A pyrazine-modified ptaa copolymer and a preparation method thereof
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- CHAIN WALK NEW MATERIAL TECH (GUANGZHOU) CO LTD
- Filing Date
- 2026-04-10
- Publication Date
- 2026-06-19
Smart Images
Figure CN122234355A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of organic polymers, and particularly relates to a pyrazine-modified PTAA copolymer and its preparation method. Background Technology
[0002] Organic conjugated polymers, due to their tunable structure, solution-processability, and excellent semiconductor properties, have shown broad application prospects in devices such as organic photovoltaic cells, organic field-effect transistors, and photodetectors. In donor-acceptor conjugated polymers, intramolecular charge transfer effect is the core factor determining the photoelectric properties of the material. By enhancing intramolecular charge transfer, the optical band gap of the polymer can be effectively narrowed, causing the absorption spectrum to redshift and broaden into the near-infrared region, thereby making fuller use of sunlight. At the same time, a reasonable intramolecular charge transfer design can precisely control the frontier molecular orbital energy levels of the polymer. In addition, the strength of intramolecular charge transfer also affects the pre-aggregation behavior of the polymer in solution, thereby controlling the molecular stacking and phase separation morphology of solid films, ultimately determining the charge transport efficiency and stability of the device.
[0003] However, existing organic conjugated polymers still have limitations in regulating the intensity of intramolecular charge transfer. Traditional polymer systems often struggle to achieve synergistic optimization between spectral absorption, suitable energy levels, and ideal pre-aggregation behavior, resulting in limited photoelectric conversion efficiency of devices. Therefore, developing an organic conjugated polymer that can enhance intramolecular charge transfer and simultaneously coordinate pre-aggregation behavior is a pressing technical problem to be solved in this field. Summary of the Invention
[0004] This invention discloses a pyrazine-modified PTAA copolymer and its preparation method. The polymer contains a pyrazine structure, which can induce non-covalent interactions, promote planar molecular skeletons, and help enhance intramolecular charge transfer and coordinate pre-aggregation behavior. Specifically, the pyrazine structure is an aromatic heterocycle containing two nitrogen atoms, which has significant electron-withdrawing inductive effect and conjugation effect. When it is introduced into PTAA as an acceptor unit, it can form a DA structure with the original triarylamine (donor unit) in PTAA, promoting the migration of electrons from the donor to the acceptor and significantly enhancing the intramolecular charge transfer intensity. At the same time, the nitrogen atoms in the pyrazine ring can also provide additional dipole-dipole interactions or weak hydrogen bonding, which, combined with the strong rigid structure that can form good coplanarity with adjacent aromatic rings, is conducive to the linear extension of the polymer backbone and promotes the formation of pre-aggregates with moderate size and uniform distribution.
[0005] The first objective of this invention is to provide a pyrazine-modified PTAA copolymer, characterized in that the structural formula of the pyrazine-modified PTAA copolymer is shown in formula (I):
[0006] Equation (Ⅰ);
[0007] Wherein, n is 0.5~0.99, preferably 0.7~0.85, for example, it can be 0.71, 0.72, 0.73, 0.74, 0.75, 0.76, 0.77, 0.78, 0.79, 0.80, 0.81, 0.82, 0.83, 0.84. By controlling the relative content of pyrazine structures in the PTAA copolymer within the above range, it is beneficial to enhance intramolecular charge transfer.
[0008] In some embodiments of the present invention, the pyrazine-modified PTAA copolymer has a number-average molecular weight of 8-30 kDa and a PDI of 1.5-4.0. For example, its number-average molecular weight can be 10 kDa, 12 kDa, 14 kDa, 16 kDa, 18 kDa, 20 kDa, 22 kDa, 24 kDa, 26 kDa, or 28 kDa. By controlling the number-average molecular weight of the copolymer within the above range, it is beneficial to enhance intramolecular charge transfer.
[0009] In some embodiments of the present invention, the raw materials for preparing the pyrazine-modified PTAA copolymer include 6-aminoquinoxaline.
[0010] In some embodiments of the present invention, the raw materials for preparing the pyrazine-modified PTAA copolymer further include 2,4,6-trimethylaniline and 4,4'-dibromobiphenyl.
[0011] A second objective of this invention is to provide a method for preparing the above-mentioned pyrazine-modified PTAA copolymer, comprising the following steps:
[0012] Under the action of palladium catalyst and auxiliaries, 6-aminoquinoxaline, 2,4,6-trimethylaniline and 4,4'-dibromobiphenyl undergo a polymerization reaction to obtain the pyrazine-modified PTAA copolymer.
[0013] In some embodiments of the present invention, the sum of the amounts of 6-aminoquinoxaline and 2,4,6-trimethylaniline is n1, the amount of 4,4'-dibromobiphenyl is n2, and the ratio of n1 to n2 is 1:1 to 1.1.
[0014] In some embodiments of the present invention, the molar ratio of 2,4,6-trimethylaniline to 6-aminoquinoxaline is 0.5~0.99:0.01~0.5.
[0015] In some embodiments of the present invention, the molar ratio of the palladium catalyst to the 4,4'-dibromobiphenyl is 0.005 to 0.03:1.
[0016] In some embodiments of the present invention, the structure of the palladium catalyst is shown in formula (II):
[0017] Equation (II), where R 1 R 2 It can be hydrogen, methyl, ethyl, or isopropyl independently, and R 1 R 2 They are not both hydrogen.
[0018] In some embodiments of the present invention, the auxiliary agent includes an organic base and a solvent.
[0019] In some embodiments of the present invention, the molar ratio of the organic base to the 4,4'-dibromobiphenyl is 2 to 4:1.
[0020] In some embodiments of the present invention, the ratio of the solvent to the 4,4'-dibromobiphenyl is 2L~4L:1mol.
[0021] In some embodiments of the present invention, the organic base is selected from potassium tert-butoxide.
[0022] In some embodiments of the present invention, the solvent is selected from toluene.
[0023] In some embodiments of the present invention, the polymerization reaction is carried out at a temperature of 100-120°C for 12-36 hours.
[0024] In some embodiments of the present invention, the polymerization reaction is carried out in an inert gas atmosphere.
[0025] In some embodiments of the present invention, a post-processing step is further included after the polymerization reaction is completed.
[0026] In some embodiments of the present invention, the post-processing step includes a step of precipitation with methanol.
[0027] Compared with the prior art, the present invention has the following beneficial effects: by introducing an appropriate amount of rigid pyrazine structure with significant electron-withdrawing inductive effect and conjugation effect into the PTAA backbone structure, the intramolecular charge transfer of organic conjugated polymer molecules can be significantly enhanced. At the same time, the combination of nitrogen atoms and rigid structure also helps the polymer to form pre-aggregates with moderate size and uniform distribution. Attached Figure Description
[0028] Figure 1 The pyrazine-modified PTAA copolymer prepared in Example 4 of this invention 1 H NMR spectrum. Detailed Implementation
[0029] To enable those skilled in the art to better understand the technical solutions of this invention, the technical solutions of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of this invention.
[0030] All raw materials used in this invention are commercially available.
[0031] The structure of imidazole salt ligand L1 is shown below:
[0032] ;
[0033] The structure of imidazole salt ligand L2 is shown below:
[0034] ;
[0035] The structure of imidazole salt ligand L3 is shown below:
[0036] .
[0037] Example 1
[0038] This embodiment provides a palladium catalyst C1, the preparation method of which includes the following steps:
[0039] Imidazole salt ligand L1 (1.0 mmol), potassium carbonate (10 mmol), and palladium dichloride (1.0 mmol) were added to 10 mL of N-methylimidazole and mixed at room temperature. The mixture was then heated to 80°C and stirred for 12 hours. After the reaction was completed, the liquid was removed under reduced pressure, and the crude product was dissolved in 5 mL of dichloromethane. Subsequently, 20 mL of n-hexane was added, and the resulting palladium complex precipitate was collected by filtration, washed with n-hexane (2 × 20 mL), and dried to obtain a grayish-white palladium catalyst powder C1 with a yield of 81%. The NMR C-H spectrum of palladium catalyst C1 is as follows:
[0040] 1H NMR (400 MHz, CDCl3) δ 7.50 (td, J = 1.6, 0.8 Hz, 1H), 7.12-7.07(m, 5H), 7.00 (dd, J = 5.6, 1.7 Hz, 1H), 6.85-6.81 (m, 4H), 6.60 (s, 4H), 3.82 (s, 6H), 3.72 (d, J = 0.6 Hz, 3H), 2.31 (s, 12H), 2.26 (d, J = 0.7 Hz, 6H).
[0041] 13 C NMR (101 MHz, CDCl3) δ 162.02, 156.48, 133.58, 133.45, 133.24,130.79, 130.15, 129.44, 127.53, 122.13, 116.03, 103.07, 62.77, 55.35, 35.03,21.03, 18.14.
[0042] The structure of palladium catalyst C1 is shown below:
[0043] .
[0044] Example 2
[0045] This embodiment provides a palladium catalyst C2, the preparation method of which includes the following steps:
[0046] Imidazole salt ligand L2 (1.0 mmol), potassium carbonate (8 mmol), and palladium dichloride (1.0 mmol) were added to 8 mL of N-methylimidazole and mixed at room temperature. The mixture was then heated to 70°C and stirred for 16 hours. After the reaction was completed, the liquid was removed under reduced pressure, and the crude product was dissolved in 5 mL of dichloromethane. Subsequently, 20 mL of n-hexane was added, and the resulting palladium complex precipitate was collected by filtration, washed with n-hexane (2 × 20 mL), and dried to obtain a grayish-white palladium catalyst powder C2 with a yield of 76%. The NMR C-H spectrum of palladium catalyst C2 is as follows:
[0047] 1H NMR (400 MHz, CDCl3) δ 7.50 (tt, J = 1.4, 0.7 Hz, 1H), 7.13-7.08(m, 5H), 7.00 (dd, J = 5.6, 1.7 Hz, 1H), 6.87-6.80 (m, 8H), 6.79-6.73 (m,2H), 3.82 (s, 6H), 3.72 (t, J = 0.7 Hz, 3H), 2.50 (qd, J = 7.5, 0.9 Hz, 8H), 1.26 (t, J = 7.5 Hz, 12H).
[0048] 13 C NMR (101 MHz, CDCl3) δ 162.02, 156.48, 141.57, 136.09, 130.79,129.44, 128.76, 127.53, 127.01, 122.13, 116.03, 103.07, 62.77, 55.35, 35.03,24.15, 14.23.
[0049] The structure of palladium catalyst C2 is shown below:
[0050] .
[0051] Example 3
[0052] This embodiment provides a palladium catalyst C3, the preparation method of which includes the following steps:
[0053] Imidazole salt ligand L3 (1.0 mmol), potassium carbonate (12 mmol), and palladium dichloride (1.0 mmol) were added to 12 mL of N-methylimidazole and mixed at room temperature. The mixture was then heated to 90°C and stirred for 10 hours. After the reaction was completed, the liquid was removed under reduced pressure, and the crude product was dissolved in 5 mL of dichloromethane. Subsequently, 20 mL of n-hexane was added, and the resulting palladium complex precipitate was collected by filtration, washed with n-hexane (2 × 20 mL), and dried to obtain a grayish-white palladium catalyst powder C3 with a yield of 74%. The NMR C-H spectrum of palladium catalyst C3 is as follows:
[0054] 1H NMR (400 MHz, CDCl3) δ 7.50 (tt, J = 1.5, 0.7 Hz, 1H), 7.12-7.08(m, 5H), 7.00 (dd, J = 5.6, 1.7 Hz, 1H), 6.94-6.90 (m, 4H), 6.85-6.81 (m,4H), 6.76 (dd, J = 8.8, 7.7 Hz, 2H), 3.82 (s, 6H), 3.72 (t, J = 0.7 Hz, 3H), 2.89 (hd, J = 6.8, 0.7 Hz, 4H), 1.28 (d, J = 6.9 Hz, 24H).
[0055] 13 C NMR (101 MHz, CDCl3) δ 162.02, 156.48, 144.25, 141.09, 130.79,129.44, 127.53, 127.24, 126.60, 122.13, 116.03, 103.07, 62.77, 55.35, 35.03,28.88, 24.04.
[0056] The structure of palladium catalyst C3 is shown below:
[0057] .
[0058] Example 4
[0059] This embodiment provides a pyrazine-modified PTAA copolymer, the preparation method of which includes the following steps:
[0060] 6-Aminoquinoxaline (0.2 mmol), 2,4,6-trimethylaniline (0.8 mmol), 4,4'-dibromobiphenyl (1 mmol), and KO were added to the reactor. t Bu (3 mmol), palladium catalyst C1 (0.02 mmol), and 3 mL of toluene were added, and the mixture was purged with nitrogen and reacted at 110 °C for 24 h. After the reaction was completed, the mixture was cooled to room temperature, added dropwise to methanol to precipitate, washed 2-3 times with methanol, filtered, and dried to obtain the crude polymer. The crude polymer was dissolved in THF, stirred at room temperature for 24 h, filtered, and the filtrate was added dropwise to methanol to precipitate, washed 2-3 times with methanol, filtered, and dried to obtain the yellow polymer, namely the pyrazine-modified PTAA copolymer, the structure of which is shown below:
[0061] .
[0062] Example 5
[0063] This embodiment provides a pyrazine-modified PTAA copolymer, the preparation method of which includes the following steps:
[0064] 6-Aminoquinoxaline (0.1 mmol), 2,4,6-trimethylaniline (0.9 mmol), 4,4'-dibromobiphenyl (1 mmol), and KO were added to the reactor. t Bu (3 mmol), palladium catalyst C2 (0.02 mmol), and 3 mL of toluene were added, and the mixture was purged with nitrogen and reacted at 110 °C for 24 h. After the reaction was complete, the mixture was cooled to room temperature, added dropwise to methanol to precipitate, washed 2-3 times with methanol, filtered, and dried to obtain a crude polymer. The crude polymer was dissolved in THF, stirred at room temperature for 24 h, filtered, and the resulting filtrate was added dropwise to methanol to precipitate, washed 2-3 times with methanol, filtered, and dried to obtain a yellow polymer, namely the pyrazine-modified PTAA copolymer, with the same structure as in Example 4.
[0065] Example 6
[0066] This embodiment provides a pyrazine-modified PTAA copolymer, the preparation method of which includes the following steps:
[0067] 6-Aminoquinoxaline (0.3 mmol), 2,4,6-trimethylaniline (0.7 mmol), 4,4'-dibromobiphenyl (1 mmol), and KO were added to the reactor. t Bu (3 mmol), palladium catalyst C3 (0.02 mmol), and 3 mL of toluene were added, and the mixture was purged with nitrogen and reacted at 110 °C for 24 h. After the reaction was complete, the mixture was cooled to room temperature, added dropwise to methanol to precipitate, washed 2-3 times with methanol, filtered, and dried to obtain a crude polymer. The crude polymer was dissolved in THF, stirred at room temperature for 24 h, filtered, and the resulting filtrate was added dropwise to methanol to precipitate, washed 2-3 times with methanol, filtered, and dried to obtain a yellow polymer, namely the pyrazine-modified PTAA copolymer, with the same structure as in Example 4.
[0068] Example 7
[0069] This embodiment provides a pyrazine-modified PTAA copolymer, the preparation method of which includes the following steps:
[0070] 6-Aminoquinoxaline (0.4 mmol), 2,4,6-trimethylaniline (0.6 mmol), 4,4'-dibromobiphenyl (1 mmol), and KO were added to the reactor. tBu (3 mmol), palladium catalyst C1 (0.02 mmol), and 3 mL of toluene were added, and the mixture was purged with nitrogen and reacted at 110 °C for 24 h. After the reaction was completed, the mixture was cooled to room temperature, added dropwise to methanol to precipitate, washed 2-3 times with methanol, filtered, and dried to obtain a crude polymer. The crude polymer was dissolved in THF, stirred at room temperature for 24 h, filtered, and the resulting filtrate was added dropwise to methanol to precipitate, washed 2-3 times with methanol, filtered, and dried to obtain a yellow polymer, namely the pyrazine-modified PTAA copolymer, with the same structure as in Example 4.
[0071] Example 8
[0072] This embodiment provides a pyrazine-modified PTAA copolymer, the preparation method of which includes the following steps:
[0073] 6-Aminoquinoxaline (0.5 mmol), 2,4,6-trimethylaniline (0.5 mmol), 4,4'-dibromobiphenyl (1 mmol), and KO were added to the reactor. t Bu (3 mmol), palladium catalyst C1 (0.02 mmol), and 3 mL of toluene were added, and the mixture was purged with nitrogen and reacted at 110 °C for 24 h. After the reaction was completed, the mixture was cooled to room temperature, added dropwise to methanol to precipitate, washed 2-3 times with methanol, filtered, and dried to obtain a crude polymer. The crude polymer was dissolved in THF, stirred at room temperature for 24 h, filtered, and the resulting filtrate was added dropwise to methanol to precipitate, washed 2-3 times with methanol, filtered, and dried to obtain a yellow polymer, namely the pyrazine-modified PTAA copolymer, with the same structure as in Example 4.
[0074] Example 9
[0075] This embodiment provides a pyrazine-modified PTAA copolymer, the preparation method of which includes the following steps:
[0076] 6-Aminoquinoxaline (0.2 mmol), 2,4,6-trimethylaniline (0.8 mmol), 4,4'-dibromobiphenyl (1 mmol), and KO were added to the reactor. t Bu (3 mmol), palladium catalyst C1 (0.02 mmol), and 3 mL of toluene were added, and the mixture was purged with nitrogen and reacted at 105 °C for 12 h. After the reaction was completed, the mixture was cooled to room temperature, added dropwise to methanol to precipitate, washed 2-3 times with methanol, filtered, and dried to obtain the crude polymer. The crude polymer was dissolved in THF, stirred at room temperature for 24 h, filtered, and the resulting filtrate was added dropwise to methanol to precipitate, washed 2-3 times with methanol, filtered, and dried to obtain the yellow polymer, namely the pyrazine-modified PTAA copolymer, with the same structure as in Example 4.
[0077] Example 10
[0078] This embodiment provides a pyrazine-modified PTAA copolymer, the preparation method of which includes the following steps:
[0079] 6-Aminoquinoxaline (0.2 mmol), 2,4,6-trimethylaniline (0.8 mmol), 4,4'-dibromobiphenyl (1 mmol), and KO were added to the reactor. t Bu (3 mmol), palladium catalyst C1 (0.02 mmol), and 3 mL of toluene were added, and the mixture was purged with nitrogen and reacted at 110 °C for 36 h. After the reaction was completed, the mixture was cooled to room temperature, added dropwise to methanol to precipitate, washed 2-3 times with methanol, filtered, and dried to obtain the crude polymer. The crude polymer was dissolved in THF, stirred at room temperature for 24 h, filtered, and the resulting filtrate was added dropwise to methanol to precipitate, washed 2-3 times with methanol, filtered, and dried to obtain the yellow polymer, namely the pyrazine-modified PTAA copolymer, with the same structure as in Example 4.
[0080] Comparative Example 1
[0081] This comparative example provides a PTAA polymer, the preparation method of which includes the following steps:
[0082] 2,4,6-trimethylaniline (1 mmol), 4,4'-dibromobiphenyl (1 mmol), and KO were added to the reactor. t Bu (3 mmol), palladium catalyst C1 (0.02 mmol), and 3 mL of toluene were added, and the mixture was purged with nitrogen and reacted at 110 °C for 24 h. After the reaction was completed, the mixture was cooled to room temperature, added dropwise to methanol to precipitate, washed 2-3 times with methanol, filtered, and dried to obtain the crude polymer. The crude polymer was dissolved in THF, stirred at room temperature for 24 h, filtered, and the resulting filtrate was added dropwise to methanol to precipitate, washed 2-3 times with methanol, filtered, and dried to obtain the PTAA polymer, the structure of which is shown below:
[0083] .
[0084] The following tests were performed on the copolymer / polymer obtained above:
[0085] 1. Weigh the pyrazine-modified PTAA copolymers obtained in Examples 4-10 above and the PTAA polymer obtained in Comparative Example 1, and calculate their yields. The results are shown in Table 1.
[0086] 2. GPC analysis was performed on the pyrazine-modified PTAA copolymers obtained in Examples 4-10 and the PTAA polymer obtained in Comparative Example 1 to obtain their number-average molecular weight Mn and molecular weight distribution index PDI. The results are shown in Table 1.
[0087] 3. The pyrazine-modified PTAA copolymers obtained in Examples 4-10 above were subjected to... 1¹H NMR analysis was performed, and the ratio of H on the pyrazine ring (δ 8.6~8.8) to methyl H on the trimethylbenzene ring (δ 1.8~2.6) was integrated to determine the proportion of trimethylbenzene-containing structural units in the copolymer, i.e., the n value in the copolymer structure. The results are shown in Table 1.
[0088] 4. The pyrazine-modified PTAA copolymers obtained in Examples 4-10 and the PTAA polymer obtained in Comparative Example 1 were dissolved in solvents of different polarities (toluene with ℇ=2.38, chloroform with ℇ=4.81, and tetrahydrofuran with ℇ=7.58) to prepare a concentration of 10. -6 A solution of mol / L was prepared, and then the solution was subjected to UV-Vis analysis to determine its absorption edge λ. onset Δλ 1 / 2 and the maximum absorption peak λ max1 The results are shown in Table 2;
[0089] 5. Prepare 10% concentration solutions of the pyrazine-modified PTAA copolymers obtained in Examples 4-10 and the PTAA polymer obtained in Comparative Example 1 using toluene. -3 A solution of mol / L was prepared, and then UV-Vis analysis was performed on the solution to determine its maximum absorption peak λ. max2 The results are shown in Table 2.
[0090] Table 1:
[0091]
[0092] Table 2:
[0093]
[0094] As shown in Table 1, pyrazine-modified PTAA copolymers were successfully synthesized in Examples 4-10 of this invention. As shown in Table 2, the pyrazine-modified PTAA copolymers obtained in Examples 4-10 of this invention exhibit a significant absorption edge λ compared to the PTAA polymer. onset Redshift, full width at half maximum (FWHM) Δλ 1 / 2 The broadening of the electron beam indicates a decrease in the electron transition energy of the pyrazine-modified PTAA copolymer, a significant increase in electron coupling between the electron donor and acceptor, and an increase in electron cloud overlap, i.e., enhanced intramolecular charge transfer. Simultaneously, the λ-wave length increases with increasing solvent polarity. max1The significant red shift indicates that the pyrazine-modified PTAA copolymer exhibits a significantly enhanced intramolecular charge transfer in the ground state. Furthermore, comparing the maximum absorption peaks of the copolymer / polymer in extremely dilute and concentrated solutions reveals a significant red shift in the maximum absorption peak of the pyrazine-modified PTAA copolymers obtained in Examples 4-10 in concentrated solutions, indicating that their molecular chains form ordered aggregates in concentrated solutions. In summary, the pyrazine-modified PTAA copolymers of the present invention possess enhanced intramolecular charge transfer and synchronized pre-aggregation behavior.
[0095] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that after reading this application specification, they can still modify or make equivalent substitutions to the specific implementation of the present invention, but these modifications or changes do not depart from the protection scope of the pending claims of the present invention.
Claims
1. A pyrazine-modified PTAA copolymer, characterized in that, The structural formula of the pyrazine-modified PTAA copolymer is shown in Formula (I): Equation (Ⅰ); Where n is 0.5 to 0.
99.
2. The pyrazine-modified PTAA copolymer according to claim 1, characterized in that, The value of n is 0.7 to 0.
85.
3. The pyrazine-modified PTAA copolymer according to claim 1, characterized in that, The pyrazine-modified PTAA copolymer has a number-average molecular weight of 8-30 kDa and a PDI of 1.5-4.
0.
4. The pyrazine-modified PTAA copolymer according to claim 1, characterized in that, The raw materials for preparing the pyrazine-modified PTAA copolymer include 6-aminoquinoxaline.
5. The pyrazine-modified PTAA copolymer according to claim 4, characterized in that, The raw materials for preparing the pyrazine-modified PTAA copolymer also include 2,4,6-trimethylaniline and 4,4'-dibromobiphenyl.
6. The method for preparing the pyrazine-modified PTAA copolymer according to any one of claims 1 to 5, characterized in that, Includes the following steps: Under the action of palladium catalyst and auxiliaries, 6-aminoquinoxaline, 2,4,6-trimethylaniline and 4,4'-dibromobiphenyl undergo a polymerization reaction to obtain the pyrazine-modified PTAA copolymer.
7. The method for preparing the pyrazine-modified PTAA copolymer according to claim 6, characterized in that, The sum of the amounts of 6-aminoquinoxaline and 2,4,6-trimethylaniline is n1, and the amount of 4,4'-dibromobiphenyl is n2, where n1:n2 is 1:1 to 1.
1. And / or, the molar ratio of the 2,4,6-trimethylaniline to the molar ratio of the 6-aminoquinoxaline is 0.5~0.99:0.01~0.
5.
8. The method for preparing the pyrazine-modified PTAA copolymer according to claim 6, characterized in that, The molar ratio of the palladium catalyst to the 4,4'-dibromobiphenyl is 0.005~0.03:1; And / or, the structure of the palladium catalyst is shown in formula (II) below: Equation (II), where R 1 R 2 It can be hydrogen, methyl, ethyl, or isopropyl independently, and R 1 R 2 They are not both hydrogen.
9. The method for preparing the pyrazine-modified PTAA copolymer according to claim 6, characterized in that, The additives include organic bases and solvents; And / or, the molar ratio of the organic base to the molar ratio of the 4,4'-dibromobiphenyl is 2 to 4:1; And / or, the ratio of the solvent to the 4,4'-dibromobiphenyl is 2L~4L:1mol.
10. The method for preparing the pyrazine-modified PTAA copolymer according to claim 6, characterized in that, The polymerization reaction is carried out at a temperature of 100~120℃ for a time of 12~36 hours. And / or, the polymerization reaction is carried out in an inert gas atmosphere; And / or, the polymerization reaction may include a post-processing step after completion.