A sulfone-containing aromatic amine polymer and its preparation method
By introducing a large-volume aryl sulfone structure into an aromatic amine polymer, its acid resistance and hot water stability are enhanced, solving the problem of insufficient stability of fluorescent polymers in acidic and hot water environments, and realizing effective application in complex environments.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- CHAIN WALK NEW MATERIAL TECH (GUANGZHOU) CO LTD
- Filing Date
- 2026-05-07
- Publication Date
- 2026-07-31
AI Technical Summary
Existing fluorescent polymers lack stability in acidic and hot water environments, resulting in reduced or quenched fluorescence intensity, making them unsuitable for effective application in complex environments.
Introducing bulky aryl sulfone structures on both sides of the nitrogen atom in aromatic amine polymers creates steric hindrance and strong electron-withdrawing effects, enhancing the polymer's acid resistance and hot water stability. The introduction of a C-SO2-C stabilizing structure also increases bond energy.
After acid and hot water treatment, the fluorescence intensity remains above 70% or even above 90%, and the polymer remains effective in complex environments.
Smart Images
Figure CN122127596B_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 sulfone 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 stability. For example, in acidic or hot water media, 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. This leads to inaccurate or even invalid output results and makes them unusable in complex environments.
[0004] Therefore, how to develop a novel fluorescent polymer that combines excellent fluorescence properties with improved acid resistance and hot water stability 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 sulfone groups and its preparation method. This aromatic amine polymer introduces large-volume aryl sulfone structures on both sides of the nitrogen atom, forming a significant steric hindrance effect. This physically hinders the attack of the relatively active nitrogen atom by the external medium. Simultaneously, the strong electron-withdrawing effect of the aryl sulfone structures on both sides 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. Furthermore, the stable structure formed by C-SO2-C has high bond energy and superior stability, endowing the polymer with excellent acid resistance and hot water medium stability.
[0006] The purpose of this invention is to provide an aromatic amine polymer containing a sulfone 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 12 carbon atoms. By selecting the above-mentioned R, stronger fluorescence intensity and / or, better hot water stability can be obtained.
[0010] In some embodiments of the present invention, the polymer has a weight-average molecular weight of 2 to 20 kDa and a molecular weight distribution of 1.05 to 2.4.
[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 sulfone structures, which have significantly improved intrinsic acid resistance and hot water medium 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 sulfone 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 0.3~0.99:0.01~0.7, preferably 0.5~0.99:0.01~0.5. 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. diphenyl sulfone 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 1:0.3~0.99:0.01~0.7, or preferably 1:0.5~0.99:0.01~0.5. By preferably placing the ratio within the above range, it is beneficial to obtain improved intrinsic acid resistance and hot water medium stability.
[0017] A second objective of this invention is to provide a method for preparing the above-mentioned sulfone-containing aromatic amine polymer, comprising the following steps:
[0018] alkylaniline under the action of catalysts and auxiliaries diphenyl sulfone halides It reacts with, optionally, other aryl halides X-Ar-X, to produce the sulfone-containing aromatic amine polymer;
[0019] Wherein, X in the diphenyl sulfone 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 diphenyl sulfone halide, and the other aryl halide is 1:0.3 to 1:0 to 0.7, preferably 1:0.5 to 1:0 to 0.5.
[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 sulfone-containing aromatic amine polymer of the present invention has fluorescent properties, especially after acid and hot water treatment, it can still maintain more than 70% or even more than 80% or more than 90% of the fluorescence intensity, and can be used effectively in complex 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 sulfone groups obtained in Example 1 of this invention 1 H NMR spectrum;
[0036] Figure 2 The UV absorption and fluorescence emission spectra of the sulfone-containing aromatic amine polymer 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] .
[0041] Example 1
[0042] This embodiment provides an aromatic amine polymer containing sulfone groups, the preparation method of which includes the following steps:
[0043] 4-n-dodecylaniline (1 mmol), 4,4'-dichlorodiphenyl sulfone (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 sulfone groups; its structure is shown below:
[0044] .
[0045] Example 2
[0046] This embodiment provides an aromatic amine polymer containing sulfone groups, the preparation method of which includes the following steps:
[0047] 4-n-octylaniline (1 mmol), 4,4'-dichlorodiphenyl sulfone (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 sulfone groups; its structure is shown below:
[0048] .
[0049] Example 3
[0050] This embodiment provides an aromatic amine polymer containing sulfone groups, the preparation method of which includes the following steps:
[0051] 4-N-pentylaniline (1 mmol), 4,4'-dichlorodiphenyl sulfone (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 sulfone groups; its structure is shown below:
[0052] .
[0053] Example 4
[0054] This embodiment provides an aromatic amine polymer containing sulfone groups, the preparation method of which includes the following steps:
[0055] 4-n-dodecylaniline (1 mmol), 4,4'-dichlorodiphenyl sulfone (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 sulfone groups; its structure is shown below:
[0056] .
[0057] Example 5
[0058] This embodiment provides an aromatic amine polymer containing sulfone groups, the preparation method of which includes the following steps:
[0059] 4-n-dodecylaniline (1 mmol), 4,4'-dichlorodiphenyl sulfone (0.7 mmol), 4,4'-dichlorobiphenyl (0.3 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 sulfone groups; its structure is as shown in Example 4.
[0060] Example 6
[0061] This embodiment provides an aromatic amine polymer containing sulfone groups, the preparation method of which includes the following steps:
[0062] 4-n-dodecylaniline (1 mmol), 4,4'-dichlorodiphenyl sulfone (0.5 mmol), 4,4'-dichlorobiphenyl (0.5 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 sulfone groups; its structure is as shown in Example 4.
[0063] Example 7
[0064] This embodiment provides an aromatic amine polymer containing sulfone groups, the preparation method of which includes the following steps:
[0065] 4-n-dodecylaniline (1 mmol), 4,4'-dichlorodiphenyl sulfone (0.3 mmol), 4,4'-dichlorobiphenyl (0.7 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 sulfone groups; its structure is as shown in Example 4.
[0066] Comparative Example 1
[0067] This embodiment provides an aromatic amine polymer, the preparation method of which includes the following steps:
[0068] 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:
[0069] .
[0070] Performance tests are as follows:
[0071] 1. The sulfone-containing aromatic amine polymer 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 sulfone-containing diphenyl sulfone structure was successfully introduced into the aromatic amine polymer. That is, Example 1 successfully prepared an aromatic amine polymer containing sulfone.
[0072] 2. GPC analysis was performed on the sulfone-containing aromatic amine polymers obtained in Examples 1-7 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 sulfone-containing aromatic amine polymer obtained in this invention is... w It has a molecular weight distribution coefficient in the range of 2 to 20 kDa.
[0073] 3. The solid powders of the sulfone-containing aromatic amine polymers obtained in Examples 1-7 and the aromatic amine polymer obtained in Comparative Example 1 were respectively placed in a 1 mol / L H2SO4 solution and stirred for 1 h under RT conditions, or placed in deionized water and stirred at 60°C for 2 h. After filtration, the polymers were washed 3-4 times with deionized water, filtered, and dried to obtain the polymers after acid and hot water treatment, 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. In addition, the UV absorption and fluorescence chromatograms of the sulfone-containing aromatic amine polymer obtained in Example 1 are shown below. Figure 2 As shown.
[0074] Table 1: Properties of different aromatic amine polymers
[0075]
[0076] As shown in Table 1, the sulfone-containing aromatic amine polymers with fluorescent properties obtained in Examples 1-7 of the present invention have significantly improved acid resistance and hot water stability compared with aromatic amine polymers without sulfone groups. In particular, the sulfone-containing aromatic amine homopolymers obtained in Examples 1-3 have large-volume aryl sulfone structures on both sides of all nitrogen atoms in the polymer, which have significantly improved intrinsic acid resistance and hot water stability.
[0077] 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 arylamine polymer containing a sulfone group, characterized by, The main chain of the aromatic amine polymer contains the structural segment shown in formula (Ⅰ): Formula (I); Wherein, R is selected from one of alkyl groups having 4 to 12 carbon atoms; the polymer has a weight-average molecular weight of 2 to 20 kDa and a molecular weight distribution of 1.05 to 2.
4.
2. The sulfone group-containing arylamine polymer according to claim 1, characterized by R is a straight-chain alkyl group with 12 carbon atoms.
3. The sulfone group-containing arylamine polymer according to claim 1, wherein The main chain of the aromatic amine polymer is composed of the structural segments shown in formula (Ⅰ).
4. The sulfone group-containing arylamine polymer according to claim 1, wherein 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 having 1 to 12 carbon atoms, and alkoxy groups having 1 to 12 carbon atoms.
5. The sulfone group-containing arylamine polymer according to claim 4, characterized by 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 process for preparing a sulfone group-containing arylamine polymer according to any one of claims 1 to 5, characterized by, Includes the following steps: alkylaniline under the action of catalysts and auxiliaries diphenyl sulfone halides It reacts with, optionally, other aryl halides X-Ar-X, to produce the sulfone-containing aromatic amine polymer; Wherein, X in the diphenyl sulfone 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 having 1 to 12 carbon atoms, and alkoxy groups having 1 to 12 carbon atoms.
7. The process for preparing a sulfone group-containing arylamine polymer according to Claim 6, characterized by, The molar ratio of the alkylaniline, the diphenyl sulfone halide, and the other aryl halides is 1:0.5 to 1:0 to 0.
5.
8. The method for preparing a sulfone group-containing arylamine polymer according to claim 6, characterized by, 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 a sulfone group-containing arylamine polymer according to claim 8, characterized by, 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 of claim 6, wherein the sulfone group-containing arylamine polymer is prepared by the reaction of a sulfone group-containing arylamine compound and a diisocyanate compound. 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.