A tertiary amination PTAA copolymer and its preparation method
By introducing strongly polar tertiary amine side groups into the PTAA main chain to form tertiary amination PTAA copolymers, the problem of mechanical brittleness of PTAA is solved, and the toughness and stability of the material are significantly improved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- CHAIN WALK NEW MATERIAL TECH (GUANGZHOU) CO LTD
- Filing Date
- 2026-04-24
- Publication Date
- 2026-07-17
AI Technical Summary
The main chain of poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) has high rigidity and lacks energy dissipation pathways, resulting in mechanical brittleness. It is difficult to prepare independent thin films and is prone to cracking in composite structures, which affects the long-term reliability of the material.
By introducing strongly polar tertiary amine side groups onto the PTAA backbone, tertiary amination PTAA copolymers are formed, increasing the free volume of the conjugated backbone and improving mechanical toughness.
It effectively enhances the mechanical toughness of PTAA by more than 40%, improves the material's resistance to crack propagation, and enhances the stability of thin films and composite structures.
Smart Images
Figure CN122080401B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of organic polymers, and particularly relates to a tertiary amination PTAA copolymer and its preparation method. Background Technology
[0002] Poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) is a class of conjugated polymers with triarylamine units as the main chain. Due to its good light transmittance and tunable energy levels, it has attracted widespread attention in the field of functional materials.
[0003] However, PTAA molecules have high rigidity in their main chain and aromatic ring structure in their side groups. The intermolecular forces are mainly weak van der Waals forces, lacking effective energy dissipation pathways. Under tensile or impact loads, stress easily concentrates locally and rapidly induces crack propagation, resulting in brittle fracture with low fracture energy. This mechanical brittleness not only makes it difficult to prepare and handle standalone PTAA films, but also makes them prone to cracking or peeling due to minor deformations in composite structures or coating applications, severely limiting the long-term reliability of the material.
[0004] To improve the mechanical brittleness of PTAA, existing technologies mainly employ physical blending methods, such as adding flexible polymers, nanofillers, or small molecule plasticizers. However, the compatibility between physically blended components and the PTAA matrix is often limited, and the blended system is prone to phase separation during film formation or use, leading to non-uniform or even deteriorated mechanical properties. Furthermore, the added inert components may dilute the intrinsic functional properties of PTAA.
[0005] Therefore, how to effectively improve the mechanical toughness of PTAA is a key technical problem that urgently needs to be solved in this field. Summary of the Invention
[0006] This invention discloses a tertiary amination PTAA copolymer and its preparation method. The strong polar tertiary amine side groups in the tertiary amination PTAA copolymer can increase the free volume of the conjugated main chain, play an internal toughening role, and thus effectively improve mechanical toughness.
[0007] The first objective of this invention is to provide a tertiary amination PTAA copolymer, the structural formula of which is shown in formula (I):
[0008] Equation (Ⅰ);
[0009] R is selected from or At least one of them, n is 0.018~0.82, preferably 0.27~0.62, such as 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60.
[0010] In some embodiments of the present invention, the number average molecular weight of the tertiary amination PTAA copolymer is 8~30kDa, for example 10kDa, 12kDa, 14kDa, 16kDa, 18kDa, 20kDa, 22kDa, 24kDa, 26kDa, 28kDa, and the PDI is 1.2~3.5.
[0011] In some embodiments of the present invention, R is selected from... When R is selected from this structure, it is beneficial to obtain better mechanical toughness.
[0012] A second objective of this invention is to provide a method for preparing the above-mentioned tertiary amination PTAA copolymer, characterized by comprising the following steps:
[0013] Under the action of palladium catalyst and auxiliaries, tertiary amine-substituted aniline compounds, 2,4,6-trimethylaniline and 4,4'-dibromobiphenyl undergo a polymerization reaction to obtain the tertiary amined PTAA copolymer;
[0014] The tertiary amine-substituted aniline compound is selected from at least one of 4-dimethylaminomethyl-aniline or N,N-dimethylo-phenylenediamine.
[0015] In some embodiments of the present invention, the sum of the amounts of the tertiary amine-substituted aniline compound and the 2,4,6-trimethylaniline is n1, the amount of the 4,4'-dibromobiphenyl is n2, and the ratio of n1 to n2 is 1:1 to 1.1.
[0016] In some embodiments of the present invention, the molar ratio of the tertiary amine-substituted aniline compound to the 2,4,6-trimethylaniline is 0.2~0.8:0.2~0.8.
[0017] 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.
[0018] In some embodiments of the present invention, the structure of the palladium catalyst is shown in formula (II):
[0019] 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.
[0020] In some embodiments of the present invention, the auxiliary agent includes an organic base and a solvent.
[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 molar ratio of the organic base to the 4,4'-dibromobiphenyl is 2 to 4:1.
[0023] In some embodiments of the present invention, the solvent is selected from toluene.
[0024] In some embodiments of the present invention, the ratio of the solvent to the 4,4'-dibromobiphenyl is 2L~4L:1mol.
[0025] In some embodiments of the present invention, the polymerization reaction is carried out at a temperature of 100-120°C for 12-36 hours.
[0026] In some embodiments of the present invention, the polymerization reaction is carried out in an inert gas atmosphere.
[0027] In some embodiments of the present invention, a post-processing step is further included after the polymerization reaction is completed.
[0028] In some embodiments of the present invention, the post-processing step includes a step of precipitation with methanol.
[0029] Compared with the prior art, the present invention has the following beneficial effects: the tertiary amination PTAA copolymer of the present invention can increase the free volume of the conjugated backbone, play an internal toughening role, and effectively enhance the mechanical toughness of PTAA by more than 40% or even close to 80%. Attached Figure Description
[0030] Figure 1 The tertiary amination PTAA copolymer prepared in Example 7 of this invention 1 H NMR spectrum;
[0031] Figure 2 The tertiary amination PTAA copolymer prepared in Example 11 of this invention 1 H NMR spectrum. Detailed Implementation
[0032] 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.
[0033] All raw materials used in this invention are commercially available.
[0034] The structure of imidazole salt ligand L1 is shown below:
[0035] ;
[0036] The structure of imidazole salt ligand L2 is shown below:
[0037] ;
[0038] The structure of imidazole salt ligand L3 is shown below:
[0039] .
[0040] Example 1
[0041] This embodiment provides a palladium catalyst C1, the preparation method of which includes the following steps:
[0042] 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:
[0043] 1 H 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).
[0044] 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.
[0045] The structure of palladium catalyst C1 is shown below:
[0046] .
[0047] Example 2
[0048] This embodiment provides a palladium catalyst C2, the preparation method of which includes the following steps:
[0049] 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:
[0050] 1 H 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).
[0051] 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.
[0052] The structure of palladium catalyst C2 is shown below:
[0053] .
[0054] Example 3
[0055] This embodiment provides a palladium catalyst C3, the preparation method of which includes the following steps:
[0056] 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:
[0057] 1 H 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).
[0058] 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.
[0059] The structure of palladium catalyst C3 is shown below:
[0060] .
[0061] Example 4
[0062] This embodiment provides a tertiary amination PTAA copolymer, the preparation method of which includes the following steps:
[0063] 4-Dimethylaminomethylaniline (0.2 mmol), 2,4,6-trimethylaniline (0.8 mmol), 4,4'-dibromobiphenyl (1 mmol), and KO were added to the reactor. tBu (3 mmol), catalyst C1 (0.02 mmol), and 3 mL of toluene solution were added and purged with nitrogen. The reaction was carried out at 110 °C for 24 h. After the reaction was completed, the mixture was cooled to room temperature and added dropwise to a methanol solution to precipitate. The precipitate was washed 2-3 times with methanol solution, 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. The filtrate was washed 2-3 times with methanol solution, filtered, and dried to obtain the tertiary amination PTAA copolymer, the structure of which is shown below:
[0064] .
[0065] Example 5
[0066] This embodiment provides a tertiary amination PTAA copolymer, the preparation method of which includes the following steps:
[0067] 4-Dimethylaminomethylaniline (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), catalyst C2 (0.02 mmol), and 3 mL of toluene solution were added and purged with nitrogen. The reaction was carried out at 110 °C for 24 h. After the reaction was completed, the mixture was cooled to room temperature and added dropwise to a methanol solution to precipitate. The precipitate was washed 2-3 times with methanol solution, 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 filtrate was added dropwise to methanol to precipitate. The filtrate was washed 2-3 times with methanol solution, filtered, and dried to obtain a tertiary amination PTAA copolymer with the same structure as in Example 4.
[0068] Example 6
[0069] This embodiment provides a tertiary amination PTAA copolymer, the preparation method of which includes the following steps:
[0070] 4-Dimethylaminomethylaniline (0.4 mmol), 2,4,6-trimethylaniline (0.6 mmol), 4,4'-dibromobiphenyl (1 mmol), and KO were added to the reactor. t Bu (3 mmol), catalyst C3 (0.02 mmol), and 3 mL of toluene solution were added and purged with nitrogen. The reaction was carried out at 110 °C for 24 h. After the reaction was completed, the mixture was cooled to room temperature and added dropwise to a methanol solution to precipitate. The precipitate was washed 2-3 times with methanol solution, 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 filtrate was added dropwise to methanol to precipitate. The filtrate was washed 2-3 times with methanol solution, filtered, and dried to obtain a tertiary amination PTAA copolymer with the same structure as in Example 4.
[0071] Example 7
[0072] This embodiment provides a tertiary amination PTAA copolymer, the preparation method of which includes the following steps:
[0073] 4-Dimethylaminomethylaniline (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), catalyst C2 (0.02 mmol), and 3 mL of toluene solution were added and purged with nitrogen. The reaction was carried out at 110 °C for 24 h. After the reaction was completed, the mixture was cooled to room temperature and added dropwise to a methanol solution to precipitate. The precipitate was washed 2-3 times with methanol solution, 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 filtrate was added dropwise to methanol to precipitate. The filtrate was washed 2-3 times with methanol solution, filtered, and dried to obtain a tertiary amination PTAA copolymer with the same structure as in Example 4.
[0074] Example 8
[0075] This embodiment provides a tertiary amination PTAA copolymer, the preparation method of which includes the following steps:
[0076] 4-Dimethylaminomethylaniline (0.6 mmol), 2,4,6-trimethylaniline (0.4 mmol), 4,4'-dibromobiphenyl (1 mmol), and KO were added to the reactor. t Bu (3 mmol), catalyst C2 (0.02 mmol), and 3 mL of toluene solution were added and purged with nitrogen. The reaction was carried out at 110 °C for 24 h. After the reaction was completed, the mixture was cooled to room temperature and added dropwise to a methanol solution to precipitate. The precipitate was washed 2-3 times with methanol solution, 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 filtrate was added dropwise to methanol to precipitate. The filtrate was washed 2-3 times with methanol solution, filtered, and dried to obtain a tertiary amination PTAA copolymer with the same structure as in Example 4.
[0077] Example 9
[0078] This embodiment provides a tertiary amination PTAA copolymer, the preparation method of which includes the following steps:
[0079] 4-Dimethylaminomethylaniline (0.7 mmol), 2,4,6-trimethylaniline (0.3 mmol), 4,4'-dibromobiphenyl (1 mmol), and KO were added to the reactor. tBu (3 mmol), catalyst C2 (0.02 mmol), and 3 mL of toluene solution were added and purged with nitrogen. The reaction was carried out at 110 °C for 24 h. After the reaction was completed, the mixture was cooled to room temperature and added dropwise to a methanol solution to precipitate. The precipitate was washed 2-3 times with methanol solution, 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 filtrate was added dropwise to methanol to precipitate. The filtrate was washed 2-3 times with methanol solution, filtered, and dried to obtain a tertiary amination PTAA copolymer with the same structure as in Example 4.
[0080] Example 10
[0081] This embodiment provides a tertiary amination PTAA copolymer, the preparation method of which includes the following steps:
[0082] 4-Dimethylaminomethylaniline (0.8 mmol), 2,4,6-trimethylaniline (0.2 mmol), 4,4'-dibromobiphenyl (1 mmol), and KO were added to the reactor. t Bu (3 mmol), catalyst C2 (0.02 mmol), and 3 mL of toluene solution were added and purged with nitrogen. The reaction was carried out at 110 °C for 24 h. After the reaction was completed, the mixture was cooled to room temperature and added dropwise to a methanol solution to precipitate. The precipitate was washed 2-3 times with methanol solution, 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 filtrate was added dropwise to methanol to precipitate. The filtrate was washed 2-3 times with methanol solution, filtered, and dried to obtain a tertiary amination PTAA copolymer with the same structure as in Example 4.
[0083] Example 11
[0084] This embodiment provides a tertiary amination PTAA copolymer, the preparation method of which includes the following steps:
[0085] N,N-dimethyl-o-phenylenediamine (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), catalyst C2 (0.02 mmol), and 3 mL of toluene solution were added and purged with nitrogen. The reaction was carried out at 110 °C for 24 h. After the reaction was completed, the mixture was cooled to room temperature and added dropwise to a methanol solution to precipitate. The precipitate was washed 2-3 times with methanol solution, 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 filtrate was added dropwise to methanol to precipitate. The filtrate was washed 2-3 times with methanol solution, filtered, and dried to obtain a tertiary amination PTAA copolymer, the structure of which is shown below:
[0086] .
[0087] The following test will be conducted:
[0088] 1. Weigh the tertiary amination PTAA copolymers obtained in Examples 4-11 above, calculate their yields, and the results are shown in Table 1.
[0089] 2. GPC analysis was performed on the tertiary amination PTAA copolymers obtained in Examples 4 to 11 above to obtain their number-average molecular weight Mn and molecular weight distribution index PDI. The results are shown in Table 1.
[0090] 3. The tertiary amination PTAA copolymers obtained in Examples 4-11 above were subjected to... 1 1H NMR analysis was performed, and the ratio of methyl H on the tertiary amine / methylene H adjacent to the tertiary amine to methyl H on trimethylbenzene was integrated to determine the proportion of tertiary amine structural units in the copolymer, i.e. the n value in the copolymer structure. The results are shown in Table 1.
[0091] 4. Referring to ASTM D3878, the tertiary amination PTAA copolymers obtained in Examples 4-11, and PTAA (Mn approximately 9.34 kDa, PDI 1.42, as a comparative example) were subjected to double cantilever beam tests. The films were obtained by coating with a 10 mg / mL chlorobenzene solution at a rate of 50 μL / cm², with a notch designed to be 10 mm long and a displacement rate of 1 mm / min. The fracture energy G of the film was calculated based on the obtained load-displacement curve. c (J·m -2 The results are shown in Table 1.
[0092] Table 1: Properties of the tertiary amination PTAA copolymers obtained in Examples 4-10 and comparative sample
[0093]
[0094] As shown in Table 1, Examples 4-11 of the present invention successfully synthesized tertiary amination PTAA copolymers, and the resulting copolymers have enhanced mechanical toughness.
[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 tertiary amination PTAA copolymer, characterized in that, The structural formula of the tertiary amination PTAA copolymer is shown in Formula (I): Equation (Ⅰ); Where R is selected from or At least one of them, where n is 0.018 to 0.82; The tertiary amination PTAA copolymer has a number average molecular weight of 8~30kDa and a PDI of 1.2~3.
5.
2. The tertiary amination PTAA copolymer according to claim 1, characterized in that, The R is selected from .
3. The method for preparing the tertiary amination PTAA copolymer according to claim 1, characterized in that, Includes the following steps: Under the action of palladium catalyst and auxiliaries, tertiary amine-substituted aniline compounds, 2,4,6-trimethylaniline and 4,4'-dibromobiphenyl undergo a polymerization reaction to obtain the tertiary amined PTAA copolymer; The tertiary amine-substituted aniline compound is selected from at least one of 4-dimethylaminomethyl-aniline or N,N-dimethylo-phenylenediamine.
4. The method for preparing the tertiary amination PTAA copolymer according to claim 3, characterized in that, The sum of the amounts of the tertiary amine-substituted aniline compound and the 2,4,6-trimethylaniline is n1, and the amount of the 4,4'-dibromobiphenyl is n2, with a ratio of n1:n2 of 1:1 to 1.
1.
5. The method for preparing the tertiary amination PTAA copolymer according to claim 3, characterized in that, The molar ratio of the tertiary amine-substituted aniline compound to the 2,4,6-trimethylaniline is 0.2~0.8:0.2~0.
8.
6. The method for preparing the tertiary amination PTAA copolymer according to claim 3, characterized in that, The molar ratio of the palladium catalyst to the 4,4'-dibromobiphenyl is 0.005 to 0.03:
1.
7. The method for preparing the tertiary amination PTAA copolymer according to claim 3, characterized in that, The additives include organic bases and solvents.
8. The method for preparing the tertiary amination PTAA copolymer according to claim 7, characterized in that, The organic base is selected from potassium tert-butoxide.
9. The method for preparing the tertiary amination PTAA copolymer according to claim 7, characterized in that, The molar ratio of the organic base to the 4,4'-dibromobiphenyl is 2 to 4:
1.
10. The method for preparing the tertiary amination PTAA copolymer according to claim 7, characterized in that, The solvent is selected from toluene; and / or the ratio of the solvent to the 4,4'-dibromobiphenyl is 2L~4L:1mol.