A ketone-containing arylamine polymer and a method for preparing the same
By introducing a large-volume aryl ketone structure into the aromatic amine polymer, the problem of easy degradation of fluorescent polymers in acidic and oxidizing media was solved, and high stability and fluorescence intensity were maintained.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- CHAIN WALK NEW MATERIAL TECH (GUANGZHOU) CO LTD
- Filing Date
- 2026-05-11
- Publication Date
- 2026-06-09
AI Technical Summary
Existing fluorescent polymers are easily degraded in acidic and oxidizing media, resulting in a significant decrease in fluorescence intensity, making them unsuitable for effective application in complex chemical environments.
Introducing bulky aryl ketone structures on both sides of the nitrogen atom in aromatic amine polymers creates a steric hindrance effect and enhances electron-withdrawing properties, thereby improving the polymer's acid resistance and oxidative stability.
After treatment with acidic and oxidizing media, the fluorescence intensity remains above 65%, and the polymer can still be used effectively in complex chemical environments.
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Figure CN122167731A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of polymer chemistry technology, and particularly relates to an aromatic amine polymer containing ketone groups and its preparation method. Background Technology
[0002] Fluorescent polymers, with their excellent photoluminescence properties, high sensitivity, fast response and good processability, have shown broad application prospects in fields such as information anti-counterfeiting and optoelectronic devices.
[0003] However, in actual service, fluorescent polymers generally face the prominent problem of insufficient chemical corrosion resistance: in acidic, oxidizing media and other environments, the polymer molecular chains are prone to degradation, fluorescent groups are destroyed or photophysical properties are attenuated, resulting in a significant reduction or even complete quenching of fluorescence intensity, which in turn leads to inaccurate or even invalid output results, and ineffective application in complex chemical environments.
[0004] Therefore, how to develop a novel fluorescent polymer that combines excellent fluorescence properties with intrinsic acid resistance and stability in oxidizing media is a technical problem that urgently needs to be solved in this field. Summary of the Invention
[0005] To address the shortcomings of the prior art, this invention provides an aromatic amine polymer containing ketone groups and its preparation method. This aromatic amine polymer contains ketone groups and introduces large-volume aryl ketone structures on both sides of the nitrogen atom, forming a significant steric hindrance effect. This physically hinders the attack of the more reactive nitrogen atom by acidic or oxidizing media. At the same time, the strong electron-withdrawing effect of the aryl ketone structures on both sides also disperses the positive charge of the nitrogen atom, thereby enhancing the nitrogen atom's resistance to protonation and further improving the polymer's acid resistance. Thus, a fluorescent polymer with intrinsic acid resistance and oxidizing media stability is obtained.
[0006] The purpose of this invention is to provide an aromatic amine polymer containing a ketone group, wherein the main chain of the aromatic amine polymer contains the structural segment shown in formula (Ⅰ):
[0007] Equation (Ⅰ);
[0008] Wherein, R is selected from one of the alkyl groups having 4 to 12 carbon atoms.
[0009] In some embodiments of the present invention, R is a straight-chain alkyl group having 4 to 12 carbon atoms, preferably a straight-chain alkyl group having 8 to 12 carbon atoms. By selecting the above-mentioned R, stronger fluorescence intensity and / or, better resistance to oxidation media stability can be obtained.
[0010] In some embodiments of the present invention, the polymer has a weight-average molecular weight of 4 to 12 kDa and a molecular weight distribution of 1.2 to 2.5.
[0011] In some embodiments of the present invention, the main chain of the aromatic amine polymer is composed of the structural segments shown in formula (Ⅰ), that is, the aromatic amine polymer is a homopolymer. In this case, all nitrogen atoms in the polymer are flanked by large-volume aryl ketone structures, which have significantly improved intrinsic acid resistance and oxidizing media stability.
[0012] In some embodiments of the present invention, the main chain of the aromatic amine polymer further contains the structural segment shown in formula (II), that is, the resulting aromatic amine polymer containing ketone groups is a copolymer.
[0013] Equation (II);
[0014] Wherein, Ar is selected from , At least one of R1, R2, R3, R4, R5, R6, R7, R8, R9, and R 10 R 11 R 12 It is independently selected from H, alkyl groups with 1 to 12 tertiary carbon atoms, and alkoxy groups with 1 to 12 tertiary carbon atoms.
[0015] In some embodiments of the present invention, the values of n in formula (I) and m in formula (II) in the main chain of the aromatic amine polymer are independently selected from 2 to 100, that is, independently selected from any integer between 2, 3, 4, 5 and 100.
[0016] In some embodiments of the present invention, the ratio of n in formula (I) to m in formula (II) in the main chain of the aromatic amine polymer is 0.5~0.99:0.01~0.5, more preferably 0.7~0.99:0.01~0.3. This ratio can be achieved by controlling the reactive monomers of the aromatic amine polymer; specifically, it can be achieved by controlling the alkylaniline in the reactive monomers. benzophenone halides The molar ratio of X (selected from F, Cl, or Br) and other aryl halides X-Ar-X (X selected from F, Cl, or Br) is 1:0.5~0.99:0.01~0.5, or preferably 1:0.7~0.99:0.01~0.3. Furthermore, by preferably placing the ratio within the above range, it is beneficial to obtain improved intrinsic resistance to acidic and oxidizing media.
[0017] A second objective of this invention is to provide a method for preparing the above-mentioned aromatic amine polymer containing a ketone group, comprising the following steps:
[0018] alkylaniline under the action of catalysts and auxiliaries benzophenone halides It reacts with, optionally, other aryl halides X-Ar-X, to produce the ketone-containing aromatic amine polymer;
[0019] Wherein, X in the benzophenone halide and the other aryl halides are independently selected from F, Cl or Br;
[0020] Ar in the other aryl halides is selected from... , At least one of R1, R2, R3, R4, R5, R6, R7, R8, R9, and R 10 R 11 R 12 It is independently selected from H, alkyl groups with 1 to 12 tertiary carbon atoms, and alkoxy groups with 1 to 12 tertiary carbon atoms.
[0021] In some embodiments of the present invention, the molar ratio of the alkylaniline, the benzophenone halide, and the other aryl halides is 1:0.5 to 1:0 to 0.5, preferably 1:0.7 to 1:0 to 0.3.
[0022] In some embodiments of the present invention, the catalyst includes a palladium-based catalyst.
[0023] In some embodiments of the present invention, the palladium catalyst has the structural formula shown in formula (Ⅲ):
[0024] Equation (Ⅲ); where R 1 R 2 It can be hydrogen, methyl, ethyl, or isopropyl independently, and R 1 R 2 They are not both hydrogen.
[0025] In some embodiments of the present invention, the amount of catalyst used is 1 to 8 mol% of the amount of the alkylaniline.
[0026] In some embodiments of the present invention, the auxiliary agent includes an organic base and a solvent.
[0027] In some embodiments of the present invention, the organic base is selected from potassium tert-butoxide (KO). t Bu).
[0028] In some embodiments of the present invention, the amount of the organic base used is 2 to 5 times the amount of the alkylaniline.
[0029] In some embodiments of the present invention, the solvent is selected from at least one of toluene and N,N-dimethylacetamide.
[0030] In some embodiments of the present invention, the polymerization reaction is carried out at a temperature of 80-120°C.
[0031] In some embodiments of the present invention, the polymerization reaction takes 18 to 30 hours.
[0032] Compared with the prior art, the present invention has the following beneficial effects:
[0033] The ketone-containing aromatic amine polymers of the present invention have fluorescent properties, and in particular, they can maintain a fluorescence intensity of more than 65% or even more than 80% even after treatment with acidic or oxidizing media, and can be used effectively in complex chemical environments. Attached Figure Description
[0034] The accompanying drawings are provided to further illustrate the present application and form part of the specification. Together with the embodiments of the present application, they serve to explain the present application but do not constitute a limitation thereof. In the drawings:
[0035] Figure 1 The aromatic amine polymer containing ketone groups obtained in Example 1 of this invention 1 H NMR spectrum;
[0036] Figure 2 The UV absorption and fluorescence emission spectra of the aromatic amine polymer containing ketone groups obtained in Example 1 of this invention are shown. Detailed Implementation
[0037] 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.
[0038] Unless otherwise specified, all raw materials used in this invention are obtained commercially.
[0039] The structure of the palladium catalyst of the present invention is shown below: .
[0040] Example 1
[0041] This embodiment provides an aromatic amine polymer containing a ketone group, the preparation method of which includes the following steps:
[0042] 4-n-dodecylaniline (1 mmol), 4,4'-dichlorobenzophenone (1 mmol), and KO were added to the reactor. tBu (3 mmol), palladium catalyst (0.06 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, and the resulting filtrate was added dropwise to a methanol solution to precipitate. The filtrate was washed 2-3 times with methanol solution, filtered, and dried to obtain a light yellow polymer, namely an aromatic amine polymer containing ketone groups; its structure is shown below:
[0043] .
[0044] Example 2
[0045] This embodiment provides an aromatic amine polymer containing a ketone group, the preparation method of which includes the following steps:
[0046] 4-n-octylaniline (1 mmol), 4,4'-dichlorobenzophenone (1 mmol), and KO were added to the reactor. t Bu (3 mmol), palladium catalyst (0.06 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, and the resulting filtrate was added dropwise to a methanol solution to precipitate. The filtrate was washed 2-3 times with methanol solution, filtered, and dried to obtain a light yellow polymer, namely an aromatic amine polymer containing ketone groups; its structure is shown below:
[0047] .
[0048] Example 3
[0049] This embodiment provides an aromatic amine polymer containing a ketone group, the preparation method of which includes the following steps:
[0050] 4-N-pentylaniline (1 mmol), 4,4'-dichlorobenzophenone (1 mmol), and KO were added to the reactor. t Bu (3 mmol), palladium catalyst (0.06 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, and the resulting filtrate was added dropwise to a methanol solution to precipitate. The filtrate was washed 2-3 times with methanol solution, filtered, and dried to obtain a light yellow polymer, namely an aromatic amine polymer containing ketone groups; its structure is shown below: .
[0051] Example 4
[0052] This embodiment provides an aromatic amine polymer containing a ketone group, the preparation method of which includes the following steps:
[0053] 4-n-dodecylaniline (1 mmol), 4,4'-dichlorobenzophenone (0.9 mmol), 4,4'-dichlorobiphenyl (0.1 mmol), and KO were added to the reactor. t Bu (3 mmol), palladium catalyst (0.06 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, and the resulting filtrate was added dropwise to a methanol solution to precipitate. The filtrate was washed 2-3 times with methanol solution, filtered, and dried to obtain a light yellow polymer, namely an aromatic amine polymer containing ketone groups; its structure is shown below:
[0054] .
[0055] Example 5
[0056] This embodiment provides an aromatic amine polymer containing a ketone group, the preparation method of which includes the following steps:
[0057] 4-n-dodecylaniline (1 mmol), 4,4'-dichlorobenzophenone (0.7 mmol), 4,4'-dichlorobiphenyl (0.3 mmol), and KO were added to the reactor. t Bu (3 mmol), palladium catalyst (0.06 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, and the resulting filtrate was added dropwise to a methanol solution to precipitate. The filtrate was washed 2-3 times with methanol solution, filtered, and dried to obtain a light yellow polymer, i.e., an aromatic amine polymer containing ketone groups; its structure is as shown in Example 4.
[0058] Example 6
[0059] This embodiment provides an aromatic amine polymer containing a ketone group, the preparation method of which includes the following steps:
[0060] 4-n-dodecylaniline (1 mmol), 4,4'-dichlorobenzophenone (0.5 mmol), 4,4'-dichlorobiphenyl (0.5 mmol), and KO were added to the reactor. tBu (3 mmol), palladium catalyst (0.06 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, and the resulting filtrate was added dropwise to a methanol solution to precipitate. The filtrate was washed 2-3 times with methanol solution, filtered, and dried to obtain a light yellow polymer, i.e., an aromatic amine polymer containing ketone groups; its structure is as shown in Example 4.
[0061] Comparative Example 1
[0062] This embodiment provides an aromatic amine polymer, the preparation method of which includes the following steps:
[0063] 4-n-dodecylaniline (1 mmol), 4,4'-dichlorobiphenyl (1 mmol), and KO were added to the reactor. t Bu (3 mmol), palladium catalyst (0.06 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, and the resulting filtrate was added dropwise to a methanol solution to precipitate. The filtrate was washed 2-3 times with methanol solution, filtered, and dried to obtain a pale yellow polymer, namely an aromatic amine polymer; its structure is shown below:
[0064] .
[0065] Performance tests are as follows:
[0066] 1. The aromatic amine polymer containing ketone groups obtained in Example 1 above was subjected to... 1 H NMR analysis, structure as follows Figure 1 As shown. By Figure 1 It can be seen that the integral area at the chemical shift of 6.8~7.8 ppm is about 6 times the integral area of the methylene H (a in the figure) connected to the benzene ring. This indicates that the benzophenone structure containing the ketone group was successfully introduced into the aromatic amine polymer. That is, the aromatic amine polymer containing the ketone group was successfully prepared in Example 1.
[0067] 2. GPC analysis was performed on the aromatic amine polymers containing ketone groups obtained in Examples 1-6 and the aromatic amine polymer obtained in Comparative Example 1. The obtained M w The PDI results are shown in Table 1. As can be seen from Table 1, the weight-average molecular weight M of the ketone-containing aromatic amine polymers obtained in Examples 1-6 of this invention is... w It has a molecular weight distribution coefficient in the range of 4 to 12 kDa.
[0068] 3. The solid powders of the ketone-containing aromatic amine polymers obtained in Examples 1-6 and the aromatic amine polymer obtained in Comparative Example 1 were respectively placed in a 1 mol / L H2SO4 solution and an 84 disinfectant stock solution. After stirring for 1 h under RT conditions, the mixtures were filtered, washed 3-4 times with deionized water, filtered again, and dried to obtain the polymers treated with acid and oxidant, respectively. Fluorescence properties of the polymers before and after treatment were analyzed using THF as the solvent at a concentration of 0.02 mg / mL and the maximum UV absorption wavelength as the excitation wavelength. The retention rate of the fluorescence intensity after treatment relative to that before treatment was calculated, and the results are shown in Table 1. Additionally, the UV absorption and fluorescence chromatograms of the ketone-containing aromatic amine polymer obtained in Example 1 are shown below. Figure 2 As shown.
[0069] Table 1: Properties of different aromatic amine polymers
[0070]
[0071] As shown in Table 1, the aromatic amine polymers containing ketone groups with fluorescent properties obtained in Examples 1-6 of the present invention have significantly improved acid resistance and oxidative stability compared to aromatic amine polymers without ketone groups. In particular, the aromatic amine homopolymers containing ketone groups obtained in Examples 1-3 have large-volume aryl ketone structures on both sides of all nitrogen atoms in the polymer, which have significantly improved intrinsic acid resistance and oxidative stability.
[0072] 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. An aromatic amine polymer containing a ketone group, characterized in that, The main chain of the aromatic amine polymer contains the structural segment shown in formula (Ⅰ): Equation (Ⅰ); Wherein, R is selected from one of the alkyl groups having 4 to 12 carbon atoms.
2. The aromatic amine polymer containing a ketone group according to claim 1, characterized in that, R is a straight-chain alkyl group with 8 to 12 carbon atoms.
3. The aromatic amine polymer containing a ketone group according to claim 1, characterized in that, The main chain of the aromatic amine polymer is composed of the structural segments shown in formula (Ⅰ).
4. The aromatic amine polymer containing a ketone group according to claim 1, characterized in that, The main chain of the aromatic amine polymer also contains the structural segment shown in formula (II): Equation (II); Wherein, Ar is selected from , At least one of R1, R2, R3, R4, R5, R6, R7, R8, R9, and R 10 R 11 R 12 It is independently selected from H, alkyl groups with 1 to 12 tertiary carbon atoms, and alkoxy groups with 1 to 12 tertiary carbon atoms.
5. The aromatic amine polymer containing a ketone group according to claim 4, characterized in that, The ratio of n in formula (Ⅰ) to m in formula (Ⅱ) in the main chain of the aromatic amine polymer is 0.5~0.99:0.01~0.
5.
6. The method for preparing the aromatic amine polymer containing a ketone group according to any one of claims 1 to 5, characterized in that, Includes the following steps: alkylaniline under the action of catalysts and auxiliaries benzophenone halides It reacts with, optionally, other aryl halides X-Ar-X, to produce the ketone-containing aromatic amine polymer; Wherein, X in the benzophenone halide and the other aryl halides are independently selected from F, Cl or Br; Ar in the other aryl halides is selected from... , At least one of R1, R2, R3, R4, R5, R6, R7, R8, R9, and R 10 R 11 R 12 It is independently selected from H, alkyl groups with 1 to 12 tertiary carbon atoms, and alkoxy groups with 1 to 12 tertiary carbon atoms.
7. The method for preparing the aromatic amine polymer containing a ketone group according to claim 6, characterized in that, The molar ratio of the alkylaniline, the benzophenone halide, and the other aryl halides is 1:0.5 to 1:0 to 0.
5.
8. The method for preparing the aromatic amine polymer containing a ketone group according to claim 6, characterized in that, The catalyst includes palladium-based catalysts; And / or, the amount of the catalyst used is 1 to 8 mol% of the molar amount of the alkylaniline; And / or, the adjuvants include organic bases and solvents.
9. The method for preparing the aromatic amine polymer containing a ketone group according to claim 8, characterized in that, The organic base is selected from potassium tert-butoxide; And / or, the amount of the organic base used is 2 to 5 times the amount of the alkylaniline; And / or, the solvent is selected from at least one of toluene and N,N-dimethylacetamide.
10. The method for preparing the aromatic amine polymer containing a ketone group according to claim 6, characterized in that, The polymerization reaction is carried out at a temperature of 80-120°C; and / or the polymerization reaction is carried out for a duration of 18-30 hours.