Porphyrinyl conjugated organic polymer containing disordered structure and preparation method of porphyrinyl conjugated organic polymer
By regulating the structure and composition of porphyrin-based conjugated organic polymer, the problem of poor solubility in organic reagents is solved, and good dispersion and nonlinear optical properties in solid organic reagents are achieved, and its application in optical plastics is expanded.
Patent Information
- Application Number
- CN202510640133.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-19
- Publication Date
- 2025-07-29
AI Technical Summary
The existing porphyrin-based covalent organic frameworks have poor solubility in organic reagents, which affects their value in practical applications, and the development of nonlinear optical materials is difficult to achieve mass production and wide application.
By preparing porphyrin-conjugated organic polymers containing disordered structures, the Alder method and Schiff base reaction are used to regulate the molar ratio of 5,10,15,20-tetrade (4-aminophenyl)porphyrin to terephthalaldehyde, destroy its structure and introduce functional groups, and improve its dispersion and nonlinear optical properties in solid organic reagents.
The prepared polymer has good dispersion and nonlinear optical properties in solid-state organic reagents, and is suitable for optical plastics, expanding its application potential in the field of nonlinear optics.
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Figure CN120383715A_ABST
Abstract
Description
Technical Field
[0001] A porphyrin-based conjugated organic polymer containing a disordered structure and a preparation method thereof belong to the technical field of polymer nonlinear optical materials. The polymer is characterized in that the polymer is a porphyrin-based polymer with a network structure obtained by a Schiff base reaction between a porphyrin monomer and a terephthalaldehyde monomer. The porphyrin monomer in the material is 5,10,15,20-tetrakis(4-aminophenyl)porphyrin. The preparation method comprises the following steps: firstly preparing 5,10,15,20-tetrakis(4-nitrophenyl)porphyrin by an Alder method; then reducing the 5,10,15,20-tetrakis(4-nitrophenyl)porphyrin to 5,10,15,20-tetrakis(4-aminophenyl)porphyrin using sodium sulfide nonahydrate; and finally subjecting the 5,10,15,20-tetrakis(4-aminophenyl)porphyrin to a Schiff base reaction with terephthalaldehyde by a liquid phase synthesis method to prepare the porphyrin-based conjugated organic polymer containing a disordered structure. The material is a nonlinear optical material. This preparation method can produce polymers with nonlinear optical properties, and the conjugation of porphyrin-based conjugated organic polymers containing disordered structures can be regulated by changing the molar ratio of 5,10,15,20-tetrakis(4-aminophenyl)porphyrin and terephthalaldehyde during the reaction, thereby achieving control over their nonlinear optical properties. Technical Background
[0002] With the advent of lasers, laser technology has advanced rapidly, keeping pace with the advancement of human society. It has found widespread application in military, medical, and consumer applications. At the same time, nonlinear optical materials with laser protection properties have become a focus of research for many researchers. However, due to difficulties in mass production and limited application scope, there are very few nonlinear optical materials that can be truly applied in practical applications. Therefore, the development of nonlinear optical materials with practical application value is urgent.
[0003] Porous organic polymers are polymers with a network structure constructed through covalent bonds, including crystalline covalent organic frameworks, amorphous conjugated organic polymers, covalent triazine frameworks, and porous aromatic frameworks. Covalent organic frameworks are used as nonlinear optical materials because they have a more regular structure and good conjugation. Compared with amorphous conjugated organic polymers, they have better carrier mobility and a larger π-conjugated structure, resulting in excellent nonlinear optical properties. Furthermore, because they are porous organic polymers, they have structural and optoelectronic properties that can be adjusted. Different functional monomers can be used to give the covalent organic framework different properties.
[0004] Due to its 18π electron conjugate structure, porphyrin has a large nonlinear absorption coefficient, fast response speed, and excellent photothermal stability, making it a popular material for research by many scientific researchers in the field of nonlinear optics. A large number of studies have shown that the nonlinear optical properties of porphyrin depend on the degree of its conjugation. Constructing covalent organic frameworks with porphyrin as monomers can effectively expand the π-conjugated plane of porphyrin and enhance the nonlinear optical properties of porphyrin, which makes porphyrin-based covalent organic frameworks exhibit better nonlinear optical properties than porphyrin molecules. However, due to its obvious π-conjugated structure, porphyrin-based covalent organic frameworks have obvious stacking and poor solubility in organic reagents, seriously affecting their application value in actual use. Therefore, considering the differences in the structures and solubilities of graphene and graphene oxide, by destroying the structure of porphyrin-based covalent organic frameworks and endowing a large number of functional groups on their surfaces, it is expected to improve the solubility of porphyrin-based covalent organic frameworks in organic reagents and increase their application value in actual use. Summary of the Invention
[0005] The present invention relates to a porphyrin-based conjugated organic polymer containing a disordered structure and a preparation method thereof. The prepared composite exhibits good nonlinear optical properties and good dispersibility in solid organic reagents, and can be used to prepare optical plastics, having extremely strong application potential in the practical application of the field of nonlinear optics. Its structural formula is shown as follows:
[0006]
[0007] The conjugation of a porphyrin-based conjugated organic polymer containing a disordered structure can be regulated by controlling the ratio between 5,10,15,20-tetra(4-aminophenyl)porphyrin and terephthalaldehyde.
[0008] The preparation method of a porphyrin-based conjugated organic polymer containing a disordered structure in the present invention is as follows: First, 5,10,15,20-tetra(4-nitrophenyl)porphyrin is prepared by the Alder method, then 5,10,15,20-tetra(4-nitrophenyl)porphyrin is reduced to 5,10,15,20-tetra(4-aminophenyl)porphyrin using sodium sulfide nonahydrate, and finally 5,10,15,20-tetra(4-aminophenyl)porphyrin and terephthalaldehyde are subjected to a Schiff base reaction by the liquid-phase synthesis method to prepare a porphyrin-based conjugated organic polymer containing a disordered structure.
[0010] The technical effect of the present invention is that a porphyrin-based conjugated organic polymer containing a disordered structure has good dispersibility in solid organic reagents and good nonlinear optical properties, which can be verified by Z-scan. Description of the Drawings
[0011] Figure 1FT-IR transmission spectrum of 5,10,15,20-tetra(4-aminophenyl) porphyrin.
[0012] Figure 2 FT-IR transmission spectra of DPCOP1, DPCOP2 and DPCOP3.
[0013] Figure 3 (A) Survey X-ray photoelectron spectra of DPCOP1, DPCOP2 and DPCOP3; (B) XPS C1s spectra of DPCOP1, DPCOP2 and DPCOP3; (C) XPS N1s spectra of DPCOP1, DPCOP2 and DPCOP3.
[0014] Figure 4 Small-angle X-ray diffraction patterns of DPCOP1, DPCOP2 and DPCOP3.
[0015] Figure 5 (A) Scanning electron microscope images of DPCOP1; (B) Scanning electron microscope images of DPCOP2; (C) Scanning electron microscope images of DPCOP3.
[0016] Figure 6 Z-scan curves of DPCOP1, DPCOP2 and DPCOP3.
[0017] Figure 7 Photographs of the NLO resin films of DPCOP1, DPCOP2 and DPCOP3. (A) NLO resin film of DPCOP1; (B) NLO resin film of DPCOP2; (C) NLO resin film of DPCOP3. Detailed implementation mode
[0018] A porphyrin-based conjugated organic polymer with disordered structure and its preparation method according to the present invention (taking the ratio of 5,10,15,20-tetra(4-aminophenyl) porphyrin to terephthalaldehyde as 1:1.9 as an example, DPCOP1), the detailed implementation mode is as follows:
[0019] 5,10,15,20-Tetrakis(4-aminophenyl)porphyrin (TAPP) was synthesized by the Adler method. The specific process is as follows: 4-Nitrobenzaldehyde (4.0 g, 26.5 mmol), lactic acid (15 mL), and nitrobenzene (20 mL) were successively added to a 100 mL two-necked flask and heated to reflux. Pyrrole (1.83 mL, 26.5 mmol) dissolved in nitrobenzene (20 mL) was added dropwise through a constant pressure dropping funnel. After the addition of the pyrrole solution was completed, stirring was continued at 135 °C for 2 h. After the reaction was completed, the temperature was lowered to 60 °C, ethanol (60 mL) was added, and stirring was carried out for 15 min. Subsequently, the mixed solution was allowed to stand for 12 h, and solid-liquid separation was carried out by vacuum filtration. The filter cake was washed with ethanol until the filtrate was colorless and placed in a vacuum drying oven overnight to obtain 1.08 g of a dark purple solid.
[0020] TAPP was obtained by reducing the above-prepared 5,10,15,20-tetrakis(4-nitrophenyl)porphyrin with Na2S·9H2O. The specific preparation process is as follows: 5,10,15,20-Tetrakis(4-nitrophenyl)porphyrin (0.5 g, 0.6 mmol), Na2S·9H2O (5.2 g, 21.6 mmol), NH4Cl (160 mg, 2.8 mmol), and DMF (30 mL) were successively added to a 100 mL single-necked flask and stirred at 80 °C for 8 h. After the reaction was completed, it was cooled to room temperature, and the mixed solution was poured into ice water (500 mL) for sedimentation. Vacuum filtration was carried out to collect the solid, and the filter cake was washed with deionized water until the filtrate was colorless. The filter cake was placed in a vacuum drying oven overnight. The crude product was purified by dichloromethane in a Soxhlet extractor, and the liquid was collected and the solvent was removed by vacuum distillation to obtain a dark purple solid powder. The obtained crude product was purified by column chromatography, and the eluent was dichloromethane and methanol (V:V, 70:1). The product of the first color band was collected to obtain 0.287 g of a bright purple solid powder, and the yield was 70.8%.
[0021] The reaction formula is:
[0022] A porphyrin-based covalent organic polymer with a disordered structure was prepared by the Schiff base synthesis method. The specific preparation process is as follows: Specifically, terephthalaldehyde (38.22 mg, 0.29 mmol) and TAPP (100 mg, 0.15 mmol) were placed in a stainless steel autoclave lined with polytetrafluoroethylene in a nitrogen protection environment in a ratio of 1.9:1 and dissolved with 5 mL of o-dichlorobenzene. It was heated to 120 °C and maintained for 72 h. After the reaction was completed, it was cooled to room temperature, and solid-liquid separation was carried out by centrifugation. The insoluble matter was collected, washed with DMF until the filtrate was colorless, and dried overnight in a vacuum drying oven at 60 °C to obtain DPCOP1 black solid powder.
[0023] The reaction formula is:
[0024] First, a certain amount of azobisisobutyronitrile was dissolved in an appropriate amount of methyl methacrylate. The solution was stirred at 65 °C for prepolymerization until a certain viscosity was reached. Secondly, the DMF solution mixed with DPCOP1 was added to the prepolymer solution and stirred to disperse evenly. Finally, the above-mentioned mixed solution was injected into a mold coated with a release agent, placed in an oven, heated at 70 °C for 3 h, at 80 °C for 2 h, and at 90 °C for 1 h, and then naturally cooled to room temperature after heating. After demolding, an optical plastic resin sheet with a thickness of 2 mm doped with a nonlinear optical sample was obtained.
[0025] Figure 1 The FT-IR spectrum of 5,10,15,20-tetrakis(4-aminophenyl)porphyrin is as shown, where the stretching vibration peaks of N-H are at 3426 and 3321 cm -1 The stretching vibration peak of C-H bond on the benzene ring is attributed to the peak at 3028 cm -1 The stretching vibration peaks of the benzene ring skeleton are at 1600, 1516 and 1475 cm -1 The stretching vibration peak of the benzene ring skeleton is represented by the peak at 1294 cm -1 The stretching vibration peak of C-N single bond is attributed to the peak at 1294 cm -1 The stretching vibration peaks are for the porphyrin skeleton.
[0026] Figure 2 The infrared spectra of DPCOP1, DPCOP2, and DPCOP3, compared with the infrared spectrum of 5,10,15,20-tetrakis(4-aminophenyl)porphyrin ( Figure 1 ) show that the stretching vibration peak of N-H in TAPP corresponding to 3320 cm -1 is significantly weakened, and a new characteristic peak appears at 1620 cm -1 , which is attributed to the stretching vibration peak of C=N in the imine, and the characteristic peak at 1697 cm -1 is attributed to the stretching vibration peak of C=O, preliminarily proving that DPCOP1, DPCOP2, and DPCOP3 have been successfully synthesized.
[0027] Figure 3 The X-ray photoelectron spectroscopy (XPS) of DPCOPx is shown. Among them, (A) is the total XPS spectrum of DPCOP1, DPCOP2, and DPCOP3, and it can be found that the elements C, N, and O exist in the sample. At Figure 3(B), the C1s spectra of DPCOP1, DPCOP2, and DPCOP3 are mainly divided into three parts. The characteristic peak at 285.95 eV belongs to the C in C=N of the imine bond in DPCOPx, and the one at 284.75 eV belongs to the sp2 hybridized carbon in DPCOPx. For DPCOP2 and DPCOP3, a new characteristic peak appears at 288.6 eV, which belongs to the C in C-NH2 remaining in TAPP. As Figure 3 (C) shows, in the N1s spectra, DPCOP1, DPCOP2, and DPCOP3 also consist of three parts. The peak at 399.85 eV belongs to the N in C-NH2 on the benzene ring in TAPP. The peak at 399.1 eV belongs to the N in the imine bond C=N in DPCOP1, DPCOP2, and DPCOP3; another peak at 397.9 eV belongs to the N in the pyrrole ring in the porphyrin ring. Moreover, the ratio of the peak areas of C=N and -NH2 in DPCOPx decreases in the order of DPCOP1, DPCOP2, and DPCOP3, indicating that the change in the feeding ratio of terephthalaldehyde and TAPP during the preparation process has an obvious effect on the structure of PCOPx. In summary, the successful synthesis of PCOPx is proved.
[0028] Figure 4 XRD patterns of DPCOP1, DPCOP2, and DPCOP3. Obvious diffraction peaks appear at 2θ = 6.2° for DPCOP1 and DPCOP2, corresponding to the
[200] crystal plane, indicating that DPCOP1 and DPCOP2 have good crystallinity and a long-range ordered structure. For DPCOP3, a diffuse diffraction peak is observed at 2θ = 7.5°, and correspondingly, a broad peak in the range of diffraction angle 2θ = 10° - 30° indicates the presence of amorphous carbon, suggesting that as the feeding ratio of terephthalaldehyde and TAPP decreases during the preparation process, the structural order of DPCOPx decreases, attributed to the generation of structural defects that disrupt the order of the DPCOPx structure.
[0029] Figure 5 SEM images of DPCOP1, DPCOP2, and DPCOP3. DPCOP1 exhibits a spherical structure morphology formed by the stacking of irregular flaky substances ( Figure 5 (A)), DPCOP2 shows a morphology of a mixture of parallel arranged flaky substances and amorphous substances ( Figure 5 (B)), and DPCOP3 shows a mixed morphology of irregular flaky substances and amorphous substances ( Figure 5 (C)), indicating that by adjusting the feeding ratio of terephthalaldehyde and TAPP during the preparation process, different micro-morphologies of DPCOPx can be obtained.
[0030] Figure 6 Open-aperture Z-scan test curves of DPCOP1, DPCOP2, DPCOP3 and TAPP in a DMF suspension (concentration: 0.05 g / L). As the Z-axis coordinate of the sample changes from -50 mm to 0 mm during the test, it can be found that the normalized transmittance of DPCOP1 at the focal position is 0.35, DPCOP2 is 0.52, DPCOP3 is 0.64, and TAPP is 0.95. As the sample continues to move to 50 mm, the normalized transmittances of DPCOP1, DPCOP2, DPCOP3 and TAPP return to 1 again. The relevant NLO performance parameter results are listed in Table 1. All DPCOPx show larger β values than TAPP, which is attributed to the extended π-conjugated system of DPCOPx, promoting the delocalization of π electrons, and the construction of DPCOPx can effectively inhibit the aggregation between TAPP molecules, indicating that the nonlinear optical properties of TAPP can be effectively improved by constructing DPCOPx. The β values of DPCOPx show a decreasing trend in the order of DPCOP1, DPCOP2, DPCOP3, which may be attributed to the decrease in the structural orderliness of the DPCOPx group, the decrease in the conjugation degree, and the decrease in the nonlinear absorption performance. Table 1 NLO properties of TAPP and three polymers DPCOPx in DMF a c = 0.05 g / L
[0031] To improve the practicality of DPCOPx, DPCOPx was incorporated into PMMA at different concentrations, and DPCOPx / PMMA optical plastics were prepared by a solution casting technique. Their optical photos are as Figure 7 shown. The prepared optical plastics show different colors due to the concentration differences, and the color distribution is uniform and transparent, indicating that by changing the ratio of 5,10,15,20-tetra(4-aminophenyl)porphyrin and terephthalaldehyde during the preparation of DPCOPx, the conjugation of DPCOPx is destroyed, and there are a large number of amino functional groups on its surface, thereby improving the dispersibility of DPCOPx in the solid matrix and endowing it with excellent compatibility and processability.
Claims
1. A porphyrin-based conjugated organic polymer containing a disordered structure, characterized in that The polymer is a porphyrin-based conjugated organic framework containing disordered structures formed by the Schiff base reaction of 5,10,15,20-tetra(4-aminophenyl)porphyrin and terephthalaldehyde. Its English name is Porphyrin-based conjugated organic polymers containing disordered structures, abbreviated as DPCOPx (x = 1, 2, 3). The structural formula of the porphyrin-based conjugated organic framework containing disordered structures is as follows:
2. The preparation method of a porphyrin-based conjugated organic polymer containing disordered structures according to claim 1 is characterized in that: 5,10,15,20-tetra(4-aminophenyl)porphyrin and terephthalaldehyde are weighed respectively according to different molar ratios. Under a nitrogen atmosphere, different proportions of 5,10,15,20-tetra(4-aminophenyl)porphyrin and terephthalaldehyde are respectively added into the polytetrafluoroethylene inner lining of a stainless steel autoclave, dissolved with o-dichlorobenzene, and reacted under heating conditions. After the reaction is completed, it is cooled to room temperature, and solid-liquid separation is carried out by centrifugation. The insoluble matter is collected, and the insoluble matter is washed with DMF by filtration until the filtrate is colorless, and dried overnight in a vacuum drying oven at 60 °C to obtain a black solid powder.
3. The preparation method of a porphyrin-based conjugated organic polymer containing a disordered structure according to claim 2, characterized in that The ratios of 5,10,15,20-tetra(4-aminophenyl)porphyrin and terephthalaldehyde are 1:1.9, 1:1.7 and 1:1.5 respectively, and the generated products are defined as DPCOP1, DPCOP2 and DPCOP3 respectively.
4. The preparation method of a porphyrin-based conjugated organic polymer containing a disordered structure according to claim 2, characterized in that The volume of o-dichlorobenzene added is 5 mL.
5. The preparation method of a porphyrin-based conjugated organic polymer containing a disordered structure according to claim 2, characterized in that The heating temperature range is 120 °C to 150 °C.
6. The preparation method of a porphyrin-based conjugated organic polymer containing a disordered structure according to claim 2, characterized in that The heating time is 72 h to 96 h.
7. The preparation method of a porphyrin-based conjugated organic polymer containing a disordered structure according to claim 2, characterized in that The rotation speed and time of the centrifugation operation are 10000 r / min and 10 min respectively.
8. A porphyrin-based conjugated organic polymer containing a disordered structure according to claim 1, characterized in that This polymer has good dispersibility in solid organic reagents (such as polymethyl methacrylate) and can be used to prepare optical resin sheets.
9. The porphyrin-based conjugated organic polymer containing disordered structures described in claim 1 has obvious nonlinear absorption properties and can improve the dispersibility of the porphyrin-based conjugated organic polymer in organic reagents.