in vacuo at 100 °C for 15 h to obtain the target product.

[0132] Example 5:

[0133] This example provides a synthesis method of 4,4'-((2',5'-bis((5-(3-nitro-1H-pyrrol-1-yl)pentyl)oxy)-[1,1':4',1”-terphenyl]-4,4”-diyl)bis(oxy))dianiline:

[0134]

[0135] (1) Add 13.796 g (60 mmol) of 1,5-dibromopentane and 100 mL of dry tetrahydrofuran to a dry three-necked flask, cool down to 0 °C, add 10.099 g (90 mmol) of potassium tert-butoxide, stir at a constant temperature and introduce helium for protection. Mix 2.242 g (20 mmol) of 3-nitro-1H-pyrrole and 10 mL of tetrahydrofuran to form a solution, slowly dropwise add it, and after the addition is completed, react for 5 h. Concentrate the reaction solution by a rotary evaporator to obtain a crude product. Purify it by silica gel column chromatography, elute with dichloromethane to obtain a solid, and dry it in vacuo at 80 °C for 6 h to obtain product 1, whose structure is as follows:

[0136]

[0137] (2) Weigh 2.611 g (10 mmol) of product 1, 1.607 g (6 mmol) of 2,5-dibromobenzene-1,4-diol, 2.883 g (30 mmol) of sodium tert-butoxide, and 100 mL of dichloromethane, add them to a dry three-necked flask, stir, and introduce helium for protection. Heat up to 75 °C and reflux for 12 h. After the reaction is completed, filter off the inorganic salts by suction filtration, collect the crude product by vacuum filtration, purify the crude product by column chromatography with dichloromethane as the mobile phase and silica gel as the stationary phase, collect the product and evaporate to dryness to obtain a solid, and dry it in vacuo at 90 °C for 10 h to obtain product 2. Its structure is as follows:

[0138]

[0139] (3) Weigh 6.283 g (10 mmol) of product 2 and 5.726 g (30 mmol) of 4-(4-aminophenoxy)phenyl]boronic acid and add them to a three-necked flask. Add 50 mL of dichloromethane, then add 22.5 mL of an aqueous solution of anhydrous potassium carbonate (2 mol / L) and an appropriate amount of Aliquat 336. Stir and purge with helium for protection. After heating to 100 °C, add 0.16 g of tetrakis(triphenylphosphine)palladium, and reflux for 30 h. Take the organic phase of the reaction solution, rotary evaporate to remove the solvent, perform column chromatography purification using ethyl acetate as the mobile phase and silica gel as the stationary phase, collect the product and rotary dry to obtain a solid, and dry it in vacuo at 100 °C for 12 h to obtain the target product.

[0140] Example 6:

[0141] This example provides a synthesis method of 1,1'-(((2,5-diamino-1,4-phenylene)bis(oxy))bis(hexane-6,1-diyl))bis(1H-pyrrole-3-carbonitrile), and the steps are as follows:

[0142]

[0143] (1) Add 14.638 g (60 mmol) of 1,6-dibromohexane and 100 mL of dry N-methylpyrrolidone to a dry three-necked flask. Cool to 0 °C, add 4.484 g (70 mmol) of n-butyllithium, stir at a constant temperature and purge with neon for protection. Mix 1.842 g (20 mmol) of 3-cyano-1H-pyrrole and 20 mL of N-methylpyrrolidone to form a solution, and slowly add dropwise. After the addition is complete, react for 7 h. Concentrate the reaction solution by a rotary evaporator to obtain a crude product. Purify it by silica gel column chromatography, select n-hexane and dichloromethane as the eluents, elute successively with n-hexane:dichloromethane = 1:1, 1:2 (volume ratio), collect the product and rotary dry to obtain a solid, and dry it in vacuo at 80 °C for 18 h to obtain product 1. Its structure is as follows:

[0144]

[0145] (2) Weigh 2.552 g (10 mmol) of product 1, 0.981 g (7 mmol) of 4,6-diaminobenzene-1,3-diol, 3.366 g (30 mmol) of potassium tert-butoxide and 100 mL of dehydrated ethanol and add them to a dry three-necked flask. Stir and purge with argon for protection. Heat to 100 °C and reflux for 14 hours. After the reaction is completed, filter off the inorganic salts by suction filtration, collect the crude product by vacuum filtration. Purify the crude product by column chromatography using dichloromethane as the mobile phase and silica gel as the stationary phase, collect the product and rotary dry to obtain a solid, and dry it in vacuo at 100 °C for 12 h to obtain the target product.

[0146] Example 7:

[0147] This example provides a synthesis method of 4-((5-(3,4-diethyl-1H-pyrrol-1-yl)pentyl)oxy)benzene-1,2-diamine, and the synthesis steps are as follows:

[0148]

[0149] (1) Add 13.796 g (60 mmol) of 1,5-dibromopentane and 150 mL of dry N,N-dimethylformamide to a dry three-necked flask, cool down to 0 °C, add 3.367 g (60 mmol) of potassium hydroxide, stir constantly at a constant temperature and introduce argon for protection. Mix 2.464 g (20 mmol) of 3,4-diethyl-1H-pyrrole and 10 mL of N,N-dimethylformamide to form a solution, and slowly dropwise add it. After the dropping is completed, react for 5 h. Concentrate the reaction solution by a rotary evaporator to obtain a crude product. Purify it by silica gel column chromatography, select dichloromethane as the eluent, wash it with dichloromethane, collect the product and spin it dry to obtain a solid, and dry it in vacuo at 70 °C for 10 h to obtain Product 1. Its structure is as follows:

[0150]

[0151] (2) Weigh 2.722 g (10 mmol) of Product 1, 3.023 g (12 mmol) of 3,4-diaminophenol, 4.146 g (30 mmol) of anhydrous potassium carbonate and 70 mL of dehydrated N,N-dimethylformamide and add them to a dry three-necked flask, stir and introduce argon for protection, heat up to 80 °C for reflux, and react for 13 h. After the reaction is completed, filter off the inorganic salts by suction filtration, collect the crude product by vacuum filtration, purify the crude product by column chromatography with dichloromethane as the mobile phase and silica gel as the stationary phase, collect the product and spin it dry to obtain a solid, and dry it in vacuo at 80 °C for 12 h to obtain the target product.

[0152] Example 8:

[0153] This example provides a synthesis method of 5,5'-((6,6'-bis(2-aminopyrimidin-5-yl)-[1,1'-binaphthalene]-2,2'-diyl)bis(oxy))bis(1-(3-acetyl-1H-pyrrol-1-yl)pentan-3-one), and the synthesis steps are as follows:

[0154]

[0155] (1) 14.636 g (60 mmol) of 1,5-dibromopentan-3-one and 100 mL of dry N,N-dimethylformamide were added to a dry three-necked flask. The temperature was lowered to 0 °C, 3.927 g (70 mmol) of potassium hydroxide was added, and the mixture was stirred at a constant temperature while nitrogen was introduced for protection. 1.637 g (15 mmol) of 3-acetyl-1H-pyrrole and 10 mL of N,N-dimethylformamide were mixed into a solution, which was slowly added dropwise. After the addition was completed, the reaction was carried out for 6 h. The reaction solution was concentrated by a rotary evaporator to obtain a crude product. It was purified by silica gel column chromatography. n-Hexane and dichloromethane were selected as the eluents, and elution was carried out with n-hexane:dichloromethane = 1:3 (volume ratio). The product was collected and dried by rotary evaporation to obtain a solid, which was dried in vacuo at 60 °C for 20 h to obtain Product 1. Its structure is as follows:

[0156]

[0157] (2) 1.122 g (10 mmol) of Product 1, 2.665 g (6 mmol) of 6,6'-dibromo-[1,1'-binaphthalene]-2,2'-diol, 1.122 g (20 mmol) of potassium hydroxide and 90 mL of dehydrated N,N-dimethylacetamide were weighed and added to a dry three-necked flask. The mixture was stirred while nitrogen was introduced for protection, and the temperature was raised to 90 °C for reflux, and the reaction was carried out for 18 h. After the reaction was completed, the inorganic salts were removed by suction filtration, and the crude product was collected by vacuum filtration. The crude product was purified by column chromatography using dichloromethane as the mobile phase and silica gel as the stationary phase. The product was collected and dried by rotary evaporation to obtain a solid, which was dried in vacuo at 80 °C for 20 h to obtain Product 2. Its structure is as follows:

[0158]

[0159] (3) 8.257 g (10 mmol) of Product 2 and 3.334 g (24 mmol) of 2-aminopyrimidine-5-boronic acid were weighed and added to a three-necked flask. 30 mL of N,N-dimethylacetamide was added, and then 40 mL of an aqueous solution of potassium hydroxide (2 mol / L) and an appropriate amount of Aliquat 336 were added. The mixture was stirred while nitrogen was introduced for protection. After the temperature was raised to 75 °C, 0.15 g of palladium acetate was added, and the reaction was carried out under reflux for 22 h. The organic phase of the reaction solution was taken, the solvent was removed by rotary evaporation, and the product was purified by column chromatography using ethyl acetate as the mobile phase and silica gel as the stationary phase. The product was collected and dried by rotary evaporation to obtain a solid, which was dried in vacuo at 100 °C for 12 h to obtain the target product.

[0160] Example 9:

[0161] This example provides a method for synthesizing 1-(2-(2-((6,6”-diamino-[2,1':7',2”-ternaphthalen]-3'-yl)oxy)ethoxy)ethyl)-1H-pyrrole-3-carbaldehyde, and the synthesis steps are as follows:

[0162]

[0163] (1) Add 13.915 g (60 mmol) of 1-bromo-2-(2-bromoethoxy)ethane and 200 mL of dry tetrahydrofuran to a dry three-necked flask, cool down to 0 °C, add 9.114 g (60 mmol) of cesium fluoride, stir at a constant temperature and introduce argon for protection. Mix 1.427 g (15 mmol) of 1H-pyrrole-3-carbaldehyde and 10 mL of tetrahydrofuran to form a solution, slowly drip it, and react for 4 h after the dripping is completed. Concentrate the reaction solution by a rotary evaporator to obtain a crude product. Purify it by silica gel column chromatography, use dichloromethane as the mobile phase and silica gel as the stationary phase for column chromatography purification, collect the product and spin-dry it to obtain a solid, and dry it in vacuo at 70 °C for 10 h to obtain Product 1. Its structure is as follows:

[0164]

[0165] (2) Weigh 2.722 g (10 mmol) of Product 1, 4.530 g (15 mmol) of 4,6-dibromonaphthalen-2-ol, 6.076 g (40 mmol) of cesium fluoride and 100 mL of dehydrated tetrahydrofuran and add them to a dry three-necked flask, stir and introduce argon for protection, heat up to 75 °C and reflux for 12 h. After the reaction is completed, filter off the inorganic salts by suction filtration, collect the crude product by vacuum filtration, purify the crude product by silica gel column chromatography using dichloromethane as the mobile phase and silica gel as the stationary phase, collect the product and spin-dry it to obtain a solid, and dry it in vacuo at 80 °C for 15 h to obtain Product 2. Its structure is as follows:

[0166]

[0167] (3) Weigh 4.671 g (10 mmol) of Product 2 and 3.624 g (30 mmol) of 6-aminonaphthalene-2-boronic acid and add them to a three-necked flask, add 100 mL of tetrahydrofuran, then add 30 mL of an aqueous solution of anhydrous sodium carbonate (2 mol / L) and an appropriate amount of Aliquat 336, stir and introduce argon for protection, heat up to 75 °C and then add 0.15 g of [1,1'-bis(diphenylphosphino)ferrocene] dichloropalladium, and reflux and react for 28 h. Take the organic phase of the reaction solution, evaporate the solvent by rotary evaporation, purify it by silica gel column chromatography using ethyl acetate as the mobile phase and silica gel as the stationary phase, and dry it in vacuo at 60 °C for 12 h to obtain the target product.

[0168] Example 10:

[0169] This example provides a synthesis method of 5”-(4-((4-(3-heptyl-1H-pyrrol-1-yl)pentan-2-yl)oxy)phenyl)-[1,1':3',1”:3”,1”':3”',1””-quinquephenyl]-4,4””-diamine. The synthesis steps are as follows:

[0170]

[0171] (1) Add 13.796 g (60 mmol) of 2,4-dibromopentane and 100 mL of dry tetrahydrofuran to a dry three-necked flask. Cool the temperature to 0 °C, add 6.359 g (60 mmol) of sodium carbonate, stir constantly at a constant temperature and introduce argon gas for protection. Mix 3.586 g (20 mmol) of 3-octyl-1H-pyrrole and 10 mL of tetrahydrofuran to form a solution, and slowly add it dropwise. After the addition is completed, react for 5 h. Concentrate the reaction solution by a rotary evaporator to obtain a crude product. Purify it by silica gel column chromatography. Select n-hexane and dichloromethane as eluents, and elute successively with n-hexane:dichloromethane = 1:1, 1:2 (volume ratio). Collect the product and spin it dry to obtain a solid, and dry it in vacuo at 100 °C for 6 h to obtain Product 1. Its structure is as follows:

[0172]

[0173] (2) Weigh 2.722 g (10 mmol) of Product 1, 4.584 g (12 mmol) of 3',5'-dibromo-[1,1'-biphenyl]-4-ol, 2.240 g (40 mmol) of sodium carbonate and 100 mL of dehydrated tetrahydrofuran and add them to a dry three-necked flask. Stir and introduce argon gas for protection, heat up to 80 °C and reflux for 16 h. After the reaction is completed, filter off the inorganic salts by suction filtration, collect the crude product by vacuum filtration. Purify the crude product by column chromatography using dichloromethane as the mobile phase and silica gel as the stationary phase. Collect the product and spin it dry to obtain a solid, and dry it in vacuo at 120 °C for 11 h to obtain Product 2. Its structure is as follows:

[0174]

[0175] (3) Weigh 4.913 g (10 mmol) of product 2 and 4.687 g (22 mmol) of 3'-aminobiphenyl-4-boronic acid and add them to a three-necked flask. Add 70 mL of tetrahydrofuran, then add 35 mL of an aqueous solution of sodium carbonate (2 mol / L) and an appropriate amount of Aliquat 336. Stir and purge with argon. After heating to 90 °C, add 0.15 g of dichloropalladium bis(acetonitrile). Reflux for 20 h. Take the organic phase of the reaction solution, rotary evaporate to remove the solvent, and purify by column chromatography with ethyl acetate as the mobile phase and silica gel as the stationary phase. Dry in vacuo at 80 °C for 12 h to obtain the target product.

[0176] Example 11:

[0177] This example provides a synthesis method of methyl 1-(3-((2',5'-bis(5-aminonaphthalen-1-yl)-[1,1'-biphenyl]-4-yl)oxy)-2-methoxypropyl)-1H-pyrrole-3-carboxylate. The synthesis steps are as follows:

[0178]

[0179] (1) Add 13.915 g (60 mmol) of 1,3-dibromo-2-methoxypropane and 120 mL of dry tetrahydrofuran to a dry three-necked flask. Cool to -5 °C, add 2.16 g (90 mmol) of sodium hydride, stir at a constant temperature and purge with argon. Mix 2.503 g (20 mmol) of methyl 1H-pyrrole-3-carboxylate and 10 mL of tetrahydrofuran to form a solution, and slowly add it dropwise. After the addition is complete, react for 7 h. Concentrate the reaction solution by rotary evaporator to obtain a crude product. Purify by silica gel column chromatography, select n-hexane and dichloromethane as eluents, and elute successively with n-hexane:dichloromethane = 1:2, 1:4 (volume ratio). Collect the product and rotary dry to obtain a solid. Dry in vacuo at 100 °C for 6 h to obtain product 1. Its structure is as follows:

[0180]

[0181] (2) Weigh 2.761 g (10 mmol) of product 1, 4.264 g (13 mmol) of 2',5'-dibromo-[1,1'-biphenyl]-4-ol, 2.883 g (30 mmol) of sodium tert-butoxide and 100 mL of dehydrated tetrahydrofuran and add them to a dry three-necked flask. Stir and purge with argon. Heat to 75 °C and reflux for 12 h. After the reaction is completed, filter off the inorganic salts by suction filtration, collect the crude product by vacuum filtration, purify the crude product by column chromatography with dichloromethane as the mobile phase and silica gel as the stationary phase, collect the product and rotary dry to obtain a solid. Dry in vacuo at 100 °C for 10 h to obtain product 2. Its structure is as follows:

[0182]

[0183] (3) Weigh 5.232 g (10 mmol) of product 2 and 4.301 g (23 mmol) of 5-aminonaphthalene-1-boronic acid and add them to a three-necked flask. Add 50 mL of tetrahydrofuran, then add 30 mL of an aqueous solution of anhydrous potassium carbonate (2 mol / L) and an appropriate amount of Aliquat 336. Stir and purge with argon. After heating to 90 °C, add 0.15 g of bis(triphenylphosphine)palladium dichloride and reflux for 22 h. Take the organic phase of the reaction solution, rotary evaporate to remove the solvent, perform column chromatography purification using ethyl acetate as the mobile phase and silica gel as the stationary phase, collect the product and rotary dry to obtain a solid, and dry it in vacuo at 80 °C for 12 h to obtain the target product.

[0184] Example 12:

[0185] This example provides a method for synthesizing 2-(3-(3-ethyl-1H-pyrrol-1-yl)propoxy)benzene-1,4-diamine, and the synthesis steps are as follows:

[0186]

[0187] (1) Add 12.113 g (60 mmol) of 1,3-dibromopropane and 100 mL of dry ethanol to a dry three-necked flask. Cool to 0 °C, add 2.16 g (90 mmol) of sodium hydride, stir at a constant temperature and purge with argon. Mix 1.903 g (20 mmol) of 3-ethyl-1H-pyrrole and 10 mL of ethanol to form a solution, and slowly add it dropwise. After the addition is complete, react for 4 h. Concentrate the reaction solution by rotary evaporator to obtain a crude product. Purify it by silica gel column chromatography, select n-hexane and dichloromethane as the eluent, elute with n-hexane:dichloromethane = 1:1, collect the product and rotary dry to obtain a solid, and dry it in vacuo at 80 °C for 10 h to obtain product 1. Its structure is as follows:

[0188]

[0189] (2) Weigh 2.161 g (10 mmol) of product 1, 1.614 g (13 mmol) of 2,5-diaminophenol, 2.883 g (30 mmol) of sodium tert-butoxide and 100 mL of dehydrated ethanol and add them to a dry three-necked flask. Stir and purge with argon. Heat to 75 °C and reflux for 12 hours. After the reaction is completed, filter off the inorganic salts by suction filtration, collect the crude product by vacuum filtration, perform column chromatography purification on the crude product using dichloromethane as the mobile phase and silica gel as the stationary phase, collect the product and rotary dry to obtain a solid, and dry it in vacuo at 90 °C for 12 h to obtain the target product.

[0190] Example 13:

[0191] This example provides a synthesis method of 3,3'-bis(3-(3,4-dimethyl-1H-pyrrol-1-yl)-2-methylpropoxy)-[1,1'-biphenyl]-4,4'-diamine. The synthesis steps are as follows:

[0192]

[0193] (1) Add 12.955 g (60 mmol) of 1,3-dibromo-2-methylpropane and 100 mL of dry tetrahydrofuran to a dry three-necked flask. Cool the temperature to 0 °C, add 1.44 g (60 mmol) of sodium hydride, stir at a constant temperature and introduce argon for protection. Mix 1.427 g (15 mmol) of 3,4-dimethyl-1H-pyrrole and 10 mL of tetrahydrofuran to form a solution, and slowly add the solution dropwise. After the addition is completed, react for 5 h. Concentrate the reaction solution by a rotary evaporator to obtain a crude product. Purify it by silica gel column chromatography, select n-hexane and dichloromethane as eluents, elute with n-hexane:dichloromethane = 1:1, collect the product and spin-dry it to obtain a solid, and dry it in vacuo at 80 °C for 10 h to obtain Product 1. Its structure is as follows:

[0194]

[0195] (2) Weigh 2.301 g (10 mmol) of Product 1, 1.514 g (7 mmol) of 4,4'-diamino-[1,1'-biphenyl]-3,3'-diol, 3.366 g (30 mmol) of potassium tert-butoxide and 100 mL of dehydrated ethanol and add them to a dry three-necked flask. Stir and introduce argon for protection, heat up to 90 °C and reflux for 12 hours. After the reaction is completed, filter off the inorganic salts by suction filtration, collect the crude product by vacuum filtration, purify the crude product by column chromatography using dichloromethane as the mobile phase and silica gel as the stationary phase, collect the product and spin-dry it to obtain a solid, and dry it in vacuo at 100 °C for 15 h to obtain the target product.

[0196] Example 14:

[0197] This example provides a synthesis method of 1,5-bis((3-(1H-pyrrol-1-yl)butan-2-yl)oxy)-4,8-diaminoanthracene-9,10-dione. The synthesis steps are as follows:

[0198]

[0199] (1) Add 12.955 g (60 mmol) of 2,3-dibromobutane and 90 mL of dry N,N-dimethylformamide to a dry three-necked flask. Cool the temperature to 0 °C, add 5.765 g (90 mmol) of n-butyllithium, stir at a constant temperature and introduce argon for protection. Mix 1.006 g (15 mmol) of 1H-pyrrole and 10 mL of N,N-dimethylformamide to form a solution, and slowly add it dropwise. After the addition is completed, react for 4 h. Concentrate the reaction solution by a rotary evaporator to obtain a crude product. Purify it by silica gel column chromatography, select dichloromethane as the eluent, wash it with dichloromethane, collect the product and spin-dry it to obtain a solid, and dry it in vacuo at 80 °C for 10 h to obtain Product 1. Its structure is as follows:

[0200]

[0201] (2) Weigh 2.021 g (10 mmol) of Product 1, 2.162 g (8 mmol) of 1,5-diamino-4,8-dihydroxyanthracene-9,10-dione, 3.366 g (30 mmol) of potassium tert-butoxide and 100 mL of N,N-dimethylformamide and add them to a dry three-necked flask. Stir and introduce argon for protection, heat up to 100 °C and reflux for 12 hours. After the reaction is completed, filter off the inorganic salts by suction filtration, collect the crude product by vacuum filtration. Purify the crude product by column chromatography with dichloromethane as the mobile phase and silica gel as the stationary phase, collect the product and spin-dry it to obtain a solid, and dry it in vacuo at 80 °C for 12 h to obtain the target product.

[0202] Example 15:

[0203] In a clean room, add 1.5901 g (4 mmol) of 4-(4-(1H-pyrrol-1-yl)butoxy)-3-(aminomethyl)aniline and 16 mL of dry N,N-dimethylformamide to a round-bottom flask under argon protection. After stirring to dissolve it, add 1.7770 g (4 mmol) of 4,4′-(hexafluoroisopropylidene)diphthalic anhydride, and the solid content is about 20%. React at 0 °C for 8 h to obtain the corresponding polyamic acid (PAA) colloidal solution.

[0204] Add 4.8 mmol of triethylamine to the obtained PAA colloidal solution to completely ionize the PAA. Add 80 mL of dry N,N-dimethylformamide, 3.2203 g (48 mmol) of 1H-pyrrole monomer and 18.1207 g (52 mmol) of sodium dodecylbenzenesulfonate to the ionized PAA colloidal solution and stir evenly. Add the above solution to an electrophoresis device and carry out electrochemical oxidative polymerization for 6 h to obtain crosslinked polyamic acid. Immerse the crosslinked polyamic acid in a mixed solution of acetic anhydride and triethylamine and carry out an imidization reaction at 80 °C for 1 h, and then place it in an oven at 80 °C for drying to obtain the intrinsic conductive crosslinked PI.

[0205] The molecular structural formula of the intrinsic conductive crosslinked PI in this embodiment is as follows:

[0206]

[0207] Example 16:

[0208] In a clean room, 1.6462 g (4 mmol) of 5'-((5-(1H-pyrrol-1-yl)pentyl)oxy)-[1,1':3',1”-terphenyl]-4,4”-diamine and 20 mL of dry N,N-dimethylformamide were added to a round-bottom flask under argon protection. After stirring to dissolve it, 1.7770 g (4 mmol) of 4,4′-(hexafluoroisopropylidene)diphthalic anhydride was added, and the solid content was about 15%. The reaction was carried out at 0 °C for 8 h to obtain the corresponding polyamic acid (PAA) solution.

[0209] 4.8 mmol of triethylamine was added to the obtained PAA solution to completely ionize the PAA. 80 mL of dry N,N-dimethylformamide, 3.2203 g (48 mmol) of 1H-pyrrole monomer, and 18.1207 g (52 mmol) of sodium dodecylbenzenesulfonate were added to the ionized PAA solution and stirred evenly. The above solution was added to an electrophoresis device for electrochemical oxidative polymerization for 10 h to obtain crosslinked polyamic acid. The crosslinked polyamic acid was soaked in a mixed solution of acetic anhydride and triethylamine, and imidization reaction was carried out at 80 °C for 1 h, and then dried in an oven at 80 °C to obtain the intrinsic conductive crosslinked PI.

[0210] The molecular structural formula of the intrinsic conductive crosslinked PI in this embodiment is as follows:

[0211]

[0212] Example 17:

[0213] In a clean room, 1.7023 g of 5'-((6-(1H-pyrrol-1-yl)hexyl)oxy)-[1,1':3',1”-terphenyl]-4,4”-diamine and 16 mL of dry N,N-dimethylformamide were added to a round-bottom flask under argon protection. After stirring to dissolve it, 1.7770 g (4 mmol) of 4,4′-(hexafluoroisopropylidene)diphthalic anhydride was added, and the solid content was about 18%. The reaction was carried out at 0 °C for 8 h to obtain the corresponding polyamic acid (PAA) solution.

[0214] 4.8 mmol of triethylamine was added to the obtained PAA solution to completely ionize PAA. 80 mL of dry N,N-dimethylformamide, 3.2203 g (48 mmol) of 1H-pyrrole monomer, and 18.1207 g (52 mmol) of sodium dodecylbenzenesulfonate were added to the ionized PAA solution and stirred evenly. The above solution was added to an electrophoresis device, and electrochemical oxidative polymerization was carried out for 12 h to obtain crosslinked polyamic acid. The crosslinked polyamic acid was soaked in a mixed solution of acetic anhydride and triethylamine, and imidization reaction was carried out at 80 °C for 1 h, and then dried in an oven at 80 °C to obtain intrinsic conductive crosslinked PI.

[0215] The molecular structural formula of the intrinsic conductive crosslinked PI in this example is as follows:

[0216]

[0217] Example 18:

[0218] In a clean room, 2.3668 g (4 mmol) of 1-(2-(2-((6,6”-diamino-[2,1':7',2”-ternaphthalen]-3'-yl)oxy)ethoxy)ethyl)-1H-pyrrole-3-carbaldehyde and 21.4 mL of dry N,N-dimethylacetamide were added to a round-bottomed flask under argon protection. After stirring and dissolving it, 1.7770 g (4 mmol) of 4,4,4′-(hexafluoroisopropylidene)diphthalic anhydride was added, and the solid content was about 18%. The reaction was carried out at 0 °C for 8 h to obtain the corresponding polyamic acid (PAA) solution.

[0219] 4 mmol of triethylamine was added to the obtained PAA solution to completely ionize PAA. 80 mL of dry N,N-dimethylacetamide, 3.3627 g (30 mmol) of 3-nitro-1H-pyrrole, and 5.7636 g (30 mmol) of citric acid were added to the ionized PAA solution and stirred evenly. The above solution was added to an electrophoresis device, and electrochemical oxidative polymerization electrophoresis was carried out for 15 h to obtain crosslinked polyamic acid by oxidative polymerization. The crosslinked polyamic acid was soaked in a mixed solution of acetic anhydride and triethylamine, and imidization reaction was carried out at 100 °C for 2 h, and then dried in an oven at 90 °C to obtain intrinsic conductive crosslinked PI. The molecular structural formula of the intrinsic conductive crosslinked PI in this example is as follows:

[0220]

[0221] Example 19:

[0222] In a clean room, 3.4200 g (4 mmol) of 5,5'-((6,6'-bis(2-aminopyrimidin-5-yl)-[1,1'-binaphthalene]-2,2'-diyl)bis(oxy))bis(1-(3-acetyl-1H-pyrrol-1-yl)pentan-3-one) and 28.1 mL of dry N,N-dimethylformamide were added to a round-bottom flask under argon protection. After stirring to dissolve it, 1.2889 g (4 mmol) of 3,3',4,4'-benzophenonetetracarboxylic dianhydride was added, and the solid content was about 15%. The reaction was carried out at -10 °C for 24 h to obtain the corresponding polyamic acid (PAA) colloidal solution.

[0223] 4.8 mmol of triethylamine was added to the obtained PAA colloidal solution to completely ionize the PAA. 50 mL of dry N,N-dimethylformamide, 1.9469 g (24 mmol) of 3-methyl-1H-pyrrole, and 8.3634 g (24 mmol) of sodium dodecylbenzenesulfonate were added to the ionized PAA colloidal solution and stirred evenly. The above solution was added to an electrophoresis device, and electrochemical oxidative polymerization electrophoresis was carried out for 8 h to obtain crosslinked polyamic acid.

[0224] The obtained crosslinked polyamic acid was placed in a vacuum oven for thermal imidization. The temperature-rising program was as follows: from room temperature to 100 °C and then held at a constant temperature for 1 h, from 100 °C to 200 °C and then held at a constant temperature for 1 h, from 200 °C to 300 °C and then held at a constant temperature for 1 h, from 300 °C to 350 °C and then held at a constant temperature for 0.5 h. After cooling, the intrinsic conductive crosslinked PI could be taken out.

[0225] The molecular structural formula of the intrinsic conductive crosslinked PI in this example is as follows:

[0226]

[0227] Example 20:

[0228] In a clean room, 2.5891 g (4 mmol) of methyl 1-(3-((2',5'-bis(5-aminonaphthalen-1-yl)-[1,1'-biphenyl]-4-yl)oxy)-2-methoxypropyl)-1H-pyrrole-3-carboxylate and 26.6 mL of dry N,N-dimethylformamide were added to a round-bottom flask under argon protection. After stirring to dissolve it, 1.1769 g (4 mmol) of [5,5'-diisobenzofuran]-1,1',3,3'-tetrone was added, and the solid content was about 13%. The reaction was carried out at -5 °C for 24 h to obtain the corresponding polyamic acid (PAA) colloidal solution.

[0229] The obtained PAA solution was subjected to an imidization reaction using the chemical imidization method. Acetic anhydride and pyridine were added to the PAA solution, and after stirring at 100 °C for 1.5 h, it was poured into ethanol to precipitate a solid. The obtained solid was placed in an oven and dried at 90 °C, and PI was obtained after cooling.

[0230] The obtained PI and 3.5581 g (32 mmol) of 3-ethyl-1H-pyrrole were dissolved in 100 mL of N,N-dimethylformamide, stirred at 0 °C, and 11.3341 g (32 mmol) of iron(III) perchlorate and 3.1385 g (32 mmol) of sulfuric acid were added. The reaction was carried out for 2 h to obtain a conductive crosslinked PI.

[0231] The molecular structural formula of the intrinsic conductive crosslinked PI in this example is as follows:

[0232]

[0233] Example 21:

[0234] In a clean room, 0.1504 g (0.2 mmol) of 5”-(4-((4-(3-heptyl-1H-pyrrol-1-yl)pentan-2-yl)oxy)phenyl)-[1,1':3',1”:3”,1”':3”',1””-quinquephenyl]-4,4””-diamine and 1.2169 g (3.8 mmol) of 2,2-bis(trifluoromethyl)benzidine diamine were added to a round-bottom flask under argon protection. 9.4 mL of dry N,N-dimethylformamide was added, and after stirring to dissolve it, 0.8725 g (4 mmol) of pyromellitic dianhydride was added, and the solid content was about 20%. The reaction was carried out at -10 °C for 36 h to obtain the corresponding polyamic acid (PAA) solution.

[0235] Ethanol was added to the obtained polyamic acid solution to precipitate polyamic acid powder, and then the polyamic acid powder was placed in a vacuum oven for thermal imidization. The temperature increase program was: from room temperature to 100 °C and kept at a constant temperature for 1 h, from 100 °C to 200 °C and kept at a constant temperature for 1 h, from 200 °C to 300 °C and kept at a constant temperature for 1 h, from 300 °C to 350 °C and kept at a constant temperature for 1 h. After cooling, it could be taken out to obtain PI.

[0236] The obtained PI and 2.6836 g (40 mmol) of 1H-pyrrole monomer were dissolved in 100 mL of N,N-dimethylformamide, stirred at 0 °C, and 10.9536 g (48 mmol) of ammonium persulfate and 13.939 g (40 mmol) of sodium dodecylbenzenesulfonate were added. The reaction was carried out for 1 h to obtain a conductive crosslinked PI.

[0237] The molecular structural formula of the intrinsic conductive cross-linked PI in this example is as follows:

[0238]

[0239] Example 22:

[0240] In a clean room, 0.2591 g (0.4 mmol) of methyl 1-(3-((2',5'-bis(5-aminonaphthalen-1-yl)-[1,1'-biphenyl]-4-yl)oxy)-2-methoxypropyl)-1H-pyrrole-3-carboxylate and 0.3173 g (3.6 mmol) of 1,4-diaminobutane were added to a round-bottom flask under argon protection. 11.6 mL of dry N,N-dimethylformamide was added, and after stirring to dissolve it, 1.8329 g (4 mmol) of 9,9-bis(trifluoromethyl)-2,3,6,7-xanthene tetracarboxylic dianhydride was added. The solid content was about 18%, and the reaction was carried out at 0 °C for 48 h to obtain the corresponding polyamic acid (PAA) colloidal solution.

[0241] The obtained PAA colloidal solution was subjected to an imidization reaction by chemical imidization method. Acetic anhydride and triethylamine were added to the PAA colloidal solution, and after stirring at 25 °C for 2 h, it was poured into methanol to precipitate a solid. The obtained solid was dried in an oven at 100 °C and cooled to obtain PI.

[0242] The obtained PI and 4.4836 g (40 mmol) of 3-nitro-1H-pyrrole monomer were dissolved in 100 mL of N,N-dimethylformamide, stirred at 0 °C, 9.1280 g (40 mmol) of ammonium persulfate and 13.939 g (40 mmol) of sodium dodecylbenzenesulfonate were added, and the reaction was carried out for 3 h to obtain conductive cross-linked PI.

[0243] The molecular structural formula of the intrinsic conductive cross-linked PI in this example is as follows:

[0244]

[0245] Example 23:

[0246] In a clean room, 1.0374 g (4 mmol) of 2-(3-(3-ethyl-1H-pyrrol-1-yl)propoxy)benzene-1,4-diamine and 12.6 mL of dry N,N-dimethylformamide were added to a round-bottom flask under argon protection. After stirring to dissolve it, 1.0727 g (4 mmol) of 1,4,5,8-naphthalenetetracarboxylic dianhydride was added, with a solid content of about 15%. The reaction was carried out at -5 °C for 48 h to obtain the corresponding polyamic acid (PAA) colloidal solution.

[0247] The obtained PAA colloidal solution was subjected to an imidization reaction by chemical imidization. Acetic anhydride and triethylamine were added to the PAA colloidal solution, and after stirring at 100 °C for 2 h, it was poured into methanol to precipitate a solid. The obtained solid was placed in an oven and dried at 100 °C, and PI was obtained after cooling.

[0248] The obtained PI and 2.6836 g (40 mmol) of 1H-pyrrole were dissolved in 100 mL of N,N-dimethylformamide, stirred at 0 °C, and 9.1280 g (40 mmol) of ammonium persulfate and 12.545 g (36 mmol) of sodium dodecylbenzenesulfonate were added, and the reaction was carried out for 4 h to obtain conductive cross-linked PI.

[0249] The molecular structural formula of the intrinsic conductive cross-linked PI in this example is as follows:

[0250]

[0251] Example 24:

[0252] In a clean room, 2.0504 g (4 mmol) of 1,5-bis((3-(1H-pyrrol-1-yl)butan-2-yl)oxy)-4,8-diaminoanthracene-9,10-dione and 14.2 mL of dry N,N-dimethylformamide were added to a round-bottom flask under argon protection. After stirring to dissolve it, 1.2409 g (4 mmol) of 4,4'-biphenylene dianhydride was added, with a solid content of about 19%. The reaction was carried out at -5 °C for 72 h to obtain the corresponding polyamic acid (PAA) colloidal solution.

[0253] The obtained PAA colloidal solution was subjected to an imidization reaction by chemical imidization. Acetic anhydride and triethylamine were added to the PAA colloidal solution, and after stirring at 50 °C for 2 h, it was poured into methanol to precipitate a solid. The obtained solid was placed in an oven and dried at 100 °C, and PI was obtained after cooling.

[0254] The obtained PI was dissolved in 100 mL of N,N-dimethylformamide together with 3.8938 g (48 mmol) of 3-methyl-1H-pyrrole, stirred at 0 °C, and 9.1280 g (40 mmol) of ammonium persulfate and 16.727 g (48 mmol) of sodium dodecylbenzenesulfonate were added. The reaction was carried out for 1 h to obtain a conductive cross-linked PI.

[0255] The molecular structural formula of the intrinsic conductive cross-linked PI in this example is as follows:

[0256]

[0257] In addition, Comparative Example 1 and Comparative Example 2 were prepared based on Example 15, as follows:

[0258] Comparative Example 1: In a clean room, 1.5901 g (4 mmol) of 4-(4-(1H-pyrrol-1-yl)butoxy)-3-(aminomethyl)aniline and 16 mL of dry N,N-dimethylformamide were added to a round-bottom flask under argon protection. After stirring to dissolve it, 1.7770 g (4 mmol) of 4,4′-(hexafluoroisopropylidene)diphthalic anhydride was added, and the solid content was about 20%. The reaction was carried out at 0 °C for 8 h to obtain the corresponding polyamic acid (PAA) solution.

[0259] The obtained PAA solution was subjected to an imidization reaction using the chemical imidization method. Acetic anhydride and triethylamine were added to the PAA solution, and after stirring at 80 °C for 1 h, it was poured into ethanol to precipitate a solid. The obtained solid was dried in an oven at 80 °C and cooled to obtain PI.

[0260] The molecular structural formula of the PI in this comparative example is as follows:

[0261]

[0262] Comparative Example 2: In a clean room, 1.5901 g (4 mmol) of 4-(4-(1H-pyrrol-1-yl)butoxy)-3-(aminomethyl)aniline and 16 mL of dry N,N-dimethylformamide were added to a round-bottom flask under argon protection. After stirring to dissolve it, 1.7770 g (4 mmol) of 4,4′-(hexafluoroisopropylidene)diphthalic anhydride was added, and the solid content was about 20%. The reaction was carried out at 0 °C for 8 h to obtain the corresponding polyamic acid (PAA) solution. The obtained PAA solution was subjected to an imidization reaction using the chemical imidization method. Acetic anhydride and triethylamine were added to the PAA solution, and after stirring at 80 °C for 1 h, it was poured into ethanol to precipitate a solid. The obtained solid was dried in an oven at 80 °C and cooled to obtain PI.

[0263] Dissolve 3.2203 g (48 mmol) of 1H-pyrrole monomer in 100 mL of dry N,N-dimethylformamide, add 18.1207 g (52 mmol) of sodium dodecylbenzenesulfonate, stir evenly, add the above solution to an electrophoresis device, carry out electrochemical oxidative polymerization for 6 h, and dry to obtain polypyrrole.

[0264] Disperse the obtained PI and polypyrrole in 30 mL of dry N,N-dimethylformamide, stir evenly, coat the solution on a glass plate, and dry to obtain a PI / polypyrrole blend material.

[0265] In addition, Comparative Example 3 and Comparative Example 4 were prepared based on Example 16, as follows:

[0266] Comparative Example 3: In a clean room, add 1.6462 g (4 mmol) of 5'-((5-(1H-pyrrol-1-yl)pentyl)oxy)-[1,1':3',1”-terphenyl]-4,4”-diamine and 20 mL of dry N,N-dimethylformamide to a round-bottom flask under argon protection. After stirring to dissolve it, add 1.7770 g (4 mmol) of 4,4′-(hexafluoroisopropylidene)diphthalic anhydride, with a solid content of about 15%, and react at 0 °C for 8 h to obtain the corresponding polyamic acid (PAA) colloidal solution.

[0267] Carry out an imidization reaction on the obtained PAA colloidal solution by chemical imidization method. Add acetic anhydride and triethylamine to the PAA colloidal solution, stir at 80 °C for 1 h, then pour it into methanol to precipitate a solid. Put the obtained solid in an oven and dry it at 80 °C, and cool to obtain PI.

[0268] The molecular structural formula of PI in this comparative example is as follows:

[0269]

[0270] Comparative Example 4: In a clean room, 1.6462 g (4 mmol) of 5'-((5-(1H-pyrrol-1-yl)pentyl)oxy)-[1,1':3',1”-terphenyl]-4,4”-diamine and 20 mL of dry N,N-dimethylformamide were added to a round-bottom flask under argon protection. After stirring to dissolve it, 1.7770 g (4 mmol) of 4,4′-(hexafluoroisopropylidene)diphthalic anhydride was added, and the solid content was about 15%. The reaction was carried out at 0 °C for 8 h to obtain the corresponding polyamic acid (PAA) solution. The obtained PAA solution was subjected to an imidization reaction by chemical imidization method. Acetic anhydride and triethylamine were added to the PAA solution. After stirring at 80 °C for 1 h, it was poured into ethanol to precipitate a solid. The obtained solid was dried in an oven at 80 °C and cooled to obtain PI.

[0271] 3.2203 g (48 mmol) of 1H-pyrrole monomer was dissolved in 100 mL of dry N,N-dimethylformamide, and 18.1207 g (52 mmol) of sodium dodecylbenzenesulfonate was added. After stirring evenly, the above solution was added to an electrophoresis device for electrochemical oxidative polymerization for 10 h, and then dried to obtain polypyrrole.

[0272] The above-obtained PI and polypyrrole were dispersed in 30 mL of dry N,N-dimethylformamide, stirred evenly, and the solution was coated on a glass plate and dried to obtain a PI / polypyrrole blend material.

[0273] In addition, Comparative Example 5 and Comparative Example 6 were prepared based on Example 17, as follows:

[0274] Comparative Example 5: In a clean room, 1.7023 g (4 mmol) of 5'-((6-(1H-pyrrol-1-yl)hexyl)oxy)-[1,1':3',1”-terphenyl]-4,4”-diamine and 16 mL of dry N,N-dimethylformamide were added to a round-bottom flask under argon protection. After stirring to dissolve it, 1.7770 g (4 mmol) of 4,4′-(hexafluoroisopropylidene)diphthalic anhydride was added, and the solid content was about 18%. The reaction was carried out at 0 °C for 8 h to obtain the corresponding polyamic acid (PAA) solution.

[0275] The obtained PAA solution was subjected to an imidization reaction by chemical imidization method. Acetic anhydride and triethylamine were added to the PAA solution. After stirring at 80 °C for 1 h, it was poured into ethanol to precipitate a solid. The obtained solid was dried in an oven at 80 °C and cooled to obtain PI.

[0276] The molecular structural formula of PI in this comparative example is as follows:

[0277]

[0278] Comparative Example 6: In a clean room, 1.7023 g (4 mmol) of 5'-((6-(1H-pyrrol-1-yl)hexyl)oxy)-[1,1':3',1”-terphenyl]-4,4”-diamine and 16 mL of dry N,N-dimethylformamide were added to a round-bottom flask under argon protection. After stirring to dissolve it, 1.7770 g (4 mmol) of 4,4′-(hexafluoroisopropylidene)diphthalic anhydride was added, and the solid content was about 18%. The reaction was carried out at 0 °C for 8 h to obtain the corresponding polyamic acid (PAA) solution. The obtained PAA solution was subjected to imidization reaction by chemical imidization method. Acetic anhydride and triethylamine were added to the PAA solution, and after stirring at 80 °C for 1 h, it was poured into ethanol to precipitate a solid. The obtained solid was dried in an oven at 80 °C and cooled to obtain PI.

[0279] 3.2203 g (48 mmol) of 1H-pyrrole monomer was dissolved in 100 mL of dry N,N-dimethylformamide, 18.1207 g (52 mmol) of sodium dodecylbenzenesulfonate was added, and it was stirred evenly at 0 °C. The above solution was added to an electrophoresis device for electrochemical oxidative polymerization for 12 h, and then dried to obtain polypyrrole.

[0280] The above-obtained PI and polypyrrole were dispersed in 30 mL of dry N,N-dimethylformamide, stirred evenly, and the solution was coated on a glass plate and dried to obtain a PI / polypyrrole blend material.

[0281] The thermal properties and conductivity of the conductive crosslinked PI prepared in Examples 15-24 and the samples of Comparative Examples 1-6 were detected, and the results are shown in Table 1 below. The test methods are as follows:

[0282] Thermogravimetric analysis (TGA): The TGA55 thermogravimetric analyzer of TA Company in the United States was used to test the weight change of the sample during the heating process. Before the test, the TGA instrument was calibrated for weight. The sample was placed in a high-temperature resistant platinum weighing pan according to the specification of an effective weight of 3 mg - 10 mg. The test atmosphere was N2 environment, the heating rate was 20 °C / min, and the test temperature range was 25 - 800 °C.

[0283] Conductivity test: The ST-2258C multi-functional digital four-probe tester of Suzhou Jingge Electronics Co., Ltd. was used to test the conductivity σ of the sample. The test atmosphere was air environment, and the probe spacing was 2 mm.

[0284] Table 1 Thermal properties and conductive properties of the samples of Examples 15-24 and Comparative Examples 1-6

[0285]

[0286]

[0287] As can be seen from Table 1, compared with the comparative example, the intrinsic conductive crosslinked PI prepared by the present invention has excellent heat resistance and electrical conductivity.

[0288] Obviously, the above-mentioned embodiments of the present invention are merely examples for clearly explaining the present invention, rather than limitations on the implementation manners of the present invention. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to enumerate all the implementation manners here. Any modifications, equivalent replacements, and improvements made within the spirit and principle of the present invention shall be included within the protection scope of the claims of the present invention.

Claims

1. An intrinsic conductive crosslinked polyimide, characterized in that, The conductive crosslinked polyimide is formed by polymerizing a diamine monomer containing a pyrrole ring side group and a dianhydride monomer to form a polyamic acid containing a pyrrole ring side group, and then through imidization and oxidative polymerization. The general molecular structure formula is one of the following general structure formulas: Where: m is 5 to 10000, n is 0 to 10000, a is 0 to 200, b is 4 to 200, c is 0 to 200, s is 1 to 10000; When the general molecular structure formula is (Ⅰ), X is selected from one of the following general structure formulas: * represents the connection position; Where M is any one of the following structural formulas: * represents the connection position, where the ether bond is connected to R2, and the other bonds are connected to the imide ring; Where Q is any one of the following structural formulas: * represents the connection position, where the ether bond is connected to R2, and the other bonds are connected to R1, and R1 is connected to the imide ring; Where R1 is any one of the following structural formulas: * represents the connection position; When the general molecular structure formula is (Ⅱ), X is selected from one of the following general structure formulas: * represents the connection position; Where A is any one of the following structural formulas: * represents the connection position, where the ether bond is connected to R2, and the other bonds are connected to the imide ring; Where E is any one of the following structural formulas: * represents the connection position, where the ether bond is connected to R2, and the other bonds are connected to R1, and R1 is connected to the imide ring; Where R1 is any one of the following structural formulas: * represents the connection position; Where R2 is any one of the following structural formulas: * represents the connection position, where: q is 1 to 7; Where R3 is one or more of the following structural formulas: * represents the connection position; Where Y is selected from one or more of the following structures: * represents the connection position; Where Z is selected from one or more of the following structural formulas: * represents the connection position.

2. The preparation method of an intrinsic conductive crosslinked polyimide according to claim 1, characterized in that The preparation steps include: S1. Preparation of diamine monomer: When the general structure formula of X is (Ⅲ) or (Ⅴ), the preparation steps are as follows: S1-1A. Synthesis of monomer 1: Add the R2 monomer with two bromine group substitutions to the solvent, add a base, dropwise add the solution of the R3 monomer with a hydrogen substitution, perform ice bath, stir and introduce an inert protective gas. After the reaction, purify and dry to obtain monomer 1, and the monomer structure is as follows: S1-2A. Synthesis of diamine monomer 2 or diamine monomer 3: Add the monomer 1 in step S1-1A to the solvent, add a base, and then add the M monomer with one hydrogen and two amino substitutions or the A monomer with two hydrogens and two amino substitutions. Stir and introduce an inert protective gas. After the reaction, purify and dry to obtain the diamine monomer 2 or diamine monomer 3 containing a pyrrole ring side group respectively, and they have the following structural characteristics: When the general structure formula of X is (Ⅳ) or (Ⅵ), the preparation steps are as follows: S1-1B. Synthesis of monomer 4 or monomer 5: Add the monomer 1 in step S1-1A to the solvent, add a base, and then add the Q monomer with one hydrogen and two bromine substitutions or the E monomer with two hydrogens and two bromine substitutions. Stir and introduce an inert protective gas. After the reaction, purify and dry to obtain monomer 4 or monomer 5 respectively, and they have the following structural characteristics: S1-2B. Synthesis of diamine monomer 6 or diamine monomer 7: The monomer 4 or monomer 5 in step S1-1B and the R1 monomer substituted with one amino group and one boric acid are added to a solvent, an alkali is added, stirred, and an inert protective gas is introduced, heated, a catalyst is added and refluxed, and after the reaction, it is purified and dried to obtain the diamine monomer 6 or diamine monomer 7 with pyrrole ring side groups, which have the following structural characteristics: S2. Preparation of polyamic acid with pyrrole ring side groups: The diamine monomer with pyrrole ring side groups obtained in S1 and the dianhydride monomer with Z structure, or the diamine monomer with pyrrole ring side groups, the diamine monomer with Y structure and the dianhydride monomer with Z structure obtained in S1 are dissolved in a strongly polar aprotic organic solvent in proportion, and stirred at a certain temperature for a certain time to obtain a homogeneous and viscous polyamic acid colloidal solution; S3. Preparation of conductive crosslinked polyimide: Any one of the following two methods is used for the preparation of conductive crosslinked polyimide: Method S3(A). The polyamic acid colloidal solution in S2 is imidized to obtain a polyimide with pyrrole ring side groups. The polyimide and one or more R3 monomers substituted with hydrogen are dissolved in a strongly polar aprotic organic solvent in proportion, an oxidant and a dopant are added in proportion, and stirred at a certain temperature for a certain time to obtain an intrinsic conductive crosslinked polyimide by oxidative polymerization; Method S3(B). The polyamic acid colloidal solution obtained in S2 is mixed with triethylamine to ionize the polyamic acid to obtain an ionized polyamic acid with pyrrole ring side groups. The obtained ionized polyamic acid and one or more R3 monomers substituted with hydrogen are dissolved in a strongly polar aprotic organic solvent in proportion, a dopant is added in proportion, and the obtained solution is added to an electrophoresis device for electrochemical oxidative polymerization for a certain time to obtain a conductive crosslinked polyamic acid, and the conductive crosslinked polyamic acid is imidized to obtain an intrinsic conductive crosslinked polyimide.

3. The preparation method of an intrinsic conductive crosslinked polyimide according to claim 2, characterized in that, The inert protective gas in steps S1-1A, S1-2A, S1-1B and S1-2B is one or more of nitrogen, helium, neon, argon, krypton, xenon and radon.

4. The preparation method of an intrinsic conductive crosslinked polyimide according to claim 2, characterized in that, The solvents in steps S1-1A, S1-2A, S1-1B and S1-2B are one or more of tetrahydrofuran, ethanol, dichloromethane, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylacetamide and N,N-dimethylformamide; the strongly polar aprotic organic solvents in step S2 are one or more of N-methylpyrrolidone, dimethyl sulfoxide, dimethyl sulfone, sulfolane, 1,4-dioxane, N,N-dimethylacetamide, N,N-dimethylformamide and m-cresol; the strongly polar aprotic organic solvents in method S3(A) and method S3(B) in step S3 are one or more of N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylacetamide and N,N-dimethylformamide.

5. The preparation method of an intrinsic conductive crosslinked polyimide according to claim 2, wherein, The base described in steps S1-1A, S1-2A, S1-1B, and S1-2B is one or more of sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium fluoride, n-butyllithium, potassium tert-butoxide, sodium tert-butoxide, and lithium hexamethyldisilazide; the R2 monomer containing two bromo substituents in step S1-1A is one of dibromomethane, 1,2-dibromoethane, 1,3-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane, 1,6-dibromohexane, 1,7-dibromoheptane, 2,4-dibromopentane, 2,3-dibromobutane, 2,3-dibromo-2,3-dimethylbutane, 1-bromo-2-(2-bromoethoxy)ethane, 1,5-dibromopentan-3-one, 1,3-dibromo-2-methylpropane, 1-bromo-3-(3-bromopropoxy)propane, 1,3-dibromo-2-methoxypropane; the hydrogen-substituted R3 monomer in steps S1-1A and S3 is selected from 1H-pyrrole, 2-methyl-1H-pyrrole, 2-acetyl-1H-pyrrole, 3-ethyl-1H-pyrrole, 3-cyano-1H-pyrrole, 3-nitro-1H-pyrrole, 3-acetyl-1H-pyrrole, 3,4-diethyl-1H-pyrrole, 3,4-difluoro-1H-pyrrole, 3-nonyl-1H-pyrrole, methyl 1H-pyrrole-3-carboxylate, 3,4-dimethyl-1H-pyrrole, 3-octyl-1H-pyrrole, 1H-pyrrole-3-carbaldehyde, 3-methyl-1H-pyrrole, where the hydrogen-substituted R3 monomer in step S1-1A is one of them, and the hydrogen-substituted R3 monomer in step S3 is one or more of them; the M monomer containing one hydrogen and two amino substituents in step S1-2A is one of 2,6-diaminopyridin-4-ol, 2,5-diaminophenol, 3,4-diaminophenol, and 2-(aminomethyl)-4-aminophenol; the A monomer containing two hydrogens and two amino substituents in step S1-2A is one of 4,6-diaminobenzene-1,3-diol, 2,5-diaminobenzene-1,4-diol, 4,4'-sulfonylbis(2-aminophenol), 5,5'-diamino-[1,1'-biphenyl]-2,2'-diol, 4,4'-diamino-[1,1'-biphenyl]-3,3'-diol, 1,5-diamino-4,8-dihydroxy-9,10-anthracenedione, 1,8-diamino-4,5-dihydroxy-9,10-anthracenedione, 4,4'-(perfluoropropane-2,2-diyl)bis(2-aminophenol); the Q monomer containing one hydrogen and two bromo substituents in step S1-1B is one of 3,5-dibromophenol, 2,5-dibromophenol, 4,6-dibromonaphthalen-2-ol, 1,6-dibromonaphthalen-2-ol, 2',5'-dibromo-[1,1'-biphenyl]-4-ol, 3',5'-dibromo-[1,1'-biphenyl]-4-ol.The E monomer containing two hydrogen and two bromine group substitutions in the step S1-1B is one of 4,5-dibromobenzene-1,2-diol, 3,6-dibromonaphthalene-2,7-diol, 2,5-dibromobenzene-1,4-diol, 6,6'-dibromo-[1,1'-binaphthalene]-2,2'-diol, 3,6-dibromophenanthrene-9,10-diol, 3,3'-dibromo-[1,1'-biphenyl]-4,4'-diol; the R1 monomer containing one amino group and one boric acid substitution in the step S1-2B is one of 4-aminophenylboronic acid, 3-aminophenylboronic acid, 2-aminophenylboronic acid, 6-aminopyridineboronic acid, 2-aminopyrimidine-5-boronic acid, [4-(4-aminophenoxy)phenyl]boronic acid, 4'-aminobiphenyl-4-boronic acid, 3'-aminobiphenyl-4-boronic acid, 4-aminonaphthalene-1-boronic acid, 5-aminonaphthalene-1-boronic acid, 6-aminonaphthalene-2-boronic acid.

6. The preparation method of an intrinsic conductive cross-linked polyimide according to claim 2, characterized in that In step S3, the oxidant described in method S3(A) is one or more of iron oxide, copper chloride, ferric trichloride, ferric perchlorate, ammonium persulfate, and hydrogen peroxide; in step S3, the dopants described in method S3(A) and method S3(B) are one or more of p-toluenesulfonic acid, dodecylbenzenesulfonic acid, hydrochloric acid, nitric acid, sulfuric acid, acetic acid, citric acid, sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, cetyltrimethylammonium bromide, and sodium p-toluenesulfonate.

7. The preparation method of an intrinsic conductive crosslinked polyimide according to claim 2, wherein, In step S1-1A, the amount of the base used is 1 to 1.5 times the amount of substance of the R2 monomer containing two bromo substituents, and the amount of substance of the R2 monomer containing two bromo substituents is 3 to 4 times the amount of substance of the R3 monomer substituted by hydrogen; in steps S1-2A and S1-1B, the amount of the base used is 2 to 4 times the amount of substance of monomer 1, and the amount of substance of the M monomer containing one hydrogen and two amino substituents and the Q monomer containing one hydrogen and two bromo substituents is 1.2 to 1.6 times the amount of substance of monomer 1, and the amount of substance of the A monomer containing two hydrogens and two amino substituents and the E monomer containing two hydrogens and two bromo substituents is 0.6 to 0.8 times the amount of substance of monomer 1; in step S1-2B, the molar ratio of monomer 4 or monomer 5 to the R1 monomer containing one amino and one boric acid substituent is 1:2 to 1:3, and the amount of the base used is 1.5 to 4 times the amount of substance of the R1 monomer containing one amino and one boric acid substituent; in step S2, the molar ratio of the diamine monomer to the dianhydride monomer added is 1:0.9 to 1:1.1, and the total mass of the diamine monomer and the dianhydride monomer accounts for 2 to 50% of the mass of the polyamic acid solution; in step S3, the molar ratio of triethylamine to the diamine monomer described in method S3(B) is 1:1 to 2:1; in step S3, the molar ratio of the R3 monomer substituted by hydrogen to the diamine monomer containing a pyrrole ring side group described in step S2 in method S3(A) and method S3(B) is 4:1 to 200:1; in step S3, the molar ratio of the R3 monomer substituted by hydrogen to the dopant in method S3(A) and method S3(B) is 1:0.8 to 1:1.2; in step S3, the molar ratio of the oxidant to the dopant described in method S3(A) is 1:0.8 to 1:1.

2.

8. The preparation method of an intrinsic conductive crosslinked polyimide according to claim 2, wherein The reaction temperature in step S1-1A is -5 to 0 °C, and the time is 4 to 8 h. The drying temperature is 40 to 120 °C, and the drying time is 6 to 30 h; the temperature in steps S1-2A and S1-1B is 50 to 100 °C, and the time is 12 to 24 h. The drying temperature is 40 to 120 °C, and the drying time is 6 to 30 h; the reaction temperature in step S1-2B is 50 to 120 °C, and the time is 10 to 48 h. The drying temperature is 40 to 120 °C, and the drying time is 6 to 30 h; the temperature of the stirring reaction in step S2 is -20 to 50 °C, and the time is 0.5 to 72 h; the temperature of the stirring reaction in method S3(A) of step S3 is 0 to 50 °C, and the time is 0.5 to 4 h; the time of the electrochemical oxidative polymerization reaction described in method S3(B) of step S3 is 0.5 to 24 h.

9. The preparation method of an intrinsic conductive crosslinked polyimide according to claim 2, characterized in that, In step S3, the imidization described in method S3(A) and method S3(B) is thermal imidization or chemical imidization.

10. The intrinsic conductive crosslinked polyimide according to claim 1, characterized in that, The conductive polyimide is applied to microelectronics, optoelectronics, military, and aerospace.

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